WO2006126666A1 - Cellulose mixed ester film, method for producing same, polarizing plate, optical compensation film, antireflection film and liquid crystal display - Google Patents

Cellulose mixed ester film, method for producing same, polarizing plate, optical compensation film, antireflection film and liquid crystal display Download PDF

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Publication number
WO2006126666A1
WO2006126666A1 PCT/JP2006/310529 JP2006310529W WO2006126666A1 WO 2006126666 A1 WO2006126666 A1 WO 2006126666A1 JP 2006310529 W JP2006310529 W JP 2006310529W WO 2006126666 A1 WO2006126666 A1 WO 2006126666A1
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Prior art keywords
film
mixed ester
cellulose mixed
cellulose
group
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PCT/JP2006/310529
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French (fr)
Japanese (ja)
Inventor
Yasuo Mukunoki
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Fujifilm Corporation
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Publication of WO2006126666A1 publication Critical patent/WO2006126666A1/en

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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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/002—Panels; Plates; Sheets
    • 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
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements

Definitions

  • the present invention relates to a method for producing a cellulose mixed ester film by melt film formation.
  • the present invention also relates to a cellulose mixed ester film excellent in optical properties. Furthermore, the present invention also relates to a polarizing plate, an optical compensation film, an antireflection film and a liquid crystal display device using the cellulose mixed ester film.
  • the cellulose mixed ester is dissolved in a chlorinated organic solvent such as dichloromethane, and this is cast on a substrate and dried. Then, a solution casting method for forming a film is mainly carried out.
  • chlorinated organic solvents dichloromethane is preferably used because it is a good solvent for cellulose acylate, has a low boiling point (about 40 ° C), and is easy to dry in the film forming process and the drying process.
  • melt-forming a cellulose mixed ester has been developed as a film forming method without using an organic solvent (see, for example, Patent Documents 1 and 2).
  • the melting point is lowered to facilitate film formation by extending the carbon chain of the ester group of cellulose ester.
  • melt film formation is made possible by changing cellulose acetate, which has been used conventionally, to cellulose pionate, cellulose petitate, or the like.
  • a retardation film was produced using a conventional cellulose ester film as a substrate, there was also an advantage that the visual field characteristics fluctuated with changes in humidity.
  • Patent Document 1 Japanese Patent Publication No. 6-501040 and
  • Patent Document 2 Japanese Patent Laid-Open No. 2000-352620
  • Patent Documents 1 and 2 describe that the weather resistance of the cellulose mixed ester film is imparted by adding fine particles and a deterioration inhibitor, but it is difficult to achieve compatibility with other performances.
  • the present inventors have made it clear.
  • the film produced according to the example of Patent Document 2 is accompanied by scratches and coloring during film transportation, deterioration in weather resistance over time, and dropout of fine particles. There was an urgent need.
  • the present invention can improve a foreign matter failure on a display screen and a change in visibility over time, which are generated when incorporated in a liquid crystal display device. It aims at providing the manufacturing method of a film, and the cellulose mixed ester film manufactured by this manufacturing method. In particular, it is useful as a protective film for a polarizing plate and a retardation film, has strength and weather resistance that can prevent coloring, Another object of the present invention is to provide a cellulose mixed ester with improved fine powder removal and a method for producing the cellulose mixed ester having good handling properties in the production process.
  • Cellulose mixed ester force Fine particles satisfying the following formulas (1) to (3-3) and having an average primary particle size of 0.005 ⁇ m to 2 ⁇ m are added to the cellulose mixed ester to 0.005. ⁇ 1.0% by mass and mixed with one or more stabilizers selected from the group consisting of phenol stabilizers, phosphorus stabilizers, thioether stabilizers, tin stabilizers and amine stabilizers Contained in an amount of 0.01 to 3% by mass relative to the ester,
  • the cellulose mixed ester is melted at 180 to 230 ° C. to extrude the die force, and includes a melt film-forming step of melt-forming to obtain a cellulose mixed ester film. .
  • A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose
  • B represents the degree of substitution of the acyl group having 3 to 22 carbon atoms with respect to the hydroxyl group of cellulose.
  • the fine particles include SiO, ZnO, TiO, SnO, AlO, ZrO, InO, MgO, BaO.
  • a method for producing a mixed ester film is a method for producing a mixed ester film.
  • Cellulose mixed ester force Fine particles satisfying the following formulas (1) to (3-3) and having an average primary particle size of 0.005 ⁇ m to 2 ⁇ m are added to the cellulose mixed ester to 0.005. ⁇ 1.0% by mass and mixed with one or more stabilizers selected from the group consisting of phenol stabilizers, phosphorus stabilizers, thioether stabilizers, tin stabilizers and amine stabilizers Contained in an amount of 0.01 to 3% by mass relative to the ester,
  • the cellulose mixed ester film is formed by melting the cellulose mixed ester at 180 to 230 ° C., extruding the die force, and forming a melt.
  • A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose
  • B represents the degree of substitution of the acyl group having 3 to 22 carbon atoms with respect to the hydroxyl group of cellulose.
  • the front letter decision (Re) is 0 to: LOnm, and the absolute value of the thickness direction letter decision (Rth) is 0 to 60 nm (5) Cellulose-mixed ester film described in 1.
  • Haze is 0.1 to 1.2%, visible light transmittance is 91% or more, and inherent in the in-plane direction at a wavelength of 590nm under an environment of 25 ° C * relative humidity 60%
  • Respective front face lettering (Re) and thickness direction lettering (Rth) at wavelengths of 400 nm and 700 nm satisfy the following formulas (A— 1) and (A— 2).
  • Re (400) and Re (700) represent frontal retardation (Re) at wavelengths of 400 nm and 700 nm
  • Rth (400) and Rth (700) are thickness-wise at wavelengths of 400 nm and 70 Onm. Represents letter decision (Rth).
  • the cellulose according to any one of (1) to (4), wherein the cellulose mixed ester is wound up with the tension being cut with a -roll, and the tension at the time of winding being 0.01 kgZcm 2 to 10 kgZcm 2 A method for producing a mixed ester film.
  • the molten mixture of the cellulose mixed ester and the fine particles is melted at 180 ° C to 230 ° C using a screw having a compression ratio of 2 to 15, and then the die.
  • the contact angle of water on the film surface (25 ° CZ relative humidity 60%) is 45 ° or less.
  • A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose
  • B ′ represents the sum of the degree of substitution of propionyl group or petityl group with respect to the hydroxyl group of cell mouth.
  • the cellulose mixed ester film Both the dynamic and static kimimi values of the particles are 0.2 to 1.5, and the average secondary particle size of the fine particles present in the cellulose mixed ester film is 0.01 m to 5 ⁇ m.
  • the cellulose mixed ester film according to any one of (5) to (8) or (13) to (16).
  • a polarizing plate comprising at least one layer of the cellulose mixed ester film according to any one of (5) to (8) or (13) to (16) laminated on a polarizing film.
  • An optical compensation film comprising the cellulose mixed ester film according to any one of (5) to (8) or (13) to (16) as a base material.
  • An antireflection film comprising the cellulose mixed ester film according to any one of (5) to (8) or (13) to (16) as a base material.
  • the handling property during the production of the cellulose mixed ester is improved, the surface defects (scratches) are greatly reduced, and the foreign matter on the display screen generated when the liquid crystal display device is incorporated. It is possible to provide a method for producing a cellulose mixed ester film capable of improving a change in visibility due to failure or aging, and a cellulose mixed ester film produced by the production method.
  • the cellulose mixed ester film of the present invention can provide a film for optical use having excellent weather resistance over time, particularly excellent durability under a high temperature environment. If a liquid crystal display device is manufactured by incorporating the cellulose mixed ester film of the present invention, it is possible to suppress changes in optical characteristics due to display unevenness, humidity, or image color.
  • FIG. 1 is a cross-sectional view showing the structure of the extruder.
  • 22 is an extruder
  • 32 is a cylinder
  • 40 is a supply port
  • A is a supply section
  • B is a compression section
  • C is a weighing section.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the method for producing a cellulose mixed ester film of the present invention is a cellulose mixed ester film having a film thickness of 20 to 200 / zm by melt-forming a cellulose mixed ester.
  • a method for producing a cellulose mixed ester film comprising:
  • Cellulose mixed ester force Fine particles satisfying the following formulas (1) to (3-3) and having an average primary particle size of 0.005 ⁇ m to 2 ⁇ m are added to the cellulose mixed ester to 0.005.
  • the present invention is characterized in that it includes a melt film forming step of melting the cellulose mixed ester at 180 to 230 ° C. to extrude the die force to form a cellulose mixed ester film by melt film formation.
  • A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose
  • B represents the degree of substitution of the acyl group having 3 to 22 carbon atoms with respect to the hydroxyl group of cellulose.
  • the cellulose mixed ester used in the production method of the present invention satisfies the following formulas (S-1) to (S-3).
  • A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose
  • B represents the degree of substitution of the acyl group having 3 to 22 carbon atoms with respect to the hydroxyl group of cellulose.
  • Glucose units in cellulose that are bonded to beta (j8) -1, 4 have free hydroxyl groups at the 2nd, 3rd and 6th positions.
  • the cellulose mixed ester is a polymer obtained by esterifying some or all of these hydroxyl groups.
  • the degree of acyl substitution means the total of the ratios of esterification of cellulose for each of the 2nd, 3rd and 6th positions (100% esterification is 1 substitution degree).
  • a + B is more preferably 2.6 ⁇ A + B ⁇ 3.0, and more preferably 2.67 ⁇ A + B ⁇ 2.97.
  • A is preferably 0 ⁇ A ⁇ 1.8 and B is preferably 1.0 ⁇ B ⁇ 2. 97 or even 1.2 ⁇ B ⁇ 2. 97 force S.
  • the substitution degree of the hydroxyl groups at the 2nd, 3rd and 6th positions of the cellulose is not particularly limited.
  • the substitution degree at the 6th position of the cellulose mixed ester is not limited. Is preferably at least 0.7, more preferably at least 0.8, particularly preferably at least 0.85, particularly preferably at least 0.90. Thereby, the solubility and heat resistance of the cellulose mixed ester can be improved.
  • the acyl group having 3 to 22 carbon atoms represented by the substituent B of the cellulose mixed ester of the present invention may be either an aliphatic acyl group or an aromatic acyl group.
  • the number of carbon atoms is preferably 3-18, and more preferably 3-12. It is particularly preferred that it is ⁇ 8.
  • these aliphatic acyl groups include an alkyl carbo yl group, an alkaryl carbo ol group, an alkyl carbo ol group, and the like.
  • the carbon number is preferably 6-22.
  • the carbon number is more preferably 6-18, and the carbon number is particularly preferably 6-12. Good.
  • Each of these acyl groups may further have a substituent.
  • Preferred examples of the acyl group include propiol group, butyryl group, pentanoyl group, hexanol group, heptanol group, otatanyl group, decanol group, dodecanol group, tridecanol group, tetradecanol group, Examples include a hexadecanol group, an octadecanol group, an isoptyryl group, a pivaloyl group, a cyclohexanecarbol group, an oleoyl group, a benzoyl group, a naphthalenecarbonyl group, a phthaloyl group, and a cinnamoyl group.
  • propiol group butyryl group, dodecanol group, otadecanoyl group, bivaloyl group, oleoyl group, benzoyl group, naphthylcarbonyl group, cinnamoyl group and the like.
  • the acyl group constituting the ester of the mixed cellulose ester of the present invention is preferably an aliphatic acyl group having 6 or less carbon atoms, and includes an acetyl group, a propionyl group, a pentyl group, a pentanoyl group, and a hexanol group.
  • the acyl group selected from the group of forces is preferred. More preferred is a acyl group selected from the group consisting of acetyl group, propiol group, butyryl group and pentanoyl group, and more preferred is selected from the group consisting of acetyl group, propionyl group and petityl group. Is an acyl group.
  • the acyl group constituting the ester of the cellulose mixed ester of the present invention may be a single species or a plurality of species. Furthermore, the cellulose mixed ester used in the present invention preferably satisfies the following formulas (S-4) to (S-6).
  • A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose
  • B ′ represents the total degree of substitution of the propionyl group and petityl group with respect to the hydroxyl group of the cell mouth.
  • the cellulose mixed ester power used in the present invention satisfies 2.6 ⁇ A + B, ⁇ 3.0, 0 ⁇ A ⁇ 1.4, and 1.0 ⁇ B' ⁇ 3 It is preferable to do.
  • the cellulose mixed ester strength used in the present invention satisfies 2.7 ⁇ A + B' ⁇ 3.0, 0 ⁇ A ⁇ 1.0 and 1.3 ⁇ B' ⁇ 3.
  • the manufacturing method of the cellulose mixed ester of this invention is demonstrated.
  • the cellulose raw material those derived from hardwood pulp, softwood pulp and cotton linter are preferably used.
  • a cellulose raw material it is preferable to use a high-purity material having a cellulose content force of S92 mass% to 99.9 mass%.
  • the cellulose raw material is in the form of a sheet or a lump, it is preferable to pulverize it.
  • the cellulosic form is fine powder force.
  • the cellulose raw material is preferably subjected to a treatment (activation) in contact with an activator prior to the acylation.
  • activator carboxylic acid or water that can use water is used.
  • the activator may be adjusted to a very high temperature and added. .
  • Preferred carboxylic acids as activators are carboxylic acids having 2 to 7 carbon atoms (eg acetic acid, propionic acid, butyric acid, 2-methylpropionic acid, valeric acid, 3-methylbutyric acid, 2-methylbutyric acid, 2, 2 —Dimethylpropionic acid (pivalic acid), hexanoic acid, 2-methylvaleric acid, 3-methylvaleric acid, 4-methylvaleric acid, 2,2-dimethylbutyric acid, 2,3-dimethylbutyric acid, 3,3-dimethyl Butyric acid, cyclopentanecarboxylic acid, heptanoic acid, cyclohexanecarboxylic acid, benzoic acid, etc.), more preferably acetic acid, propionic acid, or butyric acid.
  • sulfuric acid or the like may be added in an amount of 0.1% by mass to 10% by mass with respect to cellulose.
  • the amount of the additive added to the activator is 0.05 to: LOO mass times, preferably 0.1 to 20 times mass, and more preferably 0.3 to 20 times mass with respect to the cellulose mass. It is particularly preferred.
  • the duration of the activity is preferably 20 minutes to 72 hours, more preferably 30 minutes to 24 hours, and particularly preferably 30 minutes to 12 hours.
  • the temperature of the active liquid is preferably 0 ° C to 90 ° C, more preferably 15 ° C to 80 ° C, and particularly preferably 20 ° C to 60 ° C.
  • the step of activating cellulose can be performed under pressure or reduced pressure. Also, use electromagnetic waves such as microphone mouth waves and infrared rays as a means of heating.
  • a hydroxyl group of cellulose can be acylated by adding an acid anhydride of carboxylic acid to cellulose and reacting with Bronsted acid or Lewis acid as a catalyst.
  • the mixed cellulose ester can be obtained by mixing two carboxylic anhydrides as an acylating agent or reacting them by sequential addition; a mixed acid anhydride of two carboxylic acids (for example, acetic acid).
  • 'Propionic acid mixed acid anhydrides method; mixed acid anhydrides (for example, acetic acid and propionic acid anhydrides, for example, acetic acid and propionic acid anhydrides) as raw materials
  • mixed acid anhydrides for example, acetic acid and propionic acid anhydrides, for example, acetic acid and propionic acid anhydrides
  • a method for making a password can be used.
  • the acid anhydride of the carboxylic acid preferably has 2 to 7 carbon atoms as the carboxylic acid.
  • acetic anhydride More preferred are acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride and the like, and particularly preferred are acetic anhydride, propion Acid anhydride and butyric anhydride.
  • the mixing ratio is preferably determined according to the substitution ratio of the target cellulose mixed ester.
  • the acid anhydride should be added in an amount of 1.2 to 50 equivalents relative to the hydroxyl group of cellulose, which is usually preferred to be added in an excess amount relative to the cellulose, and 1.5 to 30 equivalents. It is more preferable to add 2-: It is particularly preferable to add LO equivalent.
  • Bronsted acid or a Lewis acid as the catalyst for the acylation used in the production of the cellulose mixed ester in the present invention.
  • the definitions of Bronsted acid and Lewis acid are described, for example, in “The Science Dictionary”, 5th edition (2000).
  • Examples of preferable Bronsted acid include sulfuric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like.
  • Preferred examples of the Lewis acid include zinc chloride, tin chloride, salt-antimony, salt-magnesium and the like.
  • the catalyst is particularly preferably sulfuric acid, more preferably sulfuric acid or perchloric acid.
  • a preferable addition amount of the catalyst is 0.1 to 30% by mass with respect to cellulose, more preferably 1 to 15% by mass, and particularly preferably 3 to 12% by mass.
  • a solvent may be added for the purpose of adjusting the viscosity, the reaction rate, the stirring property, the acyl substitution ratio, and the like.
  • a solvent dichloromethane, chloroform, carboxylic acid, acetone, ethyl methyl ketone, toluene, dimethyl sulfoxide, sulfolane and the like can be used, preferably carboxylic acid.
  • C2-C7 carboxylic acids eg acetic acid, propionic acid, butyric acid, 2 methylpropionic acid, valeric acid, 3 methylbutyric acid, 2 methylbutyric acid, 2, 2 dimethylpropionic acid (pivalic acid), hexanoic acid, 2 -Methyl valeric acid, 3-methyl valeric acid, 4-methyl valeric acid, 2,2-dimethylbutyric acid, 2,3 dimethylbutyric acid, 3,3 dimethylbutyric acid, cyclopentanecarboxylic acid) and the like.
  • Examples include acetic acid, propionic acid and butyric acid. These solvents may be used as a mixture.
  • an acid anhydride and a catalyst and, if necessary, a solvent may be mixed and mixed with force cellulose, or these may be separately mixed with cellulose one after another.
  • the cooling temperature is preferably from 50 ° C to 20 ° C, more preferably from 35 ° C to 10 ° C, particularly preferably from 25 ° C to 5 ° C.
  • the acylating agent may be added in liquid form or may be frozen and added as crystals, flakes or block solids.
  • the acylating agent may be added to the cellulose at once or dividedly.
  • cellulose may be added to the acylating agent at once or dividedly.
  • the acylating agent is added in portions, the same acylating agent or a plurality of different acylating agents may be used.
  • Preferred examples include: 1) a mixture of acid anhydride and solvent is added first, then the catalyst is added, 2) a mixture of acid anhydride and solvent and a portion of the catalyst is added first, then Add the remainder of the catalyst and the solvent mixture, 3) Add the acid anhydride and solvent mixture first, then add the catalyst and solvent mixture, 4) Add the solvent first and the acid
  • a mixture of an anhydride and a catalyst or a mixture of an acid anhydride, a catalyst, and a solvent can be added.
  • the acylation of cellulose is an exothermic reaction.
  • the maximum temperature reached during the acylation is 50 ° C to 50 ° C.
  • the degree of polymerization is preferably easy to control, preferably 30 ° C to 45 ° C, more preferably -20 ° C to 40 ° C, and particularly preferably -20 ° C to 35 ° C. is there.
  • New time is 0.5 hours to 24 hours, 1 hour to 12 hours is more preferred 1. 5 hours to 6 hours is especially preferred U ,.
  • reaction terminator any one that can decompose an acid anhydride may be used. Preferred examples include water, alcohol (eg, ethanol, methanol, propanol, isopropyl alcohol, etc.) or a composition containing them. Can be mentioned.
  • a large exotherm that exceeds the cooling capacity of the reaction apparatus may occur, which may cause the degree of polymerization of the cellulose mixed ester to decrease, or the cellulose mixed ester may precipitate in a desired form.
  • carboxylic acid such as acetic acid, propionic acid, butyric acid and water rather than adding water or alcohol directly.
  • carboxylic acid such as acetic acid, propionic acid, butyric acid and water
  • the composition ratio of the carboxylic acid and water can be used at any ratio, but the water content is 5% to 80% by mass, further 10% to 60% by mass, especially 15% to 50%. It is preferably in the range of mass%.
  • the reaction terminator may be added to the reaction vessel for the acylation, or a reactant may be added to the reaction terminator vessel.
  • the reaction terminator is preferably added over 3 minutes to 3 hours.
  • the addition time of the reaction terminator is more preferably 4 minutes to 2 hours, further preferably 5 minutes to 1 hour, and particularly preferably 10 minutes to 45 minutes.
  • the reaction vessel may or may not be cooled, but for the purpose of suppressing depolymerization, it is preferable to cool the reaction vessel to suppress the temperature rise. It is also preferable to cool the reaction terminator.
  • a neutralizing agent for example, calcium, etc.
  • a neutralizing agent for example, calcium, etc.
  • Magnesium, iron, aluminum or zinc carbonates, acetates, hydroxides or oxides) or solutions thereof may be added.
  • Solvents for the neutralizing agent include water, alcohols (eg, ethanol, methanol, propanol, isopropyl alcohol, etc.), carboxylic acids (eg, acetic acid, propionic acid, butyric acid, etc.), ketones (eg, acetone, ethyl methyl ketone, etc.).
  • Polar solvents such as dimethyl sulfoxide, and mixed solvents thereof. It can be given as an example.
  • the cellulose mixed ester obtained in this way has a force that the total substitution degree of the cellulose hydroxyl group is almost close to 3.
  • a small amount of catalyst generally, the residual amount of Cellulose mixed ester having a desired degree of acyl substitution by partially hydrolyzing the ester bond by maintaining at 20 to 90 ° C for several minutes to several days in the presence of water and an acylation catalyst such as sulfuric acid
  • cellulose sulfate is also hydrolyzed during the partial hydrolysis, the amount of sulfate bound to cellulose can be reduced by adjusting the hydrolysis conditions.
  • the catalyst remaining in the system is completely neutralized with the neutralizing agent as described above or a solution thereof, and subjected to partial hydrolysis. It is preferable to stop.
  • a neutralizing agent for example, magnesium carbonate, magnesium acetate, etc.
  • a catalyst for example, sulfate ester bound to the solution or the cell mouth. Also preferred to remove effectively.
  • the filter medium is not particularly limited, and cloth, glass filter, cellulose filter paper, cellulose cloth filter, metal filter, polymer filter (for example, polypropylene filter, polyethylene filter, polyamide filter, fluorine filter) System filters).
  • the filter aperture size is preferably 0.1 to 500 ⁇ m force S, more preferably 2 to 200 ⁇ m, and even more preferably 3 to 60 ⁇ m.
  • the obtained cellulose mixed ester solution is mixed in a poor solvent such as water or an aqueous solution of carboxylic acid (for example, acetic acid, propionic acid, butyric acid, etc.), or is mixed in a cellulose mixed ester reaction solution.
  • a poor solvent such as water or an aqueous solution of carboxylic acid (for example, acetic acid, propionic acid, butyric acid, etc.)
  • carboxylic acid for example, acetic acid, propionic acid, butyric acid, etc.
  • a cellulose mixed ester reaction solution By mixing the solvent, the cellulose mixed ester can be re-precipitated, and the desired cellulose mixed ester can be obtained by washing and stabilizing treatment.
  • the By reprecipitation purification efficiency can be improved and molecular weight distribution and apparent density can be adjusted. Reprecipitation may be carried out continuously or batchwise by a fixed amount.
  • the produced cellulose mixed ester is preferably washed.
  • the cleaning can be performed with any material that can remove impurities, but usually water or warm water is used.
  • the temperature of the washing water is preferably 5 ° C to 100 ° C, more preferably 15 ° C to 90 ° C, and particularly preferably 30 ° C to 80 ° C.
  • the cleaning process may be performed in a so-called batch system in which filtration and replacement of the cleaning liquid are repeated, or may be performed using a continuous cleaning apparatus. It is also preferable to reuse the waste liquid generated in the reprecipitation and washing steps as a poor solvent for reprecipitation, or to recover and reuse a solvent such as carboxylic acid by means such as distillation.
  • the progress of the cleaning may be traced by any means, but preferable examples include methods such as hydrogen ion concentration, ion chromatography, electrical conductivity, ICP, elemental analysis, and atomic absorption spectrum.
  • blended acid in cellulose mixed ester sulfuric acid, perchloric acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, etc.
  • neutralizing agent eg calcium, magnesium, iron, aluminum or zinc
  • reaction product of neutralizing agent and catalyst carboxylic acid (acetic acid, propionic acid, butyric acid, etc.), reaction product of neutralizing agent and carboxylic acid, etc. Therefore, it is effective for improving the stability of the mixed ester of cellulose (especially, the decomposition of ester bond at high temperature and high humidity).
  • the cellulose mixed ester after washing by hot water treatment has a weak alkali (for example, carbonic acid such as sodium, potassium, calcium, magnesium, aluminum, etc.) in order to further improve the stability or reduce the carboxylic acid odor. It is also preferable to treat with an aqueous solution of a salt, bicarbonate, hydroxide, oxide or the like.
  • the amount of residual impurities can be controlled by the amount of cleaning liquid, cleaning temperature, time, stirring method, shape of cleaning container, composition and concentration of stabilizer.
  • the water content of the cellulose mixed ester is preferred and the amount is adjusted. It is preferable to dry the cellulose mixed ester.
  • the drying method is not particularly limited as long as the desired moisture content can be obtained, but it is preferable that the drying method be carried out efficiently by using means such as heating, air blowing, decompression and stirring alone or in combination.
  • the drying temperature is preferably 0 to 200 ° C, more preferably 40 to 180 ° C, and particularly preferably 50 to 160 ° C. At this time, drying at a temperature lower than the glass transition point (Tg) of the cellulose mixed ester is preferable. Drying at a temperature lower by 10 ° C. or more than Tg is more preferable.
  • the cellulose mixed ester in the present invention obtained by drying preferably has a water content of 2% by mass or less, more preferably 1% by mass or less, and 0.5% by mass or less. Particularly preferred.
  • cellulose mixed ester When cellulose mixed ester is used as a raw material for film production, it is preferably in the form of particles or powder.
  • the cellulose mixed ester after drying may be pulverized or sieved in order to make the particle size uniform and improve the handleability.
  • 90% by mass or more of the particles used is 0.5mn! It preferably has a particle size of ⁇ 5mm. Also, more than 50% by mass of the particles used are lmn! Preferably it has a particle size of ⁇ 4 mm. It is preferable that the cellulose mixed ester particles have a nearly spherical shape as much as possible.
  • the polymerization degree of the cellulose mixed ester preferably used in the present invention is an average polymerization degree of 100 to 700, preferably 120 to 550, more preferably 120 to 400, and The average degree of polymerization is preferably 130 to 350.
  • the average degree of polymerization was determined by gel permeation chromatography (Uda et al., Kazuo Uda, Hideo Saito, Journal of Textile Science, 18th No. 1, pages 105-120, 1962). It can be measured by methods such as molecular weight distribution measurement by GPC). Further details are described in JP-A-9-95538.
  • cellulose mixed esters may be used alone or in combination of two or more. Such adjustment of the degree of polymerization can also be achieved by removing low molecular weight components. Removal of low molecular weight components can be performed by washing the cellulose mixed ester with an appropriate organic solvent.
  • the cellulose mixed ester in the present invention may be one obtained by appropriately mixing polymer components other than the cellulose mixed ester! / ⁇ .
  • the polymer component to be mixed is excellent in compatibility with the cell mouth mixed ester, but has a transmittance of 8 when the film is preferred. It is preferably 0% or more, more preferably 90% or more, and still more preferably 92% or more.
  • the cellulose mixed ester used in the present invention is preferably one having a weight average molecular weight MwZ number average molecular weight Mn ratio of 1.5 to 5.5, particularly preferably 1.5 to 5.0. More preferably, it is 2.0 to 4.5, and a selenorose mixed ester of 2.0 to 4.0 is preferably used.
  • Cellulose mixed ester is the size of the signaling preferred pellet preferred to Peretsutoi spoon is lmm 3 ⁇ 10cm 3, more preferably 5 mm 3 to 5 cm 3, more preferably from 10mm 3 ⁇ 3cm 3. Then, it dries on the above-mentioned conditions.
  • a moisture-proof bag made of a prevention material such as aluminum, a SUS drum, or a container for storage.
  • cellulose mixed esters For example, JP-A-11-5851, JP-A-2002-212338, JP-A-2002-338601, etc. There is a description.
  • Other synthetic methods for cellulose mixed esters include bases (sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, pyridine, triethylamine, tert-butoxy potassium, sodium methoxide, sodium ethoxide, etc.).
  • a method of reacting with a carboxylic acid anhydride or a carboxylic acid halide in the presence, or a method using a mixed acid anhydride (such as carboxylic acid 'trifluoroacetic acid mixed anhydride, carboxylic acid' methanesulfonic acid mixed anhydride) as an acylating agent is effective when introducing an acyl group having a large number of carbon atoms or an acyl group in which liquid phase acylation using a carboxylic anhydride, acetic acid or sulfuric acid catalyst is difficult.
  • the cellulose mixed ester of the present invention contains fine particles and a stabilizer, and other various additives may be added at any stage after preparation of the melt pre-preparation force as necessary. Good.
  • additives other than fine particles and stabilizers in the present invention include heat stabilizers such as ultraviolet absorbers, salts of Group 2 metals such as calcium and magnesium, antistatic agents, flame retardants, lubricants, and oils.
  • Cellulose mixed ester in the present invention relative to the average primary particle size of 0. 005 ⁇ m ⁇ fine particles cellulose mixed ester is 2 m, and containing not from 0.005 to 1.0 mass 0/0.
  • the fine particles include inorganic compound fine particles and organic compound fine particles, and any of them may be used.
  • Examples of the inorganic compound include SiO, ZnO, TiO, SnO, AlO, ZrO, InO, and MgO.
  • Examples thereof include calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate.
  • At least one of Mo, MoO, and V 2 O is preferred, more preferably SiO, TiO, SnO
  • SiO fine particles examples include Aerozinole R972, R972V, R974, R812,
  • ZrO fine particles examples include Aerosil R976 and
  • a silicone resin in which a polymer such as a silicone resin, a fluorine resin, and an acrylic resin is preferable is particularly preferable.
  • the silicone resin those having a three-dimensional network structure are preferable.
  • Tosnor 103, 105, 108, 120, 145, 3120 and 240 above, Toshiba Silicone Co., Ltd.
  • a commercial product having a trade name such as) can be used.
  • the average primary particle size of the fine particles contained in the cellulose mixed ester in the present invention is 0.005 ⁇ m to 2 ⁇ m from the viewpoint of keeping haze low, and preferably the average primary particle.
  • the size is from 0.005 ⁇ m to 0.5 ⁇ m, particularly preferably the average primary particle size is from 0.005 ⁇ m to 0.1 ⁇ m.
  • the average primary particle size of the fine particles was measured by observing the particles of the cellulose mixed ester film with a transmission electron microscope (magnification 500,000 to 1,000,000 times), observing 100 particles, and measuring the average value. Therefore, the average primary particle size was used.
  • the method of adding these fine particles to the cellulose mixed ester is kneaded by a conventional method.
  • a process in which the fine particles are made into fine powder particles and finely dispersed by a share in the kneader or in the die during film formation is performed. It is preferable to include.
  • other functional materials for example, a plasticizer and Z or an ultraviolet absorber
  • the average secondary particle size of the fine particles in the cellulose mixed ester film finally obtained by the production method of the present invention is preferably 0.01 to 5 / ⁇ ⁇ . It is particularly preferred that the average secondary particle size is more preferably 0.02 to 1 ⁇ m, more preferably a particle size of 0.02 to 3 m.
  • the average secondary particle size of the fine particles was measured by observing the particles in the cellulose mixed ester film with a transmission electron microscope (magnification 100,000 to 1,000,000 times)! The value was taken as the average secondary particle size.
  • the fine particles comprising an inorganic compound are subjected to a surface treatment in order to stably exist in the cellulose mixed ester film.
  • the inorganic fine particles are preferably used after being subjected to a surface treatment.
  • Surface treatment methods include chemical surface treatment using a coupling agent and physical surface treatment such as plasma discharge treatment and corona discharge treatment.
  • a coupling agent is preferred.
  • an organoalkoxy metal compound eg, silane coupling agent, titanium coupling agent, etc.
  • inorganic fine particles are used as fine particles (especially when SiO is used)
  • the treatment with a silane coupling agent is particularly effective.
  • a silane coupling agent an organosilane compound represented by the following general formula (11) can be used.
  • the amount of the force coupling agent to be used is not particularly limited, but preferably 0.05 to 5% by mass, more preferably 0.01 to 3% by mass, based on the inorganic fine particles.
  • R and R ′ each independently represents a hydrogen atom, an alkyl group, an aryl group, a aryl group, Represents a fluoroalkyl group.
  • the alkyl group may have an epoxy group, amino group, acrylic group, isocyanate group, and Z or mercapto group as a functional group.
  • X is an integer of 0 to 3, preferably an integer of 0 to 2.
  • organosilane represented by the general formula (11) can include the following: The present invention is not limited to these examples.
  • two or more different organosilanes may be used in combination.
  • the coupling agent is treated by a direct treatment method for fine particles and an integral blend method.
  • the direct method is roughly classified into a dry method, a slurry method, and a spray method.
  • Fine particles obtained by the direct treatment method are excellent in that they can be added to the binder and the coupling agent can be reliably modified on the surface of the fine particles.
  • the dry method is generally carried out by uniformly dispersing fine particles in an alcohol aqueous solution, organic solvent or aqueous solution of a silane coupling agent, followed by drying. It is preferable to use a Henschel mixer, a super mixer, a ready mixer, a V-type blender, an open-agitator or the like. Among these agitators, open-one is particularly preferable. Fine particles and a small amount of water, Alternatively, it is preferable that the organic solvent containing water and the coupling agent are mixed and stirred in an open-head manner to remove water and further finely dispersed.
  • the slurry method is a method of adding a coupling agent to the slurry when there is a step of slurrying the fine particles in the production of the fine particles, and has an advantage that it can be processed in the production process.
  • the spray method is a method of adding a coupling agent to the fine particles in the fine particle drying step, and has an advantage that it can be treated in the production step, but has a problem in uniformity of treatment.
  • the integral blend method is described as follows.
  • the integral blend method is a method of adding a coupling agent into fine particles and a binder, and it is a simple method that needs to be well kneaded.
  • the fine particles in the present invention are characterized by containing 0.005 to 1.0 mass% with respect to the cellulose mixed ester.
  • the content of the fine particles is preferably 0.01 to 0.8% by mass, more preferably 0.02 to: L 0% by mass.
  • the cellulose mixed ester in the present invention contains 0.01 to 3% by mass of one or more stabilizers with respect to the cellulose mixed ester.
  • the stabilizer used in the present invention is one or more selected from the group consisting of a phenol stabilizer, a phosphorus (phosphite) stabilizer, a thioether stabilizer, a soot stabilizer and an amine stabilizer. It is a stabilizer.
  • a compound having a stabilizing effect other than these can be added as long as the required performance is not impaired.
  • phosphorus stabilizer compounds described in [0023] to [0039] of JP-A No. 2004-182979 can be used more preferably.
  • Specific examples of the phosphite ester stabilizer include JP-A-51-70316, JP-A-10-306175, JP-A-57-78431, JP-A-54-157159. And compounds described in JP-A-55-13765.
  • other stabilizers are described in detail on pages 17 to 22 of the Inventors Association Technical Report (Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Inventions)! It can be preferably used.
  • any known phenol-based stabilizer can be used.
  • Preferred phenolic stabilizers include hindered phenolic stabilizers.
  • Examples of hindered phenol stabilizers include, for example, 1, 3, 5 tris (3, 5 di-tert-butyl-4-hydroxybenzyl) -s tridian-2, 4, 6- (1H, 3H, 5H) Trione, 1, 1, 3 tris (2-methyl-4-hydroxy-1-5-tert-butylphenyl) butane, tetrakis [methylene (3,5-ditert-butyl-4-hydroxyhydracinnamate)] methane, and 3 , 9 Bis ⁇ 2- [3- (3-tert-Butyl-4-hydroxy-5-methylphenol) propio-loxy] 1,1 dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro [5,5] undecane 2,6 di-tert-butyl-p-cresol, 2,2,2,
  • High molecular weight polycyclic hindered phenolic anti-oxidants are more preferred. More preferred is 1,1,3 tris (2-methyl-4-hydroxy-5-tertbutylphenol) butane. These are Sumitomo Chemical's Sumitizer 1 BHT, Sumilizer 1 BP-76, Sumilizer 1 BBM- S, Sumizer 1 GA-80, and Chinoku 'Specialty' Chemicals, Inc. Irganox 1076, Irg anox 1000, Irganox 3114, Commercially available as Irganox 245.
  • any conventionally known phosphorus stabilizer can be used.
  • preferred phosphorus stabilizers include bis (2,6 di tert-butyl-4-methylphenol) pentaerythritol monodiphosphite, tris (2,4 di tert- Butylphenol) phosphite, distearyl 'pentaerythritol diphosphite, trioctadecyl phosphite, trinoyl phosphite, triphenyl phosphite, 9, 10 dihydro 9 oxa 10 phospha' phenanthrene 10-oxy Side, tetrakis (2,4 di-tert-butylphenol) 4,4'-biphenol-range phosphate.
  • phosphite antioxidants are more preferable. More preferred is bis (2,6-di-tert-butyl 4-methyl propyl) pentaerythritol-di-phosphite. These are commercially available from Asahi Denka as Adekatab 1178, 2112, PEP-8, PEP-24G, PEP-36G, HP-10, and Sandostab P-EPQ from Clariant. It is.
  • any known thioether stabilizer can be used.
  • preferred thioether stabilizers include tetrakis [methylen-3- (dodecylthio) propionate] methane, 3,3,4 monodipropionic acid, dilauryl thiodipropionate, distearyl thiodipropionate. Can be mentioned. These are marketed by Sumitomo Chemical as Sumilizer I TPL, TPM, TPS, TDP.
  • any known tin-based stabilizer can be used.
  • Specific examples of preferred tin-based stabilizers include octyl tin maleate polymer, monostearyl tin tris (isooctyl thioglycolate), and dibutyl tin dilaurate.
  • any known amine stabilizer can be used.
  • preferred amine stabilizers include 2,2 'methylenebis [4- (1, 1, 3, 3-tetramethylbutyl) 6-[(2H benzotriazole-2-yl) phenol]], tetrakis (2, 2, 6, 6—tetramethyl-4-piperidyl) 1, 2, 3, 4 butanetetracarboxylate, ferulic ⁇ naphthylamine, ⁇ — ⁇ , ⁇ -sec butyl- ⁇ -phee-rangeamamine, N— N, -diphenyl-p-phenylenediamine, N-phenyl-N, monocyclohexyl p-phenylenediamine, N-isopropyl N, monophenyl-- p-phenyldiamine, 4-benzoyloxy 2--2-6-6 —Tetramethylpiperazine, bis (2—2—6—6-tetramethyl-4-piperidine
  • the stabilizer used in the present invention is preferably a combination of a high molecular weight polycyclic hindered phenolic acid oxidant and a phosphate ester type acid oxidant. More preferably, 1,1,3 tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane and bis (2,6-ditertbutyl-4-methylphenol) pentaerythritol phosphite are used. It is a combination.
  • the addition amount of the stabilizer in the present invention is 0.01 to 3% by mass based on the cellulose mixed ester. More preferably, the content is 0.03 to 2% by mass. More preferably, it is 0.05-1.5 mass%.
  • the added amount of the stabilizer is less than 0.01% by mass, the effect of the stabilizer is obtained, and there is a problem that the coloring becomes intense.
  • the amount of stabilizer added is more than 3% by mass, there is a problem that the surface condition deteriorates.
  • additives for example, plasticizers, ultraviolet inhibitors, deterioration inhibitors, fine particles, optical property modifiers, etc.
  • plasticizers for example, plasticizers, ultraviolet inhibitors, deterioration inhibitors, fine particles, optical property modifiers, etc.
  • additives for example, plasticizers, ultraviolet inhibitors, deterioration inhibitors, fine particles, optical property modifiers, etc.
  • plasticizers for example, plasticizers, ultraviolet inhibitors, deterioration inhibitors, fine particles, optical property modifiers, etc.
  • fine particles fine particles
  • optical property modifiers etc.
  • the crystal melting temperature (Tm) of the cellulose mixed ester can be lowered.
  • the molecular weight of the plasticizer used in the present invention is not particularly limited, and may be a low molecular weight or a high molecular weight.
  • the plasticizer include phosphate esters, alkylphthalylalkyl glycolates, carboxylic acid esters, and fatty acid esters of polyhydric alcohols. These plasticizers may be solid or oily. In other words, the melting point and boiling point are particularly limited Is not to be done. When performing melt film formation, it is particularly preferable to use a non-volatile material.
  • phosphate ester examples include, for example, triphenyl phosphate, tributyl phosphate, tribubutychetyl phosphate, tricresyl phosphate, trioctyl phosphate, trinaphthyl phosphate, trixylyl phosphate, trisulol.
  • examples include tobiphenol phosphate, credinorephenol-norephosphate, otachinoresphie-norephosphate, biphenyl-diphenyl phosphate, and 1,4-phenol-tetraphenyl phosphate. It is also preferable to use the phosphoric ester plasticizer described in claims 3 to 7 of JP-T-6-501040.
  • alkyl phthalyl alkyl glycolates include, for example, methyl phthalyl methyl glycolate, ethino retinalino ethinore glycolate, propino phthalino repropenore glycolate
  • carboxylic acid ester examples include phthalic acid esters such as dimethyl phthalate, jetyl phthalate, dibutyl phthalate, dioctyl phthalate and jetyl hexyl phthalate, Citrates such as acetytributyl butylate, adipates such as dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, disodecyl adipate, bis (butyl diglycol adipate), Aromatic polycarboxylic acid esters such as tetraoctylbi-mouth melitate and trioctyl trimellitate, dibutyl adipate, dioctyl adipate, dibutyl sebacate, dioctyl sebacate, jetty Aliphatic polycarboxylic esters such as lucerate, dibutyl
  • aliphatic polyesters composed of dalicol and dibasic acid such as polyethylene adipate, polybutylene adipate, polyethylene succinate, and polybutylene succinate, and aliphatic polyesters composed of oxycarboxylic acid such as polylactic acid and polydaricholic acid
  • high molecular weight plasticizers such as aliphatic polyesters that also have rataton power, such as polystrength polylataton, polypropiolatatone, polyvalerolatatone, and vinyl polymers such as polyvinylpyrrolidone. These plasticizers can be used alone or in combination with a low-part plasticizer.
  • the polyhydric alcohol plasticizer is a glycerin-based ester compound such as glycerin ester or diglycerin ester, polyethylene glycol or polypropylene glycol, which has good compatibility with cellulose fatty acid ester and a remarkable thermoplastic effect.
  • a polyalkylene glycol a compound in which an acyl group is bonded to a hydroxyl group of the polyalkylene glycol.
  • Specific glycerin esters include glycerin diacetate stearate, glycerin diacetate palmitate, glycerin diacetate myristate, glycerin diacetate laurate, glycerin diacetate force plate, glycerin diacetate nonanate, glycerin diacetate otanoate, glycerin Diacetate heptanoate, glycerol diacetate hexanoate, glycerol diacetate pentanoate, glycerol diacetate phosphate, glycerol acetate dicaprate, glycerol acetate dinonanoate, glycerol acetate dioctanoate, glycerol acetate diheptano Acetate, glycerol acetate dicaproate, glycerol acetate divalerate, glycerol acetate Dibutylate, glycerol di
  • glycerin diacetate power prelate glycerin diacetate pelargonate, glycerin diacetate power plate, glycerin diacetate laurate, glycerin diacetate myristate, glycerin diacetate panoleate, glycerin diacetate stearate, glycerin diacetate alcohol Is preferred.
  • diglycerin ester examples include diglycerin tetraacetate, diglycerin tetrapropionate, diglycerin tetrabutylate, diglycerin tetravalerate, diglycerin tetrahexanoate, diglycerin tetraheptanoate, Diglycerin Tetracaprylate, Diglycerin Tetrapelargonate, Diglycerin Tetrapulonate, Diglycerin Tetralaurate, Diglycerin Tetramyristate, Diglycerin Tetrapalmitate, Diglycerin Triacetate Propionate, Diglycerin Triacetate Butyrate, Diglycerin Triacetate valerate, diglycerin triacetate hexanoate, diglycerin triacetate heptanoate, diglycerin triacetate capri Rate, diglycerin triacetate pelargonate, diglycerin triacetate force plate, diglycerin triacetate laurate, diglycerin
  • diglycerin tetraacetate, diglycerin tetrapropyrate, diglycerin tetrapropylate, diglycerin tetracaprylate, and diglycerin tetralaurate are preferable.
  • polyalkylene glycol examples include, but are not limited to, polyethylene glycol and polypropylene glycol having an average molecular weight of 200 to 1000, and these can be used alone or in combination.
  • Specific examples of a compound in which an acyl group is bonded to a hydroxyl group of polyalkylene glycol include polyoxyethylene acetate, polyoxyethylene propionate, polyoxyethylene butyrate, polyoxyethylene valerate, and polyoxyethylene strength proate.
  • the addition amount of the plasticizer is preferably 0 to 20% by mass, more preferably 0 to 18% by mass, and most preferably 2 to 15% by mass with respect to the cellulose mixed ester.
  • the content of the plasticizer is more than 20% by mass, the thermal fluidity of the cellulose mixed ester is improved, the plasticizer oozes out on the surface of the melt-formed film, and the glass transition temperature is heat resistant. Degree Tg may decrease.
  • the cellulose mixed ester film may be added with a deterioration preventing agent (for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal deactivator, an acid scavenger, an amine) or an ultraviolet light inhibitor.
  • a deterioration preventing agent for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal deactivator, an acid scavenger, an amine
  • an ultraviolet light inhibitor for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal deactivator, an acid scavenger, an amine
  • a deterioration preventing agent for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal deactivator, an acid scavenger, an amine
  • UV inhibitors for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal deactivator, an acid scavenger, an amine
  • the addition amount of these is preferably 0.01 to 1% by mass of the melt (dope) to be prepared, and more preferably 0.01 to 0.2% by mass.
  • the addition amount is less than 0.01% by mass, the effect of the deterioration inhibitor is hardly recognized. If the added amount exceeds 1% by mass, bleed-out (bleeding) of the deterioration preventing agent to the film surface may be observed.
  • a particularly preferred deterioration preventing agent butylated hydroxytoluene (BHT) can be mentioned.
  • the cellulose mixed ester of the present invention preferably contains one or more ultraviolet absorbers.
  • the ultraviolet absorber is preferably excellent in the ability to absorb ultraviolet rays having a wavelength of 380 nm or less, and from the viewpoint of liquid crystal display properties, the absorption of visible light having a wavelength of 400 nm or more is small. Examples thereof include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like.
  • the ultraviolet absorber is a benzotriazole compound or a benzophenone compound. Of these, benzotriazole compounds are preferred because they have less unnecessary coloration with respect to cellulose mixed esters.
  • Preferable ultraviolet absorbers include 2, 6 tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate], Triethylene glycol bis [3- (3-tert-butyl-5-methyl 4-hydroxyphenol) propionate], 1, 6 hexanediol bis [3- (3, 5 di-tert-butyl-4 hydroxyphenol) propionate], 2, 4 bis- (n-octylthio) 6- (4-hydroxy-3,5 di tert-butyl-lino) 1, 3, 5 triazine, 2, 2 Thiodiethylenebis [3- (3,5 di tert-butynole 4-hydroxyphenyl) propionate], Octadecyl 3- (3,5-di-tert-butyl 4-hydroxyphenol) propionate, N, N , Monohexamethylenebis (3,5-di-tert-butyl 4-hydroxy
  • UV absorber 2, 6 di tert-butyl-p cresol, pentaerythrityl-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenol) propionate]
  • Triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenol) propionate] is most preferred.
  • hydrazine-based metal deactivators such as N, N, bis [3- (3,5-di-tert-butyl-4-hydroxyphenol) propiol] hydrazine are tris (2,4 di-tert- Phosphorus processing stabilizers such as butylphenol) phosphite may be used in combination.
  • the addition amount of these compounds is preferably from 1 ppm to 3.0% by mass with respect to the cellulose mixed ester, and more preferably from 10 ppm to 2%.
  • UV absorbers are available as the following commercial products. As benzotriazoles, TINUBIN P (manufactured by Chinoku Specialty Chemicals), TINUBIN 23 4 (manufactured by Chiba Specialty Chemicals), TINUBIN 320 (manufactured by Chiba Specialty Chemicals), TINUBIN 326 (Chinoku) Specialty Chemicals), TINUBIN 327 (Ciba's Specialty Chemicals), TINUBIN 328 (Ciba's Specialty Chemicals), and Sumisorp 340 (Sumitomo Chemical Co., Ltd.).
  • benzophenone-based ultraviolet absorbers include Seasorb 100 (Cipro Kasei), Seasorb 101 (Cipro Kasei), Seasorb 101S (Cipro Kasei), Seasorb 102 (Cipro Kasei), Seasorb 103 (manufactured by Sipro Kasei Co., Ltd.), Adekas type LA-51 (manufactured by Asahi Denka Co., Ltd.), Chemisorp 111 (manufactured by Chemipro Kasei Co., Ltd.), UVINUL D-49 (manufactured by BASF) and the like.
  • oxalic acid-based UV absorbers TINUBIN 312 (Ciba ' Specialty Chemicals) and TINUBIN 315 (Chinoku's Specialty Chemicals).
  • a salicylic acid ultraviolet absorber Seasorb 201 (manufactured by Sipro Kasei Co., Ltd.) and Seasorb 202 (manufactured by Sipro Kasei Co., Ltd.) are listed, and as a cyanoacrylate-based ultraviolet absorber, Seasorb 501 (manufactured by Sipro Kasei) ), UVINUL N-539 (manufactured by BASF).
  • the cellulose mixed ester of the present invention may contain an optical adjusting agent (lettering control agent, particularly a letter raising agent) for controlling optical anisotropy.
  • an aromatic compound having at least one aromatic ring as a letter control agent in order to adjust the letter determination of the cellulose mixed ester film.
  • the aromatic compound is used in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the cellulose mixed ester.
  • the aromatic compound is preferably used in the range of 0.05 to 15 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass, with respect to 100 parts by mass of the cell mouth monosulfate. Two or more aromatic compounds may be used in combination.
  • the aromatic ring of the aromatic compound includes an aromatic heterocycle in addition to an aromatic hydrocarbon ring.
  • the aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring).
  • Aromatic heterocycles are generally unsaturated heterocycles.
  • the aromatic heterocycle is preferably a 5-membered, 6-membered or 7-membered ring, more preferably a 5-membered or 6-membered ring.
  • Aromatic heterocycles generally have the most double bonds.
  • a nitrogen atom particularly preferred is a nitrogen atom, an oxygen atom or a sulfur atom.
  • aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine Rings, pyridazine rings, pyrimidine rings, pyrazine rings and 1, 3, 5 triazine rings are included.
  • the cellulose mixed ester in the present invention preferably contains a polymer having a fluorine atom.
  • the polymer having a fluorine atom can exhibit an action as a release agent and has a low It may be a molecular weight compound or a polymer.
  • the polymer having a fluorine atom examples include the polymers described in JP-A-2001-269564.
  • the polymer having a fluorine atom is preferably a polymer obtained by polymerizing a monomer containing an ethylenically unsaturated monomer (monomer A) containing a fluorinated alkyl group as an essential component. It is a coalescence.
  • the fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) related to the polymer is not particularly limited as long as it is a compound having an ethylenically unsaturated group and a fluorinated alkyl group in the molecule. ,.
  • those containing an acrylic ester group and its related groups are suitable, and specific examples include fluorinated (meth) acrylates represented by the following general formula (1).
  • (meth) acrylate is a generic term for metatalylate, attalylate, fluoro acrylate, and chlorinated acrylate.
  • Rf is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group, and Rf may be linear or branched, and may be an oxygen atom and Z or It may have a functional group containing a nitrogen atom in the main chain
  • R 1 is H, an alkyl group which may be fluorinated, C or F
  • X is a divalent linkage Represents a group
  • n represents an integer of 0 or more.
  • the preferred carbon number of the perfluoroalkyl group of Rf is 1 to 18, more preferably 4 to 18, still more preferably 6 to 14, and most preferably 6 to 12.
  • the partially fluorinated alkyl group preferably has a perfluoroalkyl group in part, and the preferred range of the carbon number of the perfluoroalkyl group is the same as described above.
  • Examples of functional groups include NH—N (CH) N (C H) N (C H) —
  • the alkyl group which may be fluorinated for R 1 may be any of an unsubstituted alkyl group, a perfluoroalkyl group and a partially fluorinated alkyl group. Preference is given to unsubstituted alkyl groups and partially fluorinated alkyl groups. Preferred as an unsubstituted alkyl group is a methinore group. [0105] Preferred as the divalent linking group that X can take is one (CH)-, -CH CH (OH)-(
  • R 2 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
  • n is an integer of 0 or more, 0 to 25 dynamics, 1 to 15 is more preferable, and 1 to 10 is particularly preferable.
  • the linking groups represented by each X may be the same or different.
  • the fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) may be used alone or in combination of two or more.
  • the fluorinated alkyl group in the ethylenically unsaturated monomer (monomer A) containing a fluorinated alkyl group is particularly preferably 6 to 18 carbon atoms from the viewpoint of releasability (peelability). Is 6 to 14, particularly 6 to 12.
  • the amount of the fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) introduced into the polymer (I) is not particularly limited, but it is preferably 10% by mass or more. More preferred is a content of 20% by mass or more.
  • a polyoxyalkylene group-containing unsaturated monomer (monomer B) can be contained in the polymer having a fluorine atom.
  • the polyoxyalkylene group-containing ethylenically unsaturated monomer (monomer B) is not particularly limited as long as it is a compound having a polyoxyalkylene group and an ethylenically unsaturated group in one molecule.
  • the oxyalkylene group an ethylene oxide group and a Z or propylene oxide group are preferable.
  • the degree of polymerization is usually 1 to: L00, preferably 5 to 50.
  • the ethylenically unsaturated group is a (meth) acrylic acid from the viewpoint of availability of raw materials, compatibility with formulations in various coating compositions, ease of controlling such compatibility, or polymerization reactivity. Those containing a stealth group and its related groups are suitable.
  • an ethylenically unsaturated monomer (monomer C) having two or more unsaturated bonds can be contained in one molecule.
  • Ethylene unsaturated monomer (monomer C) having two or more unsaturated bonds in one molecule is not particularly limited. It is appropriately selected depending on the composition of the matrix resin, solvent and the like.
  • Ethylenically unsaturated groups include (meth) acrylic ester groups and from the viewpoints of availability of raw materials, compatibility with formulations in various coating compositions, ease of controlling such compatibility, or polymerization reactivity. The one containing the related group is suitable! / Speak.
  • polymer having a fluorine atom preferably used in the present invention are shown below, but the polymer having a fluorine atom that can be used in the present invention is not limited thereto.
  • PF-10 2 Tridecafluorohexyl-ethyl acrylate: Poly (average degree of polymerization 5) Oxyethylene acrylate: 2-butyl acrylate: Methinoremethacrylate: Tetraethylene glycol Dimethacrylate: 30-25-25-15-5 ( (Molar ratio, molecular weight 3500) PF-11: 2-Tridecafluorohexyl-ethyl acrylate. Poly (average degree of polymerization 5) Oxyethylene metatalate ⁇ ⁇ ⁇ 2-hexyl acrylate.
  • Ethylene glycol dimethacrylate 30Z25Z25Z10 (molar ratio, molecular weight 6000)
  • PF-12 2-tridecafluorohexyl-ethyl acrylate.
  • Noremetatalylate 30 ⁇ 25 ⁇ 25 ⁇ 20 (molar ratio, molecular weight 6000)
  • the cellulose mixed ester and additives are preferably subjected to pelletizing prior to melt film formation.
  • Pereztoy rice cake can be prepared by melting the above cellulose mixed ester and additive carotenoid at 150 ° C to 230 ° C using a twin-screw kneading extruder, then extruding the noodle into a solid and cutting it in water. it can.
  • pelletization by the underwater cutting method in which it is cut while being extruded directly from the die into water after being melted by an extruder, does not work.
  • a meshing type co-rotating twin screw extruder can be used.
  • the size of the preferred pellet lmm 2 to 300 mm 2 cross-sectional area, length lmm ⁇ 30mm is preferred instrument more preferably the cross-sectional area is 2 mm 2 100 mm 2, Ru te at the 1. 5 mm to 10 mm in length.
  • the above additives are added to the raw material inlet and vent in the middle of the extruder. Loca can also be introduced.
  • the rotation speed of the extruder is preferably 10 rpm to: LOOO rpm, more preferably 20 rpm to 700 rpm, and even more preferably 30 rpm to 500 rpm. If it is lOrpm or more, the residence time will not be too long, and it will be difficult to cause a decrease in molecular weight due to thermal deterioration and a yellowish nuisance.
  • the extrusion residence time in pelletization is 10 seconds to 60 minutes, more preferably 15 seconds to 30 minutes. If sufficient melting is possible, it is preferable that the residence time is short in that the deterioration of the fat and the yellowing can be suppressed.
  • the moisture content in the pellets is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably, prior to melt film formation, which is preferably performed by using the above-described method. , 0.01% by mass or less, and then put into the hopper of the melt extruder.
  • the hopper is preferably 20 ° C to 110 ° C or less, more preferably 40 ° C to 100 ° C or less, and further preferably 50 ° C to 90 ° C or less.
  • the hopper is preferably dehumidified air or the like and has a constant air volume and temperature, but this is not necessary as long as the desired moisture content can be obtained. More preferably, the hopper has a vacuum-sealed structure and is filled with an inert gas such as nitrogen.
  • the cellulose mixed ester resin described above is supplied into the cylinder through the supply port of the extruder.
  • the structure of the extruder 22 is shown in FIG. In the cylinder 32, the supply port 40 side force is also applied in order, the supply unit (region A) for quantitatively transporting the cellulose mixed ester resin supplied from the supply port, and the compression unit (region B) for melting and kneading and compressing the cellulose mixed ester resin. ) And a measurement part (area C) that measures melt-kneaded 'compressed cellulose mixed ester resin.
  • the inside of the extruder is inert (nitrogen etc.) in a stream of air.
  • the screw compression ratio of the extruder is set to 2.5 to 4.5, and the L / D is set to 20 to 70. I like to be determined!
  • the screw compression ratio is expressed by the volume ratio of the supply unit A and the measurement unit C, that is, the volume per unit length of the supply unit A ⁇ the volume per unit length of the measurement unit C.
  • the extrusion temperature is preferably set to 190 to 240 ° C. When the temperature in the extruder exceeds 230 ° C, it is preferable to install a cooler between the extruder and the die.
  • the screw compression ratio is too small, it will not melt and knead sufficiently, and undissolved parts will be generated, or the heat generated by shearing will be too small, resulting in insufficient melting of the crystals. Tend to remain, and bubbles tend to be mixed. As a result, when the strength of the cellulose mixed ester film is reduced, or when the film is stretched, the remaining crystals may impair the stretchability and the orientation may not be sufficiently increased. On the other hand, if the screw compression ratio is too large, the shear stress is excessive and the resin tends to deteriorate due to heat generation, so that the cellulose mixed ester film after production tends to be yellowish.
  • the screw compression ratio is preferably in the range of 2.5 to 4.5, more preferably 0.75, in order to make the cellulose mixed ester film after production hardly yellowish and the film strength is strong and the film is not easily stretched and broken. 2. 8 ⁇ 4.2, specially [preferably! / ⁇ ⁇ ] 3. The range is 0 ⁇ 4.0.
  • the LZD is preferably in the range of 20 to 70, more preferably in the range of 22 to 65. Particularly preferred is the range of 24-50.
  • the extrusion temperature is too low, the crystals are not sufficiently melted, and fine crystals are likely to remain in the cellulose mixed ester film after production, and the film strength is reduced or the film is stretched. In addition, the remaining crystals tend to hinder stretchability and fail to sufficiently raise the orientation. Conversely, if the extrusion temperature is too high, the cellulose acylate resin tends to deteriorate and the yellowness (YI value) tends to deteriorate.
  • the extrusion temperature is 180 ° C to 230 ° C, preferably 185 ° C to 230 ° C. More preferably, it is in the range of 190 ° C to 225 ° C.
  • the cellulose mixed ester film formed using the extruder having the extrusion temperature set as described above has a characteristic value having a haze of 2.0% or less and a yellow index (YI value) of 10 or less. Have.
  • the haze is an indicator of whether the extrusion temperature is too low, in other words, an indicator of the amount of crystals remaining in the cellulose mixed ester film after production, and if the haze exceeds 2.0%, The strength of the cellulose mixed ester film is reduced and breakage during stretching tends to occur.
  • the yellow index (YI value) is an index for knowing whether the extrusion temperature is too high. If the yellow index (YI value) is 10 or less, there is no problem in terms of yellowness.
  • extruder As a type of extruder, there are screw types such as full-flight, madok, and dalmage, where single-screw extruders with relatively low equipment costs are generally used.
  • the full flight type is preferred for cellulose mixed ester resin.
  • twin screw extruder that can extrude while volatilizing unnecessary volatile components by providing a vent port in the middle by changing the force screw segment, which is expensive in equipment cost.
  • Biaxial extruders can be broadly classified into the same direction and different direction types, and both can be used. The type of co-rotation with high self-cleaning performance is preferred because it is difficult to generate a staying part.
  • twin-screw extruder is expensive, it is suitable for forming cellulose acetate resin because it has high kneadability and high ability to supply the resin so that it can be extruded at low temperatures. It is possible to use cellulose acylate pellets and powder in an undried state by arranging vents appropriately. Noh. Also, it is possible to reuse film smudges, etc., produced during film formation, without drying them.
  • a preferable screw diameter is 10 mm to 300 mm, more preferably 20 mm to 250 mm, and still more preferably 30 mm to 150 mm, depending on the target extrusion amount per unit time.
  • a gear pump is provided between the extruder and the die, and a certain amount of cellulose mixed ester resin is obtained from the gear pump. Supplying is effective.
  • a gear pump is housed in a state in which a pair of gears consisting of a drive gear and a driven gear are intertwined with each other, and is formed in a housing by driving the drive gear and interposing and rotating both gears.
  • the suction loca also sucks molten resin into the cavity and discharges a certain amount of the discharge loci formed in the housing. Even if there is a slight fluctuation in the grease pressure at the tip of the extruder, the fluctuation is absorbed by using a gear pump, and the fluctuation in the grease pressure downstream of the film forming apparatus is very small, improving the thickness fluctuation.
  • a method of controlling the pressure before the gear pump to be constant by changing the rotation speed of the screw can also be used.
  • a high-precision gear pump using three or more gears that eliminates gear pump gear fluctuations is also effective.
  • Other advantages of using a gear pump are that the pressure at the screw tip can be reduced to form a film, reducing energy consumption 'preventing a rise in oil temperature', 'increasing transport efficiency', 'reducing residence time in the extruder', extrusion
  • the machine can be expected to shorten the LZD.
  • the amount of grease to which the screw force is supplied may fluctuate as the filtration pressure increases.
  • gear pumps are that the length of the equipment increases, the residence time of the resin increases, and the chain breakage occurs due to the shear stress of the gear pump, depending on the equipment selection method. ,Caution must be taken.
  • Residue of the resin is preferred until the resin enters the supply loca extruder
  • the time is 2 minutes to 60 minutes, more preferably 3 minutes to 40 minutes, and even more preferably 4 minutes to 30 minutes. Since the flow of the polymer for bearing circulation of the gear pump becomes poor, the polymer seal in the drive part and the bearing part becomes poor, causing problems such as large fluctuations in metering and liquid feed extrusion pressure. A gear pump design (especially clearance) that matches the melt viscosity of the resin is required. Further, in some cases, the stay portion of the gear pump causes deterioration of the cellulose mixed ester resin, so that a structure with as little stay as possible is preferable.
  • the polymer pipes and adapters that connect the extruder and gear pump or gear pump and die need to be designed with as little residence as possible, and the temperature dependence of the melt viscosity is high!
  • band heaters with low equipment costs are often used for heating polymer tubes, but it is more preferable to use an aluminum encased heater with less temperature fluctuation.
  • G ′, G ⁇ , tan ⁇ , and r? Maximum and minimum values in the extruder it is preferable to melt by heating the barrel of the extruder with a heater divided into 3 to 20.
  • the cellulose mixed ester resin is melted by the extruder configured as described above, and the molten resin is continuously fed to the die from the discharge roller.
  • any type of commonly used die, fishtail die or hanger-coated die may be used.
  • the exit balance of the die exit is generally 1.0 to 5.0 times the film thickness, preferably 1.2 to 3 times, and more preferably 1.3 to 2 times. If the lip clearance is too smaller than the film thickness, it tends to be difficult to obtain a good sheet by film formation. Also, if the lip clearance is too large than the film thickness, the sheet thickness accuracy tends to decrease.
  • the die is a very important facility that determines the thickness accuracy of the film.
  • the thickness can be adjusted at intervals of 40 to 50 mm, but preferably a type capable of adjusting the film thickness at intervals of 35 mm or less, more preferably at intervals of 25 mm or less.
  • cellulose acylate has a melt viscosity Because of its high temperature dependency and shear rate dependency, it is important to design a die that has as little temperature variation as possible and uneven flow velocity in the width direction as much as possible.
  • An automatic thickness adjustment die that measures the downstream film thickness, calculates the thickness deviation, and feeds the result back to the die thickness adjustment is also effective in reducing the thickness fluctuation in long-term continuous production.
  • a single-layer film production apparatus with low equipment costs is generally used. Is possible.
  • the functional layer is preferably thinly laminated on the surface layer, but the layer ratio is not particularly limited.
  • a filtration device incorporating a so-called leaf type disk filter after passing through the gear pump.
  • Filtration can be performed with a single filtration site, or multi-stage filtration with multiple power locations.
  • the filtration accuracy of the filter medium is preferably higher, but the filtration accuracy is preferably 15 ⁇ m to 3 ⁇ m, more preferably 10 ⁇ m to 3 ⁇ m, because of the increase in the pressure resistance of the filter medium and the filtration pressure due to clogging of the filter medium. is there.
  • the type of filter medium is the point force used under high temperature and pressure.
  • steel materials that are preferred to use, stainless steel, steel, etc. are particularly preferred. More preferably.
  • a sintered filter medium formed by sintering metal long fibers or metal powder can be used, and the sintered filter medium is preferred from the viewpoint of filtration accuracy and filter life.
  • the molten resin extruded from the die onto the sheet is cooled and solidified on a casting drum to obtain a film.
  • a method such as an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, a touch roll method, etc.
  • adhesion improving method may be performed on the entire surface of the melt-extruded sheet or a part thereof.
  • a method called “edge-pilling” in which only both ends of the film are brought into close contact with each other is often used, but the method is not limited to this. It is more preferable to use a plurality of casting drums and slowly cool them.
  • the diameter of the roll is preferably 50 mm to 5000 mm, more preferably 100 mm to 2000 mm, and still more preferably 150 mm to 1000 mm.
  • the interval between multiple rolls is preferably between 0.3 mm and 300 mm, more preferably lmn! -100 mm, more preferably 3 mm-3 Omm.
  • the casting drum is preferably from 60 ° C to 160 ° C, more preferably from 70 ° C to 150 ° C, and even more preferably from 80 ° C to 140 ° C. After this, peel off the casting drum force.
  • the winding speed is preferably 10 mZ min to lOO mZ min, more preferably 15 mZ min to 80 mZ min, and even more preferably 20 mZ min to 70 mZ min.
  • the film forming width is preferably 0.7 m to 5 m, more preferably lm to 4 m, and further preferably 1.3 m to 3 m.
  • the thickness of the unstretched film thus obtained is preferably 20 ⁇ m to 400 ⁇ m force S, more preferably 40 ⁇ m to 300 ⁇ m, still more preferably 50 ⁇ m to 200 ⁇ m.
  • the surface of the touch roll may be a metal roll such as rubber or Teflon.
  • the tack roll temperature is preferably 60 ° C to 160 ° C, more preferably 70 ° C to 150 ° C, and still more preferably 80 ° C to 140 ° C.
  • the sheet thus obtained is preferably trimmed at both ends and wound up.
  • the trimmed part is pulverized or, if necessary, granulated or depolymerized and re-polymerized, and then used as a raw material for film of the same type or as a raw material for film of a different type. It may be reused.
  • the trimming cutter is a rotary cutter, shear blade, Any type of material such as a gift may be used. Regarding the material, either carbon steel or stainless steel may be used. In general, it is preferable to use a cemented carbide blade or a ceramic blade because the life of the blade is long and the generation of chips is suppressed.
  • the preferred winding tension is preferably 1 kg / m width to 50 kg / width, more preferably 2 kg / m width to 40 kg / width, and even more preferably 3 kg / m width to 20 kg / width. If the winding tension is too small, it tends to be difficult to wind the film uniformly. On the other hand, if the take-up tension is too large, the film becomes stiff and not only the winding appearance is deteriorated, but also the bump portion of the film extends due to the creep phenomenon, causing the film to wavy. Or residual birefringence tends to occur easily due to film elongation.
  • the winding tension is preferably detected by tension control in the middle of the line and wound while being controlled so as to have a constant winding tension. If there is a difference in film temperature depending on the location of the film production line, the length of the film may be slightly different due to thermal expansion. It is necessary to prevent the above tension from being applied.
  • the take-up tension is a force that can be taken up at a constant tension by controlling the tension control. It is more preferable to taper the take-up tension in accordance with the diameter of the take-up to obtain an appropriate take-up tension. In general, the force that gradually decreases the tension as the winding diameter increases. In some cases, it may be preferable to increase the tension by increasing the winding diameter.
  • melt film formation is performed through a kneading / extrusion process, casting process, stretching process, relaxation process, cooling process, winding process, and processing process in which cellulose mixed ester is preheated to a predetermined temperature and mixed with additives.
  • a cellulose mixed ester film is obtained.
  • the cellulose mixed ester is sufficiently dried in advance and then charged into a hopper of a melt extruder.
  • moisture in the cellulose mixed ester The amount is 0.5% by mass or less, more preferably 0.2% by mass, and particularly 0.1% by mass or less.
  • hydrolysis of the cellulose mixed ester that develops during melting can be suppressed, and generation of foreign substances associated therewith can be suppressed.
  • Such drying can be achieved by drying the cellulose mixed ester preferably at 80 ° C to 180 ° C, preferably for 0.1 hour to 100 hours. This treatment may be performed in an air atmosphere, an inert gas (for example, nitrogen) atmosphere, or in a vacuum. Foreign substances generated during film formation can be reduced by the pretreatment.
  • drying by heating under reduced pressure is preferable. This is because the source of foreign substances is mainly due to the hydrolyzate of cellulose mixed ester with water, the dehydration reaction by sulfuric acid desorption with bound sulfuric acid, and the acid decomposition with oxygen.
  • the heating temperature of the hopper preferably used in the present invention is preferably (Tg—50 ° C) to (Tg + 30 ° C), more preferably (Tg—40 ° C) to (Tg + 10 ° C), more preferably (Tg—30 ° C) to Tg is recommended. As a result, moisture re-adsorption from the air to the cellulose mixed ester in the hopper can be suppressed. (Kneading extrusion)
  • the mixed cellulose ester is kneaded at a desired melting temperature heated in the preheating process. That is, in the present invention, in order to eliminate die lines, the melting temperature of the cellulose mixed ester in the present invention is set to 180 ° C to 230 ° C, preferably 190 ° C to 225 ° C, more preferably 190 ° C. Perform at ⁇ 220 ° C. When melted at a high temperature of 230 ° C.
  • the cellulose mixed ester in the present invention is decomposed, and a die line is generated due to the decomposition product remaining in the die, and the thickness unevenness is remarkably deteriorated. Furthermore, the coloring is remarkably generated, which causes a problem that the ear loss generated during film formation cannot be reused.
  • the method described in the examples of the prior application is improved in view of the fact that the decomposition of the cellulose mixed ester is carried out at a remarkably high temperature. Note that when the melting temperature is lowered to less than 180 ° C., poor melting occurs, and this tends to cause bumps. Therefore, in the present invention, it is also recommended to use a screw with a high compression ratio so as not to cause insolubility even at low temperatures.
  • a preferred compression ratio is 2 to 15, 3 to 15 is more preferred, 4 to 12 is even more preferred 5: L0 is particularly preferred. Usually melts at a compression ratio of less than 3 It is common.
  • the melting temperature may be a constant temperature or may be performed at a melting temperature obtained by dividing into several parts and controlling! /. More preferably, the temperature on the upstream side (hopper side) is 1 ° C to 50 ° C, more preferably 2 ° C to 30 ° C, even more preferably 3 ° C to 20 ° C from the temperature on the downstream side (T-die side) A higher temperature is preferable because decomposition of the cellulose mixed ester can be further suppressed. Further, in order to efficiently perform the melting, it is preferable to lower the temperature in order to suppress the decomposition of the cellulose mixed ester after melting, preferably at a higher temperature in the upstream portion of the liquid feeding.
  • a preferable kneading time is 2 minutes to 60 minutes, more preferably 3 minutes to 40 minutes, and further preferably 4 minutes to 30 minutes. It is also preferable to carry out the inside of the melt extruder in an inert (nitrogen, etc.) stream.
  • the molten cellulose mixed ester is preferably passed through a gear pump to remove the pulsation of the extruder. Following that, it is preferable to filter with a metal mesh filter or the like.
  • the mesh size is preferably 2 to 30 m, more preferably 2 to 20 / ⁇ ⁇ , and even more preferably 2 to LO m.
  • the filtration pressure is preferably 0.5 MPa to 15 MPa, more preferably 2 Pa to 15 MPa, and most preferably 10 Pa to 15 MPa.
  • a higher filtration pressure is preferable because the filtration time can be shortened. However, it is preferable to use a high pressure within a range in which the filter does not break.
  • the temperature during filtration is preferably 180 ° C to 230 ° C, more preferably 180 ° C to 220 ° C, and further preferably 190 ° C to 220 ° C. If the temperature at the time of filtration is less than or equal to the upper limit value, problems such as the progress of thermal degradation are unlikely to occur, so if it is greater than or equal to the preferred lower limit value, too much time is required for filtration and the thermal degradation proceeds. This is preferable because the inconvenience is not likely to occur. The time required for filtration should be as short as possible to prevent yellowing of the film.
  • the amount of filtration per minute per filter lcm 2 is 0.05-: LOOcm 3 forceful, 0.1-: LOOcm 3 is more preferable 0.5-: L 00 cm 3 is most preferable.
  • examples of the film forming die include a T-type die (T-die) and a hanger type (hanger-coated die), and a T-die is preferable.
  • the die force is also extruded in the form of a sheet onto the cooling drum that conveys it, but as described above, the die force is controlled to a temperature lower than the melting temperature. Is preferred.
  • the melt temperature can be divided into multiple parts in the melt extruder and made different. In this case, the melt temperature closest to the die is used as a reference. After this, keep a certain distance (preferably 1-50 cm) between the die and the casting drum as described above. At this time, it is preferable to put in the casing so that the temperature fluctuation during this period is small.
  • the die temperature is 5 ° C to 30 ° C lower than the melting temperature. This is characterized by the fact that the temperature of the die was lowered in order to prevent it from staying on the die and decomposing and burning the cellulose mixed ester, which would cause die line.
  • melt kneading machine power is the same temperature up to the die, or higher, and by lowering the melt viscosity, it is common to level the generated die line.
  • the mixed ester is melt-cast, it is effective to lower the temperature as described above.
  • the die and the casting drum be separated from each other by 2 to 50 cm. More preferably, it is 5 cm to 40 cm, and further preferably 7 cm to 35 cm.
  • the cellulose mixed ester is difficult to neck-in, it is preferable to take a wide space between the casting drum and the die as described above.
  • the temperature of the casting drum at this time is preferably (Tg—30 ° C) to Tg, more preferably (Tg—20 ° C) to (Tg—1 ° C), and even more preferably (Tg—15 ° C). ) To (Tg—2 ° C.). Furthermore, increasing the distance between the die and the casting drum in this way also has the effect of leveling and reducing the die line.
  • the Tg of the cellulose mixed ester of the present invention is preferably 70 ° C to 180 ° C, more preferably 80 ° C to 160 ° C, and still more preferably 90 ° C to 150 ° C.
  • Extrusion may be performed in a single layer, or a multi-layer extrusion may be performed using a multi-hold die or a field block die. After that, it is extruded onto a casting drum having an appropriately selected diameter (preferably 10 to 200 cm), number (preferably 2 to 20), and temperature (Tg-30 ° C is preferred). At this time, a sheet that has been melt-extruded with a casting drum by using an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, a touch roll method, or the like. It is preferable to increase the adhesion. Such adhesion improving method may be performed on the front surface of the melt-extruded sheet or on a part thereof.
  • the time for cooling and solidifying the molten cellulose mixed ester (melt), which is also extruded with the T-die force, on the casting drum is as long as possible. That is, the melt extruded above Tg from the T die shrinks to below Tg on the casting drum. At this time, since shrinkage in the in-plane direction is suppressed by friction between the melt and the casting drum, shrinkage in the thickness direction becomes dominant. That is, a plane orientation is formed here, and letter-thickness (Rth) in the thickness direction (hereinafter sometimes referred to as “Rth”) is developed. If this contraction is abrupt, the point is to cool slowly as described above, which easily develops Rth unevenness.
  • Rth letter-thickness
  • the number of casting drums is preferably 2 to 10, more preferably 2 to 6, and further preferably 3 to 5.
  • the temperature of these casting drums may be the same or different. More preferably, the temperature of the most upstream casting drum is lower than that of the most downstream casting drum. When three or more are disposed, the casting drum temperature between them may be higher or lower than the temperature of the preceding roll. In other words, the temperature of the uppermost stream and the lowermost stream should be lowered, and the roll temperature during that time should be set arbitrarily.
  • the diameter of these casting drums is usually 20cm to 200cm. It is preferable to form these films at a rate of 15 mZ to 300 mZ. More preferably, it is 20 mZ minutes to 200 mZ minutes, and further preferably 30 mZ minutes to 1 OOmZ minutes.
  • the cellulose mixed ester film was stripped of the casting drum force, passed through the nip roll, cut with the nip roll, and then wound up with a tension of 0.0. lkgZcm 2 ⁇ 10kgZcm more preferably preferably wound up is fitting in 2 0. 10kgZcm 2 ⁇ 9 kg / cm 2, further ⁇ This preferably 0. 10kgZcm 2 ⁇ 9kgZcm 2.
  • the winding speed is preferably 10 mZ min to lOO mZ min, more preferably 15 mZ min to 80 mZ min, and even more preferably 20 mZ min to 70 mZ min.
  • the film forming width is preferably 1.5 m to 5 m, more preferably 1.6 m to 4 m, and still more preferably 1.7 m to 3 m. Since the sheet immediately after peeling off from the casting drum is close to Tg, it is stretched by the winding tension to develop Re and Rth, and this becomes more prominent at the end than at the center.
  • the thickness of the film thus obtained is preferably 20 ⁇ m to 400 ⁇ m, more preferably 40 ⁇ m to 200 ⁇ m, and particularly preferably 50 ⁇ m to 150 ⁇ m.
  • the thickness of the obtained cellulose mixed ester film exceeds 200 micrometers, it can be set as the preferable film thickness of this invention by extending
  • the sheet thus obtained is preferably trimmed at both ends and wound up.
  • the trimmed portion is crushed or reprocessed as a raw material for film of the same type or as a raw material for film of a different type after being subjected to processing such as granulation or depolymerization and re-polymerization as necessary. May be used.
  • the cellulose mixed ester film formed into a film during the melt film-forming process is stretched.
  • the process is preferably stretched in at least one direction. Stretching is preferably performed at Tg to (Tg + 50 ° C), more preferably (Tg + l ° C) to (Tg + 30 ° C), and even more preferably (Tg + 2 ° C) to (Tg + 20 ° C).
  • the stretching ratio is preferably at least 10% to 50% stretched in one direction.
  • the draw ratio is preferably 1% to 150%, more preferably 1% to 100%, and particularly preferably 1% to 50%. These stretching operations may be performed in one stage or in multiple stages.
  • the draw ratio here is determined using the following equation.
  • Stretch ratio (%) 100 X ⁇ (Length after stretching)-(Length before stretching) ⁇ Z Length before stretching Two or more pairs of up-rolls with such a stretch that increased the peripheral speed on the exit side
  • the film may be stretched in the longitudinal direction (longitudinal stretching), or both ends of the film may be held by a chuck and spread in the orthogonal direction (longitudinal direction and perpendicular direction) (lateral stretching).
  • both Re and Rth can be increased.
  • the ratio of Re and Rth can be freely controlled by controlling the value (aspect ratio) divided by the film width in the case of longitudinal stretching.
  • the RthZRe ratio can be increased by reducing the aspect ratio.
  • transverse stretching it can be controlled by stretching in the orthogonal direction and simultaneously stretching in the longitudinal direction, or conversely relaxing. That is, the RthZRe ratio can be increased by stretching in the vertical direction, and the RthZRe ratio can be decreased by relaxing in the vertical direction.
  • Such a stretching speed is preferably 10% Z min to 10000% Z min, more preferably 20% Z min to 1000% Z min, and further preferably 30% Z min to 800% Z min.
  • the stretching temperature has a gradient in the width direction. It is preferable to have it. That is, in both the case of longitudinal stretching and the case of lateral stretching, stretching at both ends tends to proceed easily, and Re and Rth are likely to be expressed.
  • the end refers to a region of 10% of the total width, which is 6 ° C to 40 ° C, more preferably 7 ° C to 30 ° C, and more preferably 8 ° C to 25 ° from the center. Can be achieved by increasing C.
  • a hot air outlet may be added at either end, or a heat source (panel heater, infrared heater, etc.) may be added.
  • a heat source panel heater, infrared heater, etc.
  • the cooling temperature after the heat treatment varies depending on the heat treatment temperature and the film thickness, but is usually air-cooled in a temperature range of -40 ° C to (Tg-10) ° C. Preferably, it is 0 to 40 ° C.
  • the temperature difference of the cooling medium such as air that cools the front and back surfaces of the film affects the non-thermal deformability of the obtained (biaxial) stretched film. If the temperature difference of the cooling gas is too large, the difference in heat shrinkage between the front and back surfaces of the obtained (biaxial) stretched film becomes large, and the film is easily distorted and warped during heating, resulting in large deformation.
  • the temperature difference between the cooling medium such as air for cooling the front and back surfaces of the film is preferably small. However, in order to achieve the object of the present invention, the temperature difference is 5%. It is important to adjust within ° C.
  • These stretched cellulose ester films before and after stretching preferably have a longitudinal and lateral dimensional shrinkage of ⁇ 0.1% or less at 105 ° C for 5 hours. 80 ° C '
  • the haze that the dimensional shrinkage at 90% relative humidity is preferably less than ⁇ 0.5% in both length and width is preferably 1.2% or less, and more preferably 0.6% or less.
  • tear strength both vertically and horizontally preferably fixture tensile strength is at 10g or vertical, preferably it is horizontal with a on 50NZmm 2 or more members modulus vertical, that is transverse with 3KNZmm 2 or more preferable.
  • These unstretched and stretched cellulose mixed ester films can be used alone or in combination with a polarizing plate.
  • a liquid crystal layer or a layer with a controlled refractive index (low reflection layer) can be used on these films.
  • Nyanide coat layer may be provided and used.
  • the stretched film can be achieved by stretching an unstretched film.
  • a stretched film with small Re unevenness can be achieved by stretching an unstretched film (raw material) with small Re unevenness.
  • a film with reduced thickness unevenness as described above, it is possible to perform uniform stretching in both thickness and letter-decision.
  • a film with thickness unevenness as described in Japanese Unexamined Patent Publication No. 2000-352620 is stretched, the thickness unevenness is easily amplified because the film is stretched mechanically weakly and thinly, and the thickness unevenness is reduced by stretching. Forces that can make an impression Such cellulose mixed esters The reverse is true for film).
  • the film thickness of the cellulose mixed ester film of the present invention is 20 to 200 ⁇ m, more preferably 20 ⁇ m to 160 ⁇ m, and even more preferably 30 ⁇ m to 120 ⁇ m. I like 40 ⁇ 120 111. Therefore, in the case of stretching, the film thickness of the unstretched film is such that a desired cellulose mixed ester film is prepared in advance as a thick original extruded film thickness depending on the stretch ratio. Further, it is preferable that the angle 0 formed by the film forming direction (longitudinal direction) and the slow axis of Re of the film is close to 0 °, + 90 ° or ⁇ 90 °.
  • the thickness unevenness of the cellulose mixed ester film of the present invention is preferably 0 to 3 ⁇ m, more preferably 0 to 2 ⁇ m, more preferably 0 to 5 ⁇ m in both the thickness direction and the width direction.
  • fine particles are added to a cellulose mixed ester to reduce the squeegee value and improve the transportability.
  • the dynamic and static kimi values of the cellulose mixed ester film are both preferably 0.2 to 1.5, more preferably 0.2 to 1.3. Is preferably 0.256-1.
  • the kishimi value may be small or large. In both cases, the transportability is not preferable, and it is not recommended due to the occurrence of scratches.
  • the measurement of the kimimi value is determined according to the following. Samples lOOmm X 200mm and 75mm X 100mm samples were conditioned for 2 hours at 25 ° C and 60% relative humidity, and large with a Tensilon tensile tester (RTA-100, manufactured by Orientec Co., Ltd.) Secure the film on the table and place a small film with 200g weight on it. Next, the weight was pulled in the horizontal direction, the force when moving and the force when moving were measured, and the static friction coefficient and the dynamic friction coefficient were calculated, respectively, and were used as the artificial and dynamic kimi values.
  • RTA-100 Tensilon tensile tester
  • the cellulose mixed ester film containing fine particles produced by the production method of the present invention is characterized in that the surface roughness is within an appropriate range.
  • the arithmetic average roughness (Ra) of the cellulose mixed ester film is 3 ⁇ ! It is more preferable that the thickness is ⁇ 200 nm, more preferably 5 nm to 100 nm, and particularly preferably 5 ⁇ ! ⁇ 80nm.
  • Arithmetic mean roughness (Ra) can be measured with a commonly used contact or non-contact surface roughness measuring instrument.
  • the power which shows a preferable example about the optical characteristic of the cellulose mixed ester film of this invention manufactured by the manufacturing method of this invention is not limited to this.
  • Re (E) and Rth () respectively represent in-plane letter thickness and thickness direction letter decisions at the wavelength.
  • Re () is measured using KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments) with light of wavelength ⁇ nm incident in the normal direction of the film.
  • Rth ( ⁇ ) is calculated by the following method.
  • Rt (X) is the above-mentioned Re ( ⁇ ), with the in-plane slow axis (determined by KOBRA 21 ADH or WR) as the tilt axis (rotary axis) (if there is no slow axis, it is in the film plane) (In any direction of the rotation axis) with respect to the normal direction of the film (in the direction of rotation) from the normal direction to the angle of 50 ° to + 50 ° in 10 ° steps. A total of 11 points are measured, and KOBRA 21ADH or WR calculates based on the measured retardation value, average refractive index, and input film thickness value.
  • ⁇ when only the description about ⁇ is described as Re or Rth, it represents a value measured using light having a wavelength of 590 nm.
  • Re or Rth when only the description about ⁇ is described as Re or Rth, it represents a value measured using light having a wavelength of 590 nm.
  • letter data at a tilt angle larger than the tilt angle is used.
  • the Chillon value is calculated by KOBRA 21 ADH or WR after changing its sign to negative.
  • the slow axis is the tilt axis (rotation axis) (if there is no slow axis, the arbitrary direction in the film is the rotation axis), and the retardation value is measured from any two tilted directions, So Rth is calculated from the following formulas (b) and (c) based on the above values, average refractive index, and input film thickness value.
  • Re ( ⁇ ) represents the retardation value in the direction inclined by angle ⁇ from the normal direction.
  • nx represents the refractive index in the slow axis direction in the plane
  • ny represents the refractive index in the direction perpendicular to nx in the plane
  • nz represents the refractive index in the direction perpendicular to nx and ny.
  • Rth ( ⁇ ) is calculated by the following method.
  • Rth (l) is the above-mentioned Re ( ⁇ ), and the in-plane slow axis (determined by KOBRA 21 ADH or WR) is the tilt axis (rotation axis).
  • Each tilted directional force wavelength ⁇ nm is incident in steps of 10 degrees up to 50 degrees and measured at 11 points. Based on the measured letter value, average refractive index, and input film thickness value. Calculated by KOBRA 21ADH or WR.
  • KOBRA 21 8 011 or 1 ⁇ ⁇ calculates 1 ⁇ , ny, nz.
  • Nz (nx ⁇ nz) Z (nx ⁇ ny) is further calculated from the calculated nx, ny, and nz.
  • the front-face letter retardation (Re) of the cellulose mixed ester film of the present invention at a wavelength of 590 nm is preferably 0 to 10 nm, and the absolute value of the thickness direction letter retardation (Rth) is 0 to 60 nm. It is preferable. More preferably, the front letter decision (Re) is preferably from 0 to 8 nm, and the absolute value of the letter direction (Rth) in the thickness direction is ⁇ 50 nm. Re) force is 0-5nm The absolute value of letterthickness (Rth) in the thickness direction is ⁇ 40nm. The preferable Re unevenness is 0 to 5 nm, more preferably 0 to 5 ⁇ m, and still more preferably 0 to 3 ⁇ m.
  • the preferred Rth unevenness is preferably 0% to 0%, more preferably 0% to 7%, and still more preferably 0% to 5%.
  • the cellulose mixed ester film of the present invention having these optical properties is most preferable as a protective film for a polarizer.
  • the present invention can also improve the optical characteristic problem due to humidity change, and is characterized by a small difference between the optical characteristic of 10% relative humidity and the optical characteristic of 80% at 25 ° C. . That is, the cellulose mixed ester film of the present invention evaluates the amount of change due to humidity change of Re by its absolute value, and the change of Re humidity (nm) is Re (relative humidity 80%) and Re (relative humidity 10%). %), And Rth humidity change (nm) due to humidity change is expressed by the absolute value of the difference between Rth (relative humidity 80%) and Rth (relative humidity 10%).
  • the change in humidity of Re is preferably 10 nm or less, more preferably 5 nm can be realized, and lnm can also be realized. Moreover, it is preferable that the Rth humidity change is 25 nm or less, and further 20 nm can be realized, and 15 nm can also be realized. This is a preferred humidity change of 2/3 to 1/2 compared to conventional cellulose triacetate.
  • the cellulose mixed ester film of the present invention can also control the behavior of optical properties with respect to wavelength. That is, it is preferable that the absolute value of the difference between Re (400) and Re (700) at wavelengths of 400 nm and 700 nm is ⁇ 15 nm.
  • the absolute value of the difference between Rth (400) and Rth (700) The value is preferably 0-35nm! / ,.
  • the front letter-deposition (Re) and thickness-direction letter-decrease (Rth) at wavelengths of 400 nm and 700 nm of the cellulose mixed ester film of the present invention are represented by the following formula (A-1): And it is preferable to satisfy (A—2)! /.
  • the intrinsic birefringence which is a method for displaying the optical properties of the cellulose mixed ester film of the present invention, has an intrinsic birefringence in the in-plane direction at a wavelength of 590 nm in an environment of 25 ° C 'relative humidity of 60% and 0 to
  • the absolute value of the intrinsic birefringence in the thickness direction which is preferably 0.001, is preferably 0 to 0.003.
  • the absolute value of the intrinsic birefringence in the thickness direction is preferably 0 to 0.0025, and the in-plane direction intrinsic birefringence is preferably 0 to 0.0008.
  • the intrinsic birefringence is preferably 0 to 0.0006, and the absolute value of the intrinsic birefringence in the thickness direction is preferably 0 to 0.001.
  • the optical slow axis is parallel to the casting direction or the width direction and is perpendicular.
  • 0 ⁇ 3 ° is preferred as it is closer to 0 °, more preferably 0 ⁇ 1.5 °, and more preferably 0 ⁇ 0.5 °.
  • 90 ⁇ 3 ° or ⁇ 90 ⁇ 3 ° is preferred, more preferably 90 ⁇ 1.5 ° or ⁇ 90 ⁇ 1.5 °, and even more preferably 90 ⁇ 0.5 ° or one. 90 ⁇ 0.5 °.
  • the transmittance of visible light (615 nm) was measured on a 20 mm ⁇ 70 mm sample at 25 ° C. and a relative humidity of 60% with a transparency measuring device (AKA photoelectric tube colorimeter, manufactured by KOTAKI Corporation).
  • the cellulose mixed ester film of the present invention preferably has a transmittance of 90% or more, more preferably 91% or more, and particularly a transmittance of 92% or more.
  • Sample 40mm x 80mm is measured according to JIS K-6714 with a haze meter (HGM-2 DP, Suga Tester) at 25 ° C 'relative humidity 60%.
  • the cellulose mixed ester film of the present invention preferably has a haze in the range of 0 to 1.5%, more preferably 0 to 1.2%, still more preferably 0 to 0.8%, and particularly 0. 1 to 0.5% is preferred.
  • the haze of the cellulose mixed ester film of the present invention is 0.1 to 1.
  • the cellulose mixed ester film can be optionally subjected to a surface treatment to improve the adhesion between the cellulose mixed ester film and each functional layer (for example, the undercoat layer and the back layer).
  • a surface treatment for example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used.
  • the glow discharge treatment refers to so-called low-temperature plasma that occurs under a low pressure gas of 10 ⁇ 3 to 20 Torr (about 0.13 to 2666 Pa), but may be a glow discharge treatment under atmospheric pressure.
  • glow discharge treatment under low pressure is performed in US Pat. Nos. 3,462,335, 3,761,299, 4,072,769, and British patents. No. 891, 469. It is also possible to introduce specific gases such as inert gases, nitric oxides and organic compound gases. When the surface of the polymer is subjected to a glow discharge treatment, it may be performed at atmospheric pressure or under reduced pressure. Further, it may be carried out while introducing various gases such as oxygen, nitrogen, helium or argon and water into the atmosphere of the glow discharge treatment.
  • the degree of vacuum during the glow discharge treatment is preferably 0.005 to 20 Torr (0.67 to 2666 Pa) force, more preferably 0.02 to 2 Torr (2.67 to 267 Pa).
  • the voltage during glow discharge treatment is preferably 500 to 3000V, more preferably between 500 and 5000V.
  • the discharge frequency used is from DC to several thousand MHz, more preferably 50 Hz to 20 MHz, and still more preferably 1 ⁇ to 1 ⁇ .
  • the discharge treatment intensity, 0. OIKV'A 'partial Zellesiiota 2 preferably than ⁇ 5 ⁇ ⁇ ⁇ ⁇ min Zm 2 is preferably tool is 0.151 ⁇ ' min 7111 2-11 ⁇ 'min 7111 2 Dearu.
  • an ultraviolet irradiation method is also preferably used.
  • the mercury lamp used in the ultraviolet irradiation method is a high-pressure mercury lamp with quartz tube power, and the wavelength of ultraviolet light is 180 ⁇ ! Those between ⁇ 380 nm are preferred.
  • the surface temperature of cellulose mixed ester film rises to around 150 ° C. If this does not affect the performance of the support, a high-pressure mercury lamp with a dominant wavelength of 365 nm can be used as the light source.
  • a low pressure mercury lamp having a dominant wavelength of 254 ⁇ m is preferable.
  • Ozone-less high-pressure mercury lamps and low-pressure mercury lamps can also be used.
  • the irradiation light quantity is 20 to: LOOOO (miZcm 2 ) is more preferable, and preferably 50 to 2000 (m) / cm 2.
  • the irradiation light quantity is preferably from 100 to 10,000 (mjZcm 2 ), more preferably from 300 to 1500 (mjZcm 2 ).
  • corona discharge treatment is also preferable as the surface treatment of the cellulose mixed ester film of the present invention.
  • a solid state corona treatment machine manufactured by Pillar a LEPEL type surface treatment machine, a VETAPHON type treatment machine, or the like can be used.
  • the corona discharge treatment can be performed in air at normal pressure.
  • the discharge frequency during processing is 5 to 40 kHz, more preferably 10 to 30 kHz, and the waveform is preferably an AC sine wave.
  • the gap clearance between the electrode and the dielectric roll is preferably 0.1 mm to 10 mm, more preferably 1. Omn! ⁇ 2. Omm.
  • the discharge is processed above the dielectric support roller provided in the discharge zone, and the throughput is 0.3 to 0.4 ⁇ ⁇ ⁇ ⁇ min / m 2 , more preferably 0.34 to 0.38 ⁇ 38 ⁇ ⁇ ⁇ ⁇ ⁇ is the partial Zm 2.
  • the gas used for the flame treatment may be natural gas, liquefied propane gas, or city gas, but the mixing ratio with air is important.
  • Natural gas Z air is preferably mixed in a volume ratio of 1Z6 to 1Z10, preferably 1Z7 to LZ9.
  • 1Z14 ⁇ : LZ22 preferably 1Z16 ⁇ : LZ19
  • 1Z2 ⁇ : LZ8 preferably 1Z3 ⁇ : LZ7.
  • the flame treatment amount may be 1 to 50 Kcal / m 2 , more preferably 3 to 20 Kcal / m 2 .
  • the cellulose mixed ester film of the present invention is preferably used as a surface treatment of the cellulose mixed ester film of the present invention.
  • the alkali saponification treatment will be specifically described. It is preferable that the cellulose mixed ester film surface is immersed in an alkaline solution, then neutralized with an acidic solution, washed with water and dried.
  • alkaline solution examples include potassium hydroxide solution and sodium hydroxide solution.
  • the concentration of hydroxide ions is preferably 0.1 mol ZL to 4. Omol ZL, more preferably 0.5 mol ZL to 3.5 mol ZL.
  • the temperature of the alkaline solution is preferably in the range of room temperature to 90 ° C, more preferably 40 ° C to 70 ° C. In the alkali saponification treatment, after immersing in an alkali solution, it is generally washed with water, and after passing through an acidic aqueous solution, it is washed with water to obtain a surface-treated cellulose mixed ester film.
  • the acidic aqueous solution is an aqueous solution of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, black acetic acid, oxalic acid, and the like, and the concentration is preferably 0.01 molZL to 3. OmolZL. .05 molZL to 2. OmolZL is more preferable.
  • the alkali saponification time is preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and particularly preferably 40 to 210 seconds.
  • the neutralization with an acidic solution is preferably carried out for 20 to 600 seconds, more preferably 30 to 250 seconds, and particularly preferably 40 to 180 seconds. Further, the water washing after neutralization is preferably carried out for 20 to 400 seconds, more preferably 30 to 300 seconds, and particularly preferably 40 to 210 seconds.
  • the surface energy of the solid obtained by these methods is determined by the contact angle method, the wet heat method, and the adsorption method as described in "Basics and Application of Wetting" (Realize Corp., issued on Dec. 10, 1989). It is preferable to use the contact angle method.
  • the water contact angle (25 ° CZ relative humidity 60%) on the cellulose mixed ester film surface of the present invention is preferably 45 ° or less, more preferably 10 to 45 °, and even more preferably 10 to 40. A temperature of 10 to 30 ° is most preferable.
  • the cellulose mixed ester film of the present invention is a method for obtaining adhesion by directly applying a functional layer on a cellulose mixed ester film after surface activation treatment in order to adhere the functional layer.
  • an undercoat layer adheresive layer
  • a functional layer is applied thereon.
  • Various ideas have been made for the constitution of the undercoat layer. For example, it is well adhered to a support (cellulose mixed ester film) as a single layer method in which one undercoat layer is composed of one layer or as a first layer.
  • a layer hereinafter sometimes referred to as “first undercoat layer”
  • second undercoat layer that adheres well to the functional layer as a second layer is applied thereon.
  • the primer polymer used in the primer layer include water-soluble polymers, cellulose mixed esters, latex polymers, and water-soluble polyesters.
  • the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the cellulose mixed ester includes carboxymethyl cellulose. And hydroxyethyl cellulose mouth.
  • latex polymer examples include a salty vinyl-containing copolymer, a salty-vinylidene-containing copolymer, an acrylic ester-containing copolymer, an acetic acid-bule-containing copolymer, and a butagen-containing copolymer.
  • a medium-selected monomer such as butyl chloride, salt vinylidene, butadiene, methacrylic acid, acrylic acid, itaconic acid or maleic anhydride is used as a starting material.
  • oligomers or polymers such as polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, etc. can be used.
  • the aforementioned water-soluble polymer for example, the aforementioned water-soluble polymer, cellulose mixed ester, latex polymer, water-soluble polyester, and the like can be used.
  • the cellulose mixed ester film of the present invention is preferably provided with a hydrophilic binder layer that also has a hydrophilic binder force for adhering to a polarizer.
  • the hydrophilic binder include a COOM group-containing butyl-maleic acid copolymer compound, or a hydrophilic cellulose derivative (for example, methylcellulose, carboxymethylcellulose, hydroxyalkylcellulose, etc.), a polybutyl alcohol derivative (for example, Butyl acetate, butyl alcohol copolymer, polybuluacetal, polybule formal, polybulb benzal, etc.) Latin, casein gum arabic, etc.), and hydrophilic group-containing polyester derivatives (for example, sulfone group-containing polyester copolymers).
  • the undercoating layer optionally applied to the cellulose mixed ester film of the present invention can contain inorganic or organic fine particles as a matting agent to such an extent that the transparency of the functional layer is not substantially impaired.
  • Inorganic particulate matting agents include silica (SiO 2), titanium dioxide (TiO 2), calcium carbonate
  • Um, magnesium carbonate, etc. can be used.
  • examples of the organic fine-particle matting agent include polymethylmetatalylate, cellulose acetate propionate, polystyrene, a processing solution-soluble one described in US Pat. No. 4,142,894, US Pat.
  • the polymers described in 396, 706 can be used.
  • These fine particle matting agents preferably have an average particle size of 0.01 to 10 m. More preferably, it is 0.05 to 5 / ⁇ ⁇ .
  • the content is preferably 0.5 to 600 mg / m 2, more preferably 1 to 400 mg Zm 2 .
  • the undercoat liquid may be a generally well-known coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, or US Patent No. It can be applied by an etching coating method using a hopper described in the specification of 2, 681, 294.
  • an antistatic layer is provided on at least one layer of the film, or a hydrophilic binder layer for adhering to the polarizer is provided. It is preferable.
  • the conductive material contained in the conductive layer is preferably a conductive metal oxide or a conductive polymer.
  • the vapor deposition may be a transparent conductive film formed by sputtering.
  • the conductive metal oxide include ZnO, Ti 2 O, SnO, Al 2 O, In 2 O, SiO 2, MgO, BaO, MoO, and V 2 O, or a combination of these.
  • a mixed oxide is preferred, and ZnO, SnO or V 2 O is particularly preferred.
  • hetero atoms of the composite oxide addition of Al, In, Ta, Sb, Nb, halogen, and Ag is effective, and the addition amount is preferably in the range of 0.01 mol% to 25 mol%.
  • the volume resistivity of these conductive metal oxide powders is preferably 10 7 ⁇ 'cm, particularly preferably 10 5 ⁇ 'cm or less.
  • the primary particle size of the metal oxide powder is 100 A to 0.2 m. It is preferable to contain 0.01% to 20% by volume of a powder having a specific structure.
  • the amount of the conductive fine particles (metal oxide powder) used is preferably 0.01-5. Og / m 2 is particularly preferable. 0.005: Lg / m 2 is preferable.
  • the conductive fine particle-dispersing binder is not particularly limited as long as it has a film-forming ability, and examples thereof include proteins such as gelatin and casein; carboxymethylenosenolellose, hydroxye, and the like.
  • Cellulose compounds such as chinorecenolose, acetylenolosenolose, dicetinolecellulose, triacetylcellulose; sugars such as dextran, agar, sodium alginate, starch derivatives, polybulu alcohol, polyvinyl acetate, polyacrylate,
  • synthetic polymers such as polymethacrylic acid ester, polystyrene, polyacrylamide, poly-N-butylpyrrolidone, polyester, polychlorinated butyl, and polyacrylic acid.
  • the conductive layer may contain an ion conductive substance.
  • the ion conductive substance is a substance that shows electric conductivity and contains ions that are carriers for selecting electricity. Examples thereof include ionic polymer compounds and metal oxide sols containing electrolytes.
  • the electric resistance of these conductive layers is preferably 10 12 ⁇ (25 ° C., relative humidity 10%) or less, more preferably 10 1 () ⁇ or less, and particularly preferably 10 9 ⁇ or less.
  • an organic electron conductive material is also preferable. Examples thereof include polyarine derivatives, polythiophene derivatives, polypyrrole derivatives, and polyacetylene derivatives.
  • a surfactant is preferably used for forming a functional layer.
  • the surfactant used for forming the functional layer in the present invention is classified into a dispersant, a coating agent, a wetting agent, an antistatic agent, and the like depending on the purpose of use.
  • the surfactant described below is appropriately used. So that those goals can be achieved.
  • a nonionic property or an ionic property a-on, cation, betaine
  • a fluorine-based low molecular surfactant is preferably used as a coating agent in an organic solvent or as an antistatic agent.
  • the layer to be used may be a film having cellulose mixed ester power or any other functional layer.
  • functional layers include an undercoat layer, an intermediate layer, an orientation control layer, a refractive index control layer, a protective layer, an antifouling layer, an adhesive layer, a back undercoat layer, and a back layer.
  • the amount used is not particularly limited as long as it is an amount necessary to achieve the purpose, but generally 0.0001 to 5% by mass is preferable with respect to the total mass of the layer to be added. 2% by mass is preferred.
  • the coating amount of the surfactant is 0.02 per lm 2 : LOOOmg g force S girlish, 0.05-200 mg force girlish! / ⁇ .
  • the cellulose mixed ester film is applied on the film! It is preferable that a slipping agent is contained in any one of the layers, and it is particularly preferred that the cellulose mixed ester film is contained in the outermost layer.
  • a slip agent include polyorganosiloxane as disclosed in JP-B-53-292; higher fatty acid amide as disclosed in US Pat. No. 4,275,146; JP 58-33541, British Patent Nos. 927 and 446 or JP 55
  • polyorganosiloxanes are generally known polyalkylsiloxanes such as polydimethylsiloxane polyjetylsiloxane and polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenol siloxane.
  • organopolysiloxanes having an alkyl group having 5 or more carbon atoms as shown in JP-B-53-292, JP-B-55-49294, JP-A-60-140341, and the like.
  • Alkyl polysiloxane having a polyoxyalkylene group at the side chain alkoxy, hydroxy, water Modified polysiloxanes such as organopolysiloxanes having silicon, carboxyl, and amide-containing mercapto groups can also be used. Further, as shown in block copolymers having siloxane units and JP-A-60-191240. A graft copolymer having a simple siloxane unit in the side chain can also be used. When the slip agent is applied, it can be used together with a binder capable of forming a film.
  • thermoplastic resins thermosetting resins, radiation-curable resins, reactive resins, mixtures thereof, and hydrophilic binders such as gelatin
  • hydrophilic binders such as gelatin
  • a sample whose static friction coefficient is preferably 0.25 or less is conditioned for 2 hours at a temperature of 25 ° C and a relative humidity of 60%, and then 5 mm ⁇ stainless steel using a HEIDON-10 static friction coefficient measuring machine. It is a value measured using V for a sphere, and the numerical value is small!
  • the average height of the protrusions on the surface is preferably 0.005 to 10 111 m, more preferably 0.01 to 5 m.
  • a preferable protrusion may be, for example, a spherical shape or an indefinite shape as long as it has an average height of the protrusion.
  • the matting agent used is not particularly limited in its composition, and may be inorganic or organic, or a mixture of two or more.
  • the matting agent may be either an inorganic compound or an organic compound, for example, fine powder of an inorganic substance such as normosulfate, manganese colloid, titanium dioxide, strontium barium sulfate, or silicon dioxide; Examples thereof include silicon dioxide (such as synthetic silica) obtained by gelation, and titanium dioxide (rutile type anatase type) produced by titanium slug and sulfuric acid.
  • the matting agent can be obtained by pulverizing an inorganic substance having a relatively large particle size, for example, 20 m or more, and then classifying (vibration filtering, air classification, etc.).
  • Examples of the matting agent include polytetrafluoroethylene, cellulose acetate, Examples include pulverized and classified products of organic polymer compounds such as polystyrene, polymethylmetatalylate, polypropylmetatalylate, polymethyltalarylate, polyethylene carbonate, and starch.
  • a high molecular compound synthesized by a suspension polymerization method a high molecular compound made spherical by a spray drying method or a dispersion method, or an inorganic compound can also be used.
  • the cellulose mixed ester film of the present invention can be provided with a transparent hard coat layer.
  • a transparent hard coat layer an actinic radiation curable resin layer or a thermosetting resin layer is preferably used.
  • the actinic radiation curable resin layer is a layer mainly composed of a resin (active radiation curable resin) that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays and electron beams. .
  • active radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may be used.
  • the ultraviolet curable resin examples include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, and an ultraviolet curable polyol acrylate resin. Or UV curable epoxy resin.
  • JP-A-2003-039014 a coated film is wound or gripped in the width direction and dried, and a coating solution containing an actinic ray-hardening substance is cured, so that high flatness is obtained. This invention is applicable to the present invention.
  • the cellulose mixed ester film of the present invention may be provided with an antireflection layer to form an antireflection film.
  • an antireflection layer to form an antireflection film.
  • Various configurations such as a single layer and a multilayer are known as the antireflection layer, but a multilayer structure generally has a structure in which a high refractive index layer and a low refractive index layer are alternately laminated.
  • Examples of the configuration include two layers of the high refractive index layer Z and the low refractive index layer in order from the transparent substrate side, or three layers with different refractive indexes, the medium refractive index layer (transparent substrate or Are higher in refractive index than the hard coat layer, lower in refractive index than the high refractive index layer !, layer) Z high refractive index layer Z low refractive index layer, etc.
  • a layer with an antireflection layer has also been proposed. Among them, from the viewpoint of durability, optical properties, cost and productivity, it is preferable to apply the high refractive index layer Z, the middle refractive index layer Z, and the low refractive index layer in this order on the substrate having the hard coat layer. It is a configuration.
  • the cellulose mixed ester film of the present invention may be provided with an antiglare layer. Since the antiglare layer has a structure having irregularities on the surface, the antiglare function is expressed by scattering light on the surface of the antiglare layer or inside the antiglare layer. It is. Preferred configurations for these layers are the embodiments shown below.
  • the antiglare layer is preferably a layer having a film thickness of 0.5 to 5. O / zm and containing one or more fine particles having an average particle size of 0.25 to 10 / ⁇ ⁇ .
  • the antiglare layer is composed of nitric acid silicate particles having an average particle size of 1.1 to 2 times the film thickness, and silicon dioxide fine particles having an average particle size of 0.005 m to 0.1 ⁇ m.
  • nitric acid silicate particles having an average particle size of 1.1 to 2 times the film thickness
  • silicon dioxide fine particles having an average particle size of 0.005 m to 0.1 ⁇ m.
  • a binder such as diacetyl cellulose, which can exhibit an antiglare function.
  • the “particles” include inorganic particles and organic particles.
  • the cellulose mixed ester film of the present invention may be subjected to anti-curl processing.
  • the anti-curl process gives the function of curling with the surface on which the curl is applied.
  • some surface coating is applied to one side of the transparent resin film. This function serves to prevent curling with the surface facing inward when different degrees and types of surface force are applied to both surfaces.
  • the anti-curl layer may be provided on the side of the substrate opposite to the side having the anti-glare layer or anti-reflection layer, or, for example, an easy-adhesion layer may be provided on one side of the transparent resin film.
  • a mode in which a force prevention process is applied to the opposite surface is also included.
  • the cellulose mixed ester film of the present invention has a functional layer described in detail on pages 32 to 45 of the Japan Institute of Invention Publication (Public Technical No. 20 01-1745, published on March 15, 2001, Japan Institute of Invention). It is preferable to compose each optical film in combination. Among them, preferred are application of a polarizing film (polarizing plate), application of an optical compensation layer (optical compensation sheet), and application of an antireflection layer (antireflection film).
  • a commercially available polarizing film is generally produced by immersing a stretched polymer in a solution of iodine or dichroic dye in a bath and allowing the iodine or dichroic dye to penetrate into the binder. It is. Iodine and dichroic dye in the polarizing film are in the binder. The polarizing performance is expressed by orienting at.
  • the dichroic dye preferably has a hydrophilic substituent (for example, sulfo, amide-containing hydroxyl).
  • a hydrophilic substituent for example, sulfo, amide-containing hydroxyl
  • the binder of the polarizing film either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used.
  • the water-soluble polymer for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polybulual alcohol, modified poly (polyethylene alcohol) described in paragraph No. [0022] of JP-A-8-338913 can be used.
  • Buyl alcohol is preferred, and gelatin, polybulu alcohol and modified polyvinyl alcohol are more preferred.
  • the binder thickness is preferably 1 m to 50 m, more preferably 2 ⁇ m to 50 ⁇ m, and further 5 ⁇ m to 30 ⁇ m.
  • the binder of the polarizing film may be crosslinked.
  • Crosslinkable boron compounds for example, boric acid and borax
  • Noinda amount of one cross-linking agent with respect to Roh Indah, 0.1 to 20 weight 0/0 are preferred.
  • the polarizing film is preferably dyed with iodine or a dichroic dye after the force for stretching the polarizing film (stretching method) or rubbing (rubbing method).
  • the stretching ratio is preferably 2.5 to 30.0 times, more preferably 3.0 to 10.0 times.
  • a parallel stretching method, or a method of stretching using a tenter projecting in an oblique direction as described in JP-A-2002-86554 can be used.
  • the cellulose mixed ester film after the saponification and a polarizing film prepared by stretching are bonded together to produce a polarizing plate.
  • the direction of laminating the polarizing film is preferably such that the casting axis direction of the cellulose mixed ester film and the stretching axis direction of the polarizing plate are 45 °.
  • the adhesive used when laminating the polarizing film and the cellulose mixed ester film is not particularly limited.
  • PVA resin modified PVA such as acetoacetyl group, sulfonic acid group, force oxyxyl group, oxyalkylene group, etc.
  • boron compound aqueous solution Among them, PVA-based resin is preferable.
  • the adhesive layer thickness is 0 after drying! ⁇ 10 ⁇ m is preferable, and 0.05 ⁇ m to 5 ⁇ m is particularly preferable.
  • the optically anisotropic layer is used to compensate for the liquid crystal compound in the liquid crystal cell in the black display of the liquid crystal display device.
  • An optically anisotropic layer is formed on the cellulose mixed ester film by forming an alignment film. It is formed by applying a layer.
  • An alignment film is provided on the surface-treated cellulose mixed ester film. This film has a function of defining the alignment direction of liquid crystalline molecules.
  • the alignment film plays the role, and is not necessarily an essential component of the present invention. That is, it is also possible to produce the polarizing plate of the present invention by transferring only the optically anisotropic layer on the alignment film in which the alignment state is fixed onto the polarizer.
  • the alignment film may be an organic compound (for example, a rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroup, or a Langmuir'Blodgett method (LB film). , ⁇ -tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.
  • an organic compound for example, a rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroup, or a Langmuir'Blodgett method (LB film).
  • LB film Langmuir'Blodgett method
  • a spin coating method, a dip coating method, a curtain coating method, an etching coating method, a rod coating method or a roll coating method is preferable, and a rod coating method is particularly preferable.
  • the film thickness after drying is preferably 0. m. Heating and drying can be performed at 20 ° C to 110 ° C. In order to form a sufficient crosslink, 60 ° C to 100 ° C is preferable, and 80 ° C to 100 ° C is particularly preferable.
  • the drying time is a force that can be carried out for 1 minute to 36 hours, preferably 1 minute to 30 minutes.
  • the pH is 4.5 to 5.5, and 5 is particularly preferable when the pH is preferably set to the optimum value for the cross-linking agent to be used.
  • the thickness of the alignment film thus obtained is preferably in the range of 0.1 to L0 m.
  • the liquid crystalline molecules of the optically anisotropic layer are aligned on the alignment film. Thereafter, if necessary, the alignment film polymer is reacted with the polyfunctional monomer contained in the optically anisotropic layer, or the alignment film polymer is crosslinked using a crosslinking agent.
  • the liquid crystalline molecules used in the optically anisotropic layer include rod-like liquid crystalline molecules and discotic liquid crystalline molecules.
  • the rod-like liquid crystal molecule and the disc-like liquid crystal molecule may be either a polymer liquid crystal or a low molecular liquid crystal, and further include those in which a low molecular liquid crystal is crosslinked and does not exhibit liquid crystallinity.
  • the rod-like liquid crystal molecules may be combined with a (liquid crystal) polymer.
  • rod-like liquid crystalline molecules are described in Chapters 4, 7 and 11 of the Chemistry of Liquid Crystal Chemistry (1994) Japan Chemistry Association, Chapter 142, and Chapter 142 of the Japan Society for the Promotion of Science. Is described in Chapter 3.
  • the birefringence of the rod-like liquid crystalline molecule is preferably in the range of 0.001 to 0.7.
  • the rod-like liquid crystalline molecules preferably have a polymerizable group in order to fix the alignment state.
  • the polymerizable group is preferably a radically polymerizable unsaturated group or a cationically polymerizable group.
  • the polymerizable groups described in paragraphs [0064] to [0086] of JP-A-2002-62427 are disclosed.
  • Group and a polymerizable liquid crystal compound are disclosed.
  • the discotic liquid crystalline molecule has a liquid crystalline property in which a linear alkyl group, an alkoxy group, and a substituted benzoyloxy group are radially substituted as a side chain of the mother nucleus with respect to the mother nucleus at the center of the molecule.
  • the compounds shown are also included.
  • the molecule or the assembly of molecules is preferably a compound having rotational symmetry and imparting a certain orientation.
  • the optically anisotropic layer formed from the discotic liquid crystalline molecules does not necessarily require that the compound finally contained in the optically anisotropic layer is a discotic liquid crystalline molecule, for example, a low molecular weight discotic liquid crystalline molecule.
  • discotic liquid crystalline molecules are described in JP-A-8-50206.
  • the polymerization of discotic liquid crystalline molecules is described in JP-A-8-27284.
  • a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline molecules.
  • the discotic core and the polymerizable group are preferably compounds that are bonded via a linking group. I can keep the state. Examples thereof include compounds described in paragraph numbers [0151] to [0168] of JP-A No. 2000-155216.
  • the optically anisotropic layer uses a plasticizer, a surfactant, a polymerizable monomer, etc. in combination with the liquid crystal molecules, and the uniformity of the coating film, the strength of the film, the orientation of the liquid crystal molecules, etc. Can be improved. It is preferable that it is compatible with liquid crystal molecules and has the ability to change the tilt angle of liquid crystal molecules without disturbing the orientation! /.
  • the optically anisotropic layer can be formed by applying a coating liquid containing liquid crystalline molecules and, if necessary, a polymerizable initiator described later and optional components on the alignment film.
  • the thickness of the optically anisotropic layer is preferably from 0.1 m to 20 ⁇ m, more preferably from 0.5 m to 15 ⁇ m: L m to: L0 m Most preferably.
  • the aligned liquid crystalline molecules can be fixed while maintaining the alignment state. It is preferable that the fixation is carried out by a polymerization reaction.
  • the polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred.
  • the optically anisotropic layer is formed by applying the coating liquid for the optically anisotropic layer as described above to the surface of the polarizing film.
  • the stress strain X cross-sectional area X elastic modulus
  • the polarizing plate according to the present invention is attached to a large liquid crystal display device, an image with high display quality can be displayed without causing problems such as light leakage.
  • the inclination angle of the polarizing film and the optical compensation layer is stretched so as to match the angle formed by the transmission axis of the two polarizing plates bonded to both sides of the liquid crystal cell constituting the LCD and the vertical or horizontal direction of the liquid crystal cell. It is preferable.
  • the normal inclination angle is 45 °. Recently, however, devices that are not necessarily 45 ° have been developed for transmissive, reflective, and transflective LCDs, and it is preferable that the stretching direction can be arbitrarily adjusted according to the design of the LCD.
  • the cellulose mixed ester film of the present invention can be used in various applications.
  • the cellulose mixed ester film of the present invention is effective when used as an optical compensation sheet for liquid crystal display devices.
  • the transmission axis of the polarizing element (described later) and the slow axis of the optical compensation sheet such as a cellulose mixed ester film are substantially parallel or perpendicular to each other. It is preferable to arrange in.
  • the arrangement of such a polarizing element and an optical compensation sheet is described in JP-A-10-48420.
  • the liquid crystal display device comprises a liquid crystal cell having a liquid crystal supported between two electrode substrates, two polarizing elements disposed on both sides thereof, and at least one sheet between the liquid crystal cell and the polarizing element. An optical compensation sheet is arranged.
  • the liquid crystal layer of the liquid crystal cell is usually formed by sealing liquid crystal in a space formed by sandwiching a spacer between two substrates.
  • the transparent electrode layer is formed on the substrate as a transparent film containing a conductive substance.
  • the liquid crystal cell may further be provided with a gas barrier layer, a hard coat layer, or an undercoat layer (used for adhesion of the transparent electrode layer). These layers are usually provided on the substrate.
  • the substrate of the liquid crystal cell generally has a thickness of 80 111 to 500 111.
  • the optical compensation sheet is a birefringent film for removing the coloration of the liquid crystal screen.
  • the cell mouth mixed ester film of the present invention itself can be used as an optical compensation sheet.
  • the function may be imparted as an antireflection layer, an antiglare layer, a ⁇ Z4 layer or a biaxially stretched cellulose mixed ester film.
  • the cellulose mixed ester film of the present invention may be used as an optical compensation sheet by superimposing a film showing birefringence (positive / negative relational force).
  • the thickness range of the optical compensation sheet is the same as the preferred thickness of the cellulose mixed ester film of the present invention described above.
  • the polarizing film of the polarizing element includes an iodine-based polarizing film and a dye-based polarizing film using a dichroic dye. Both polarizing films are generally produced using a polyvinyl alcohol film.
  • the protective film of the polarizing plate preferably has a thickness of 25 / ⁇ ⁇ to 350 / ⁇ ⁇ , more preferably 40 m to 200 m.
  • the liquid crystal display device may be provided with a surface treatment film.
  • the surface treatment film functions include hard coating, anti-fogging treatment and anti-glare. Treatment and antireflection treatment are included.
  • an optical compensation sheet in which an optically anisotropic layer containing a liquid crystal (particularly, discotic liquid crystalline molecules) is provided on a support (Japanese Patent Laid-Open No. 3-9325, the same document). 6-1 48429, 8-50206, 9-26572).
  • the cellulose mixed ester film of the present invention can also be used as a support for such an optical compensation sheet.
  • the optically anisotropic layer is preferably a layer containing discotic liquid crystal molecules that are tilted and aligned.
  • the angle formed by the disc surface of the discotic liquid crystal molecule and the support surface is preferably changed (hybridly aligned) in the depth direction of the optically anisotropic layer.
  • the optical axis of the discotic liquid crystalline molecule exists in the normal direction of the disk surface.
  • the discotic liquid crystalline molecule has birefringence in which the refractive index in the disc surface direction is larger than the refractive index in the normal direction of the disc surface.
  • the discotic liquid crystalline molecules may be aligned substantially horizontally with respect to the support surface.
  • the cellulose mixed ester film of the present invention is also effectively used as a support for an optical compensation sheet of a VA liquid crystal display device having a VA mode liquid crystal cell.
  • the optical compensation sheet used for the VA liquid crystal display device it is preferable that the direction in which the absolute value of the letter decision is minimized does not exist in the plane of the optical compensation sheet or in the normal direction.
  • the optical properties of the optical compensation sheet used in the VA liquid crystal display device are determined by the optical properties of the optically anisotropic layer, the optical properties of the support, and the arrangement of the optically anisotropic layer and the support. .
  • the in-plane lettering of the optical compensation sheet is in the range of 5 nm to 5 nm. Therefore, the absolute value of the in-plane letter decision of the two optical compensation sheets is preferably 0-5.
  • the in-plane letter decision of the optical compensation sheet is ⁇ ! It is preferable to be within the range of ⁇ lOnm.
  • the cellulose mixed ester film of the present invention has various VA so as to have such an optical characteristic range. What is necessary is just to provide the optical characteristic corresponding to a cell.
  • the range corresponds to the cell gap, and in the single-sheet cellulose mixed ester film, the Re force is 0 to 120 nm, preferably the Re force is 0 to: LOOnm, particularly 50 to 90 nm.
  • Rth is 160 to 300 nm, preferably Rth is 170 to 260 nm, particularly 180 to 240 nm.
  • the cellulose mixed ester film of the present invention should have optical characteristics corresponding to various VA cells.
  • the range corresponds to the cell gap, and in the double-type cellulose mixed ester film, Re is 20 to 80 nm, preferably Re force is 30 to 70 nm, and particularly 30 to 60 nm.
  • the Rth force is 0 to 200 nm, preferably Rth is 90 to 180 nm, and particularly 95 to 165 nm.
  • the cellulose mixed ester film of the present invention is also advantageously used as a support for an optical compensation sheet of an OC B type liquid crystal display device having an OCB mode liquid crystal cell or a HAN type liquid crystal display device having a HAN mode liquid crystal cell.
  • the optical compensation sheet used for the OCB-type liquid crystal display device or HAN-type liquid crystal display device has no direction in which the absolute value of retardation is minimum in the plane of the optical compensation sheet or in the normal direction. V is preferred.
  • the optical properties of the optical compensation sheet used in the OCB type liquid crystal display device and the HAN type liquid crystal display device are the optical properties of the optically anisotropic layer, the optical properties of the support, and the optically anisotropic layer and support. Determined by placement with the body.
  • the cellulose mixed ester film of the present invention should have optical properties corresponding to various OCB mode liquid crystal cells.
  • the range is Re force S20 nm to 100 nm, preferably Re is 30 nm to 80 nm, particularly 30 nm to 60 nm.
  • the Rth force is from 50 nm to 300 nm, preferably the Rth is from 16 Onm to 260 nm, particularly from 170 nm to 250 nm.
  • the cellulose mixed ester film of the present invention is also advantageously used as a support for an optical compensation sheet of an ASM type liquid crystal display device having a liquid crystal cell of ASM (Axially Symmetric Alligned Microcell) mode.
  • ASM mode liquid crystal cell is characterized in that the cell thickness is maintained by a position-adjustable resin spacer. Other properties are TN This is the same as the liquid crystal cell of the card.
  • ASM-mode liquid crystal cells and ASM-type liquid crystal display devices are described in a paper by Kume et al. (Kume et al., SID 98 Digest 1089 (1998)).
  • the cellulose mixed ester film of the present invention may be used as a support for an optical compensation sheet of a TN type liquid crystal display device having a TN mode liquid crystal cell.
  • TN mode liquid crystal cells and TN liquid crystal display devices have been well known for a long time.
  • the optical compensation sheet used in the TN type liquid crystal display device is described in JP-A-3-9325, JP-A-6-148429, JP-A-8-50206 and JP-A-9-26572.
  • the cellulose mixed ester of the present invention should have its optical properties within a desired range.
  • Cellulose mixed ester film was conditioned for 24 hours at 25 ° C and 60% relative humidity, and then using an automatic birefringence meter (KOBRA-21ADH: Oji Scientific Instruments), 25 ° C and relative humidity 60 %, The front letter value (Re) and the film thickness direction letter value (Rth) were calculated by the above method.
  • KOBRA-21ADH Oji Scientific Instruments
  • Humidity Rth fluctuation (% Z relative humidity%) [100 X ⁇ absolute value of difference between Rth (relative humidity 80%) and Rth (relative humidity 10%) ⁇ ZRth (relative humidity 60%)] Z70
  • the MD direction sampling 100 points were sampled at 1-m intervals in the longitudinal direction, and 1 cm square was sampled.
  • the sampling in the TD direction is 1cm square across the entire width of the film formation.
  • the samples were sampled at equal intervals.
  • the difference between the maximum value and the minimum value of each sample obtained was divided by each average value, and those expressed as percentages were designated as Re unevenness and Rth unevenness.
  • the thickness unevenness was also measured for each sample, and the difference between the maximum and minimum values in the MD and TD directions was divided by the average value, and the percentage was determined as the thickness unevenness.
  • a sample 40 mm X 80 mm was measured according to JIS K-6714 using a haze meter (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.) at 25 ° C and 60% relative humidity.
  • HGM-2DP haze meter
  • the film for which the glyphimi value was evaluated was visually observed and evaluated according to the following.
  • Sample 100mm X 100mm was saponified with 60 ° C, 2molZL sodium hydroxide and sodium hydroxide aqueous solution for 3 minutes with an automatic alkali saponification treatment device (manufactured by Shinto Kagaku Co., Ltd.) ° C, 0. Neutralized with OlmolZL dilute nitric acid for 4 minutes and washed with water for 4 minutes. Then, it was dried at 100 ° C for 3 minutes, and then naturally dried for 1 hour. The following visual standard and haze value before and after saponification treatment were evaluated for alkali hydrolyzability (25 ° C ⁇ relative humidity 60 %).
  • Sample 35mm X 3mm was conditioned for 24 hours at 25%, 55% and 85% relative humidity with a curl humidity chamber (HEIDON (No. YG53-168), manufactured by Shinto Kagaku Co., Ltd.), and the radius of curvature was curled. Measured with a plate. Wet curl was measured after standing for 30 minutes in water at a water temperature of 25 ° C.
  • HEIDON No. YG53-168
  • a 7 mm X 35 mm sample was measured by the Karl Fischer method using a moisture analyzer and a sample drying apparatus (CA-03, VA-05, both manufactured by Mitsubishi Ryogaku Co., Ltd.). It was calculated by dividing the amount of water (g) by the sample mass (g).
  • Specimen 30mm X 120mm is aged at 90 ° C 'relative humidity 5% for 24 hours and 120 hours, and automatic pin gauge (manufactured by Shinto Kagaku Co., Ltd.) is used to open 6mm ⁇ holes at both ends at intervals of 100mm.
  • the original size (L1) was measured to the minimum scale lZlOOOmm.
  • the dimension (L2) of the punch interval was measured by heat treatment for 24 hours and 120 hours at 90 ° C and 5% relative humidity.
  • the thermal contraction rate was determined by ⁇ (L1 -L2) / L1 ⁇ X 100.
  • Sample 70mm ⁇ was conditioned at 25 ° C 'relative humidity 90% and 40 ° C' relative humidity 90% for 24 hours respectively, and using a moisture permeation tester (KK-709007, manufactured by Toyo Seiki Co., Ltd.), JIS Z According to -020 8, the amount of water per unit area (g / m 2 ) was calculated. And moisture permeability was calculated
  • Reflected light was applied in the range of the total width X lm of the sample, and foreign matter in the film was visually detected. Then, the foreign matter (lint) was confirmed and evaluated with a polarizing microscope.
  • Two polarizing plates were placed in an orthogonal state (crossed Nicols) to block the transmitted light, and each sample was placed between two polarizing plates.
  • the polarizing plate used was a glass protective plate. Light was irradiated from one side, and the number of bright spots corresponding to the diameter per lcm 2 was counted with an optical microscope (50x) from the other side.
  • Example 20 mg of sample was placed in the DSC measurement pan. This was heated in a nitrogen stream to 30 ° C to 250 ° C in 10 ° CZ minutes, and then cooled to 30 ° C in 10 ° CZ minutes. After this, the temperature was raised again from 30 ° C to 250 ° C, and the temperature at which the baseline began to deviate from the low temperature side force was defined as Tg.
  • cellulose mixed ester As cellulose mixed ester, cellulose mixed ester A (acetyl substitution degree 1.00, propiole substitution degree 1.90, total substitution degree 2.90, viscosity average polymerization degree 180, water content 0.1 mass%, in dichloromethane solution A 6% by weight viscosity of 140 mPa's, an average particle size of 1.4 mm and a standard deviation of 0.4 mm was used.
  • Cellulose mixed ester A has a residual acetic acid content of 0.05 mass%, a residual propionic acid content of 0.03 mass%, a Ca content of 51 ppm, an Mg content of 15 ppm, and an Fe content of 0.45 ppm. In addition, it contained 0.16 ppm of sulfur as sulfate group.
  • the substitution degree of the 6-position acetyl group was 0.31, and the substitution degree of the 6-position propiol group was 0.66, which was 33.5% of the total acetyl group.
  • the weight average molecular weight Z number average molecular weight ratio was 2.7.
  • the cellulose index A has a yellow index of 0.86, a haze of 0.1, a transparency of 93.9%, and a Tg (glass transition temperature; measured by DSC) of 125 ° C. there were.
  • This cellulose mixed ester A was synthesized using cellulose collected from cotton linter as a raw material.
  • This cellulose mixed ester A was dried at 105 ° C for 5 hours to adjust the water content to 0.07% by mass, and then 2— (2,1hydroxy-1,3,5,1 t-amyl) monobenzotriazole (TINUVIN238), 2-hydroxy-l 4-n-dodecoxy benzophenone (Seethorpe 103), 2-ethyl hexyl 2 cyano 3, 3, 1 diphenyl-luke relay HUVNUL N 539) and 2 (2, 1 hydroxy 1, 3, 5, 1 di tert-amino (Fuel) 5-Black benzotriazole was added in an amount of 0.3% by mass with respect to cellulose mixed ester A, and stabilizers and fine particles were further added according to Table 1.
  • the hexa ⁇ cetyl sorbitol was 5 mass 0/0 ⁇ Ka ⁇ the cellulose mixed ester to. These were mixed and put into a hopper of a twin-screw kneading extruder, and further kneaded at 150 to 200 ° C. with a screw speed of 300 rpm and a residence time of 40 seconds to be melted. Furthermore, in a 50 ° C water bath, the die force was also extruded into a strand with a diameter of 3 mm in 200 kgZ time, soaked for 1 minute (strand solidification), then passed through 10 ° C water for 30 seconds to reduce the temperature and length. A pellet was obtained by cutting to 5 mm. The obtained pellets of cellulose mixed ester A were dried at 105 ° C. for 120 minutes, and then packed in a moisture-proof bag having aluminum laminate film strength and stored.
  • the cellulose mixed ester formed into a cylindrical pellet having a diameter of 3 mm and a length of 5 mm was dried with a vacuum dryer at 110 ° C. for 3 hours. This was put into a hopper, melted at 215 ° C, and then filtered under pressure at a speed of 0.1 lmZ with lOMPa using a sintered metal filter having a diameter of 5 m. It was confirmed that the obtained filtrate had a transparent and homogeneous composition.
  • Tg—10 ° C 107 ° C
  • Tg—10 ° C 107 ° C
  • Tg—10 ° C upstream melting temperature
  • Tg—7 ° C T die temperature
  • T—die and casting drum distance 8cm
  • solidification speed is 30 ° CZ seconds
  • casting drum temperature is first roll (upstream) (Tg—10) ° C and second roll ( Upstream (Tg 11) ° C and the third roll (upstream) (Tg-12) ° C
  • the cooling rate was 15 ° CZ seconds.
  • the melt was melt extruded over 10 minutes.
  • each level electrostatic application method (1 OkV wire was placed 10 cm from the point where the melt was cast on the casting drum) was used.
  • the solidified melt was peeled off, and taken up at a take-up tension of 6 kg / cm 2 via a roll.
  • the both ends were thickened with a thickness of 10 mm and a height of 50 m (knurling), and then wound.
  • the width was 1.5m, and 500m was rolled up for 30mZ.
  • the film thickness was prepared according to Table 1. [0236] (4) Evaluation
  • the evaluation of die streaks generated in the form of streaks in the casting direction was carried out in accordance with the following, by visually observing the film under a reflected light source.
  • D Dice lines were noticeably generated on the entire surface.
  • Dan-shaped unevenness (danmura) observed in a direction perpendicular to the casting direction was visually observed under a reflected light source and evaluated according to the following.
  • the resulting sample film 20cm x 30cm was conditioned at 25 ° C and relative humidity 60% for 3 hours, and then the casting drum surface was melt bonded to the glass plate with double-sided tape. X 10cm, lkg load, 10 round trips. Then look at the black paper surface? Observation was made and powdery foreign matters were judged according to the following.
  • the resulting sample film 5cm x 5cm was conditioned at 25 ° C and relative humidity 80% for 3 hours, and then the casting drum surface and the air surface were overlaid and sealed in a moisture-proof bag. A 10 kg load was applied to the entire film. Furthermore, let it age for 3 days at 60 ° C. 2 After returning to 5 ° C and relative humidity of 60%, the adhesion marks between the films were visually confirmed after 2 hours, and judged according to the following.
  • the obtained sample film 20 cm ⁇ 30 cm was heated at 150 ° C. for 24 hours, then returned to 25 ° C. and the relative humidity 60%, and after 2 hours, the film surface was visually confirmed and judged according to the following.
  • the cellulose mixed ester sample was first saponified as follows. That is, saponification was carried out for 1 minute using a saponification solution prepared by dissolving KOH to 1.5 molZL and then adjusting the temperature to 60 ° C. Thereafter, the mixture was washed with water for 2 minutes, neutralized with 0.1 Imol ZL of sulfuric acid for 20 seconds, and further washed with water for 2 minutes. Thereafter, a drying air of 110 ° C was sent at a wind speed of 15 mZ seconds and dried in 5 minutes. Next, the polarizing film was prepared by pasting the queried film on both sides of the polarizing film. Bonding was performed so that the stretching direction of the polarizing film and the casting direction of the cellulose mixed ester coincided.
  • the polarizing film was prepared in accordance with Example 1 of JP-A-2001-141926 by giving a peripheral speed difference between two pairs of nip rolls and stretching in the longitudinal direction to prepare a polarizing film having a thickness of 20 m. Two pairs of polarizing plates obtained in this way were prepared, arranged so that the polarizing films intersected each other, and then heated at 90 ° C. (20 days). Then, after aging for 3 hours under the conditions of 25 ° C. and 60% relative humidity, the degree of polarization reduction (%) of the orthogonal polarizing plates was evaluated.
  • the physical properties of the unstretched cellulose mixed ester film thus obtained were measured by the above-mentioned method and listed in Table 1.
  • the control sample 1-1 containing no UV absorber and fine particles had a large Kishimi value, a small Ra, and a dice line, dangling, scratched, adhesiveness and heat resistance that were extremely poor.
  • Comparative Sample 1-2 containing only the stabilizer was improved in the weather resistance, but had a problem of die streak, dangling, scratching, and adhesion.
  • Comparative Sample 1-3 which contains only fine particles, is improved in crease, but is inferior to die lines, dangling, scratches, poor adhesion, in addition to fine particles falling off, surface change, and heat resistance. there were.
  • the microparticles of the present invention and the samples 1-4 to 1-9 of the present invention containing the microparticles have small Kishimi values and moderately imparted Ra, and they have die lines, dangling, haze, transmittance, and scratches.
  • the fine powder powder, adhesion, surface change and heat resistance were all satisfied.
  • die stripes, danmura and fine particle fall are surprising effects that cannot be predicted by conventional knowledge, and the unexpected effects of the present invention have been confirmed.
  • Comparative Samples 1-10 to 1-13 which contain fine particles and a stabilizer but are outside the scope of the present invention, are die lines, danmura, haze, transmittance, scratches, fine particle powder. It was not possible to satisfy all of the drop, adhesion, surface change and thermal weather resistance. Sarayoko, Comparative Samples 1-14 and 1-15 whose downstream melt temperature is outside the scope of the present invention are also used for die lines, danmura, haze, transmittance, scratches, fine particle falling off, adhesion, surface change and It was impossible to satisfy all of the heat resistance.
  • Comparative Sample 1-15 melt-formed at 245 ° C., which is the melting temperature listed in the examples of Patent Document 2 (Japanese Patent Laid-Open No. 2000-352620), contains a stabilizer and fine particles. Nevertheless, the haze with a large kishimi value was large, and the transmittance, adhesiveness, and surface condition were poor.
  • Comparative Sample 116 which has a large average primary particle size outside the scope of the present invention, has a large secondary particle size, resulting in increased haze, reduced transmittance, worsening of scratches, falling off of fine particles, etc. It was a problem.
  • Samples 14 to 19 of the present invention have a residual acetic acid content of less than 0.01% by mass, a Ca content of less than 0.05% by mass, and a Mg content of less than 0.01% by mass. there were.
  • the film's vertical and horizontal average heat shrinkage 80 ° CZ, relative humidity 90%, Z48 hours was 0.04%, and a film that hardly caused heat shrinkage was obtained.
  • Samples 1-4 to 1-9 of the present invention also have a light weather resistance of 0.2% or less, confirming that the control sample 11 is superior to 0.15. .
  • the sample 14 has a slope width of 19.4 nm, a limit wavelength of 389.4 nm, an absorption edge of 376.5 nm, and an absorption at 380 nm of 1.4%.
  • Axial misalignment (molecular orientation axis) is 0.15 °
  • elastic modulus is 2.95 GPa in the longitudinal direction
  • tensile strength is 119 MPa in the longitudinal direction
  • elongation is 66 in the longitudinal direction.
  • the width direction was 64%
  • the alkali hydrolyzability was A
  • the curl value was 0.3 at a relative humidity of 25% and 1.0 at wet.
  • the moisture content was 1.7% by mass
  • the heat shrinkage was 0.05% in the longitudinal direction and 0.07% in the width direction.
  • the foreign object was lint less than 5 Zm.
  • the bright spot was less than 10 mm less than 0.02 mm, less than Z3m, and less than 4 mm from 0.02 to 0.05 mm, and less than 0.05 mm. These had excellent properties for optical applications. Further, no adhesion after application was observed, and the moisture permeability was good.
  • the other samples of the present invention also showed almost the same characteristic values as Sample 1-4.
  • Cellulose mixed ester A in sample 14 of the present invention of Example 1 was mixed with cellulose mixed ester B (acetyl substitution degree 1.40, propiol substitution degree 1.50, total substitution degree 2.90, viscosity average polymerization degree 130.
  • Example 1 except that the water content was changed to 0.1% by weight, 6% by weight in dichloromethane solution, 52 mPa's viscosity, average particle size 1.5 mm and standard deviation 0.5 mm.
  • Sample 2-1 of the present invention was prepared in exactly the same manner as Sample 14.
  • cellulose mixed ester A was mixed with cellulose mixed ester C (acetyl substitution degree 1.80, propionyl substitution degree 1.05, total substitution degree 2.85, viscosity average polymerization degree 250, water content 0.2 mass%, dichloromethane solution.
  • Sample 2 of the present invention in exactly the same manner as Sample 14 of Example 1 except that the powder was changed to 6% by weight of a viscosity of 125 mPa's, an average particle size of 1.4 mm and a standard deviation of 0.5 mm. — 2 was made. The results are shown in Table 1.
  • Sample 2-1 of the present invention has a slightly lower degree of polymerization. Average of fine particles in film. Secondary particle size is small. Kishimi value is small. Ra is small. Good die streak is good. It was excellent in all of the chemical properties (Re unevenness, Rth unevenness), die streak, damp unevenness, haze, transmittance, scratches, fine particle falling off, adhesion, surface change, and heat resistance.
  • Sample 2-2 of the present invention is a cellulose mixed ester having a small propiol group, and has a good force die squeeze, optical characteristics (Re unevenness, Rth unevenness), dice stripes, dam unevenness, and haze with small kishimi values.
  • Example 1 Sample 1-4 of the present invention was subjected to an alkali cane treatment under the following conditions. Immerse the film in a solution of 3molZL NaOH aqueous solution at 60 ° C for 2 minutes, then wash it with 25 ° C water for 30 seconds, and then use 0.05 molZL sulfuric acid aqueous solution (25 ° C) for 1 minute. Treated and washed again with 25 ° C water. When the contact angle (relative to pure water) of the obtained alkali saponified film was measured, it was 28 ° and the wettability was good. The contact angle before the alkaline saponification treatment is 62 °, and it can be seen that the sample of the present invention has an excellent surface treatment property.
  • Cellulose mixed ester film sample 14 of the present invention and N, ⁇ ′, ⁇ , tri-m-tolyl-1, 3, 5-triazine-2, 4, 6 triamine prepared by a separate solution casting method Of cellulose triacetate (Re is 60 nm, Rth is 200 nm, film thickness is 80 ⁇ m))
  • the method was carried out. That is, after dissolving KOH to 1.5 molZL and adjusting the temperature to 60 ° C, it was used as the Kenyaku solution. Then, 10 g / m 2 was applied onto a cellulose mixed ester film at 60 ° C. and saponified for 1 minute. Thereafter, hot water at 50 ° C.
  • the obtained saponified film of the cellulose mixed ester film of the present invention was designated as Sample 41, and the saponified film of the cellulose triacetate film was designated as Sample 4-2.
  • Example 1 of Japanese Patent Laid-Open No. 2001-141926 the peripheral speed difference between two pairs of rolls A polarizing layer having a thickness of 20 m was prepared.
  • the polarizing layer thus obtained was sandwiched between the Ken-treated cellulose mixed ester film sample 4-1 and the stretched saponified cellulose triacetate film sample 4-2, and then PVA (manufactured by Kuraray Co., Ltd.). , PVA-117H) 3% aqueous solution was used as an adhesive, and the polarizing axis and the longitudinal direction of cellulose mixed ester film samples 41 and 42 were laminated to 90 °.
  • the cellulose mixed ester film sample 41 of the present invention and the stretched and saponified cellulose triacetate film sample 4-2 are shown in FIGS. 2 to 9 of JP-A-2000-154261, as shown in FIGS.
  • the saponified cellulose mixed ester film 41 of the present invention was used, and this was used as JP-A-2002-62431.
  • the color change was evaluated on a 10-point scale (the larger the change, the greater the change), and a mark of 2 was obtained. Good performance was obtained by carrying out the present invention.
  • the cellulose mixed ester film of the present invention was stretched according to Example 47 of the Technical Journal of the Invention Association (Public Technical Number 2001 — 1745, published on March 15, 2001, Invention Association).
  • Example 47 of the Technical Journal of the Invention Association (Public Technical Number 2001 — 1745, published on March 15, 2001, Invention Association).
  • the cellulose mixed ester film 1-5 of the present invention produced in Example 1 was used in place of the senorelose triacetate film sample 1301 in Example f row 13 described in JP 2002-265636 A.
  • a bend-aligned liquid crystal cell was prepared in the same manner as in Example 13 described in JP-A-2002-265636 by preparing an optically anisotropic layer and a polarizing plate sample. The obtained liquid crystal cell had excellent viewing angle characteristics.
  • Example 1 Using the cellulose mixed ester film sample 1-8 of the present invention produced in Example 1, this film was used in place of the cellulose triacetate film sample 1401 in Example 14 described in JP-A-2002-265636.
  • a vertical liquid crystal cell was produced in the same manner as in Example 14 described in JP-A-2002-265636 by producing an optically anisotropic layer and a polarizing plate sample. The obtained liquid crystal cell had excellent viewing angle characteristics.
  • the polarizing plate produced in Example 4 of the present invention is such that the viewing side polarizing plate has a 26 "wide size and the polarizer has a long absorption axis, and the backlight side polarizing plate has a short polarizing axis.
  • the VA mode LCD TV manufactured by Sony Corporation, KDL—L26RX2
  • KDL—L26RX2 was stripped of the front and back polarizing plates and retardation plate, and the sample of the present invention was applied to the front and back sides.
  • a liquid crystal display device was fabricated by pasting together the polarizing plates prepared in 4-3, and after holding the polarizing plate, held at 50 ° C and 5 kgZcm 2 for 20 minutes and adhered.
  • the polarizing plate was arranged such that the absorption axis of the polarizing plate was in the horizontal direction of the panel, the absorption axis of the polarizing plate on the backlight side was in the vertical direction of the panel, and the adhesive surface was on the liquid crystal cell side.
  • the viewing angle (range of contrast ratio of 10 or more) was calculated from the luminance measurement of black display and white display using a measuring machine (ELDIM, EZ-Contrast 160D). . Regardless of which polarizing plate is used, the polar angle is 80 ° or better in all directions. Viewing angle characteristics were obtained. In addition, light leakage and polarizing plate peeling tests were carried out in a durability test, and it was confirmed that there were no problems.
  • the durability test conditions are as follows.
  • the sample of the present invention is prepared on an optically anisotropic film exhibiting desired optical characteristics, and the following liquid crystal mode sales monitor is peeled off the phase difference film of the television and the phase difference film of the present invention is pasted.
  • the viewing angle characteristics were investigated, excellent wide viewing angle characteristics and colors were obtained, and it was confirmed that the cellulose mixed ester of the present invention was useful.
  • Both the viewing-side polarizing plate and the backlight-side polarizing plate were punched into a rectangle so that the absorption axis was 45 ° long with respect to the long side of the polarizing plate after punching at a size of 17 ".
  • TN mode liquid crystal Remove the polarizing plates and retardation plates on the front and back of the monitor (Samsson, SyncMaster 172X), and attach the polarizing plate made of the cellulose mixed ester of the present invention on the front and back sides in combination to attach the liquid crystal display device.
  • the polarizing plate After applying the polarizing plate, it was held for 20 minutes at 50 ° C, 5 kgZcm 2 and adhered, with the optically anisotropic layer of the polarizing plate facing the cell substrate and the rubbing direction of the liquid crystal cell. Arrange it so that the rubbing direction of the optically anisotropic layer facing it is antiparallel.
  • the polarizing plate of the present invention is such that the viewing side polarizing plate is 32 "wide and the absorption axis of the polarizer is long, and the backlight side polarizing plate is rectangular so that the absorption axis of the polarizer is short.
  • IPS mode LCD TV (W32—L5000, manufactured by Hitachi, Ltd.)
  • the front and back polarizing plates and retardation plates were peeled off, and the cellulose mixed ester force of the present invention was prepared on the front and back sides.
  • the plates were pasted together to make a liquid crystal display device. It was held for 20 minutes at 5 ° C / cm 2 and adhered.
  • the absorption axis of the polarizing plate on the viewing side is in the horizontal direction of the panel
  • the absorption axis of the polarizing plate on the backlight side is in the vertical direction of the panel
  • the adhesive layer surface is on the liquid crystal cell side.
  • Average secondary particle size in film is small Small Kishimi value is small and Ra is small Dice, Danmura, Haze, Transmittance, Scratched, Fine particles Powder fall, Adhesion, Surface change and Thermal resistance
  • the optical characteristics (Re, Rth, Re unevenness, Rth unevenness) were all excellent.
  • the load at the time of stripping was about 1Z2 for Sample 1-4, where no stripping agent was added, and the film formation stability was further improved. Therefore, it has been confirmed that it is effective to contain a fluorine-based compound, particularly a polymerized product, as a release agent.
  • the synthetic cellulose mixed ester listed in Table 2 was blown and dried at 120 ° C for 3 hours to contain water. The rate was 0.1% by mass. To this, the plasticizer described in Table 2 and SiO particles (Aerosil
  • UV absorber 2 4-bis one (n- Okuchiruchio) over 6- (4 primary hydroxy one 3, 5-di one tert- Buchiruanirino) one 1, 3, 5-triazine 0.8 mass 0/0 ,
  • Another UV absorber 2 (2, -hydroxy-3,5, -di-tert-butylphenol) -5-chloro benzotriazole 0.25% by weight, and a stabilizer Tris 1,3 G tert-butyl 4-hydroxyphenol) isocyanurate 0.15 parts by mass, tetrakis (2,4 di-t-butylphenol) 1,4,4 Bibi-range phosphite 0.15 mass Parts, bis [(1, 2, 2, 6, 6, monopentamethyl mono-4-piberidyl) 2- (3,5-di-tert-butyl 4-hydroxybenzyl) 2-n-butyl malonate 0.15 parts by mass The mixture consisting of (parts by weight are parts by weight
  • the twin-screw kneading extruder was provided with a vacuum vent and evacuated (set to 0.3 atm). It was extruded into a strand with a diameter of 3 mm in a water bath and cut to a length of 5 mm.
  • the cellulose mixed ester pellets prepared by the above method were dried in a 100 ° C vacuum dryer for 3 hours. Put this in a hopper adjusted to (Tg-10) ° C, and use a single screw extruder with a screw with a compression ratio of 3.0, upstream supply (195 ° C), intermediate compression The cellulose mixed ester was melt-extruded in a part (210 ° C) and a downstream metering part (228 ° C). Next, the melted cellulose mixed ester was passed through a gear pump to remove the pulsation of the extruder, filtered through a 3 m filter, and cast onto a cast drum through a 230 ° C die.
  • the obtained cellulose mixed ester film was prepared by the following immersion method. That is, a 2.5 mol ZL NaOH aqueous solution was used as an incubation solution. The temperature was adjusted to 60 ° C., and the cellulose mixed ester film was immersed for 2 minutes. Thereafter, it was immersed in a 0.05 mol ZL sulfuric acid aqueous solution for 30 seconds and washed with water.
  • Example 1 of Japanese Patent Laid-Open No. 2001-141926 a circumferential speed difference was given between two pairs of nip rolls and stretched in the longitudinal direction to prepare a polarizing layer having a thickness of 20 m.
  • Polarizing plate B Cellulose mixed ester film Z Polarizing layer Z Cellulose mixed ester vinyl
  • a polarizing plate on one side on the viewer side is used. It peeled off and the said polarizing plate A or B was affixed instead using the adhesive.
  • a liquid crystal display device was prepared by arranging the transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side to be orthogonal to each other. The obtained liquid crystal display device was observed for light leakage, color unevenness and in-plane uniformity generated in a black display state.
  • the cellulose mixed ester film of the present invention was very excellent with no color tone change.
  • the cellulose mixed ester film of the present invention is disclosed in the Technical Report of the Society of Inventions (Public Technical Number 2001) — A low reflection film was produced according to Example 47 of 1745, published on March 15, 2001, Invention Association), and had good optical performance.
  • the cell mouth mixed ester film of the present invention was coated with a liquid crystal layer according to Example 1 of JP-A-11 316378, and a good optical compensation film was obtained.
  • the manufacturing method of the present invention die stripes, dangling irregularities, thickness irregularities, and irregularities in optical characteristics are reduced. It is possible to provide a cellulose mixed ester film that is greatly reduced. In addition, scratches caused by rubbing between the film surfaces during handling can be greatly reduced, and all of haze, transmittance, fine powder fall off, adhesion, surface condition, and heat resistance are excellent. Furthermore, if the cellulose mixed ester film of the present invention is incorporated into a liquid crystal display device, it is possible to greatly suppress changes in visibility due to display unevenness and humidity, which have been problematic in the past. Therefore, the cellulose mixed ester film of the present invention has high industrial applicability.

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Abstract

A cellulose mixed ester film having a thickness of 20-200 μm is obtained by melting a composition at 180-230˚C and extruding the molten composition from a die for film formation. The composition contains 100 parts by mass of a cellulose mixed ester having a substitution degree within a certain range, 0.005-1.0 part by mass of fine particles having an average primary particle size of 0.005-2 μm, and 0.01-3 parts by mass of one or more stabilizers selected from the group consisting of phenol stabilizers, phosphorus stabilizers, thioether stabilizers, tin stabilizers and amine stabilizers. By using such a cellulose mixed ester film in a liquid crystal display, display unevenness and visibility change due to humidity can be improved.

Description

明 細 書  Specification
セルロース混合エステルフィルムおよびその製造方法、偏光板、光学補 償フィルム、反射防止フィルム、並びに液晶表示装置  Cellulose mixed ester film and production method thereof, polarizing plate, optical compensation film, antireflection film, and liquid crystal display device
技術分野  Technical field
[0001] 本発明は、溶融製膜によるセルロース混合エステルフィルムの製造方法に関する。  The present invention relates to a method for producing a cellulose mixed ester film by melt film formation.
また、本発明は光学特性に優れたセルロース混合エステルフィルムに関する。さらに 、本発明は当該セルロース混合エステルフィルムを用いた偏光板、光学補償フィルム 、反射防止フィルムおよび液晶表示装置にも関する。  The present invention also relates to a cellulose mixed ester film excellent in optical properties. Furthermore, the present invention also relates to a polarizing plate, an optical compensation film, an antireflection film and a liquid crystal display device using the cellulose mixed ester film.
背景技術  Background art
[0002] 従来から、液晶画像表示装置に使用されるセルロース混合エステルフィルムを製造 する際に、ジクロロメタンのような塩素系有機溶剤にセルロース混合エステルを溶解し 、これを基材上に流延、乾燥して製膜する溶液流延法が主に実施されている。塩素 系有機溶剤の中でもジクロロメタンは、セルロースァシレートの良溶媒であるとともに、 沸点が低く (約 40°C)、製膜工程や乾燥工程において乾燥させ易いという利点を有 することから好ましく使用されて 、る。  Conventionally, when producing a cellulose mixed ester film used in a liquid crystal image display device, the cellulose mixed ester is dissolved in a chlorinated organic solvent such as dichloromethane, and this is cast on a substrate and dried. Then, a solution casting method for forming a film is mainly carried out. Among chlorinated organic solvents, dichloromethane is preferably used because it is a good solvent for cellulose acylate, has a low boiling point (about 40 ° C), and is easy to dry in the film forming process and the drying process. And
一方、近年では環境保全の観点から、塩素系有機溶媒を始めとする有機溶媒の排 出を抑えることが強く求められるようになつている。このため、より厳密なクローズドシス テムを採用して系から有機溶媒が漏れ出さないように努めたり、製膜工程力も有機溶 媒が漏れても外気に出す前にガス吸収塔を通して有機溶媒を吸着させたり、火力に より燃焼させたり、電子線ビームにより分解させたりするなどの処理を行って、殆ど有 機溶媒を排出することがないように対策が講じられている。し力しながら、これらの対 策を行っても完全な非排出には至らないため、さらなる改良が必要とされていた。  On the other hand, in recent years, from the viewpoint of environmental conservation, there is a strong demand to suppress the discharge of organic solvents including chlorinated organic solvents. For this reason, a more rigorous closed system is adopted to prevent the organic solvent from leaking out of the system, and even when the organic solvent leaks, the organic solvent is adsorbed through the gas absorption tower before being released to the outside air. Measures are taken so that almost no organic solvent is discharged by processing such as heating, burning with thermal power, or decomposing with an electron beam. However, further improvement was needed because these measures did not lead to complete non-emissions.
[0003] そこで、有機溶剤を用いな!/、製膜法として、セルロース混合エステルを溶融製膜す る方法が開発された (例えば、特許文献 1および 2参照)。この方法は、セルロースェ ステルのエステル基の炭素鎖を長くすることで融点を下げ溶融製膜しやすくしたもの である。具体的には、従来力 用いられていたセルロースアセテートを、セルロースプ 口ピオネートやセルロースプチレート等に変えることで溶融製膜を可能にしている。ま た、従来のセルロースエステルフィルムを基板として位相差フィルムを作製すると、湿 度変化に伴い視野特性が変動しに《なるという利点も得られるものであった。 [0003] Therefore, a method of melt-forming a cellulose mixed ester has been developed as a film forming method without using an organic solvent (see, for example, Patent Documents 1 and 2). In this method, the melting point is lowered to facilitate film formation by extending the carbon chain of the ester group of cellulose ester. Specifically, melt film formation is made possible by changing cellulose acetate, which has been used conventionally, to cellulose pionate, cellulose petitate, or the like. Ma In addition, when a retardation film was produced using a conventional cellulose ester film as a substrate, there was also an advantage that the visual field characteristics fluctuated with changes in humidity.
特許文献 1：特表平 6— 501040号公報および  Patent Document 1: Japanese Patent Publication No. 6-501040 and
特許文献 2：特開 2000— 352620号公報  Patent Document 2: Japanese Patent Laid-Open No. 2000-352620
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0004] し力しながら、これらの方法で溶融製膜したものを実施例などにしたがって実施しよ うとする場合に、セルロース混合エステルフィルムの着色防止、フィルムの搬送性、あ るいは傷付き難さなどを全て満足させることは困難である事が判った。また、特許文 献 1および 2には微粒子と劣化防止剤を添カ卩してセルロース混合エステルフィルムの 耐候性を付与することが記載されているが、他の性能との両立が困難であることが、 本発明者により明らかとなった。特に特許文献 2の実施例に従って作製したフィルム は、面状の悪化が著しく悪ぐフィルム搬送時の傷付きと着色および経時での耐候性 悪化、および微粒子の脱落を伴うものであり、その改良は急務であった。  [0004] However, when it is attempted to carry out melt film formation by these methods according to the examples, etc., it is possible to prevent the color mixing of the cellulose mixed ester film, the transportability of the film, or the scratch resistance. It turned out that it was difficult to satisfy all of them. In addition, Patent Documents 1 and 2 describe that the weather resistance of the cellulose mixed ester film is imparted by adding fine particles and a deterioration inhibitor, but it is difficult to achieve compatibility with other performances. However, the present inventors have made it clear. In particular, the film produced according to the example of Patent Document 2 is accompanied by scratches and coloring during film transportation, deterioration in weather resistance over time, and dropout of fine particles. There was an urgent need.
[0005] 具体的には、上述の特許文献によるセルロース混合エステルを用いて偏光板を作 製し液晶表示装置に組み込むと、面状不良や著しいキズによる異物ムラが発生して しまう問題や、着色やヘイズアップによる輝度低下の問題などがあり、その改良が必 要なレベルであった。このような故障は、偏光板を 15インチ以上の大型液晶表示板 に組み込んだ際に特に顕著であり、大きな課題であった。これらの問題は、溶融混練 機力 溶融物を T—ダイ (スリット）を通してキャスティングドラム上に押出し冷却固化し て製膜して巻き取り、さらに加工する過程において、セルロース混合エステルフィルム の搬送性が悪ぐセルロース混合エステルフィルム面同士で傷付けあうことが要因で ある。また、溶融製膜時の高温により着色が強くなることも要因であると推測される。  [0005] Specifically, when a polarizing plate is produced using the cellulose mixed ester described in the above-mentioned patent document and incorporated in a liquid crystal display device, the problem of foreign matter unevenness due to surface defects or significant scratches, There was a problem of brightness decrease due to haze up and so on, and it was a level that needed improvement. Such a failure was particularly prominent when a polarizing plate was incorporated into a large liquid crystal display panel of 15 inches or more, and was a big problem. These problems are caused by melt-kneading, mechanical strength, melt-extruding the molten material onto a casting drum through a T-die (slit), solidifying it, forming a film, winding it, and further processing the cellulose mixed ester film during the process. The reason is that the cellulose mixed ester film surfaces are damaged. In addition, it is presumed that the coloration becomes stronger due to the high temperature during melt film formation.
[0006] これらの従来技術の課題に鑑みて、本発明は、液晶表示装置に組み込んだときに 発生する表示画面での異物故障や経時での視認性の変化を改善することができる セルロース混合エステルフィルムの製造方法および該製造方法によって製造された セルロース混合エステルフィルムを提供することを目的とする。特に、偏光板用保護 膜や位相差膜として有用であって、着色などを防ぐことができる強 、耐候性を有し、 かつ使用する微粒子の粉落ちを改良したセルロース混合エステルと、製造工程にお けるハンドリング性が良好な該セルロース混合エステルの製造方法を提供することを 目的とする。 [0006] In view of these problems of the prior art, the present invention can improve a foreign matter failure on a display screen and a change in visibility over time, which are generated when incorporated in a liquid crystal display device. It aims at providing the manufacturing method of a film, and the cellulose mixed ester film manufactured by this manufacturing method. In particular, it is useful as a protective film for a polarizing plate and a retardation film, has strength and weather resistance that can prevent coloring, Another object of the present invention is to provide a cellulose mixed ester with improved fine powder removal and a method for producing the cellulose mixed ester having good handling properties in the production process.
課題を解決するための手段  Means for solving the problem
[0007] 本発明の前記目的は以下の構成により達成された。  [0007] The object of the present invention has been achieved by the following constitution.
(1) セルロース混合エステルを溶融製膜して膜厚 20 μ m〜200 μ mのセルロース 混合エステルフィルムを製造するセルロース混合エステルフィルムの製造方法であつ て、  (1) A method for producing a cellulose mixed ester film in which a cellulose mixed ester film having a thickness of 20 μm to 200 μm is produced by melt-forming a cellulose mixed ester.
前記セルロース混合エステル力 下記式 ー1)〜（3— 3)を満たし、且つ、平均一 次粒子サイズが 0. 005 μ m〜2 μ mである微粒子を前記セルロース混合エステルに 対して 0. 005〜1. 0質量％含有するとともに、フエノール系安定剤、リン系安定剤、 チォエーテル系安定剤、スズ系安定剤およびアミン系安定剤からなる群より選択され る 1種類以上の安定剤をセルロース混合エステルに対して 0. 01〜3質量％含有して おり、  Cellulose mixed ester force Fine particles satisfying the following formulas (1) to (3-3) and having an average primary particle size of 0.005 μm to 2 μm are added to the cellulose mixed ester to 0.005. ˜1.0% by mass and mixed with one or more stabilizers selected from the group consisting of phenol stabilizers, phosphorus stabilizers, thioether stabilizers, tin stabilizers and amine stabilizers Contained in an amount of 0.01 to 3% by mass relative to the ester,
更に、前記セルロース混合エステルを 180〜230°Cで溶融してダイ力も押し出し、 溶融製膜してセルロース混合エステルフィルムを得る溶融製膜工程を含むことを特 徴とするセルロース混合エステルフィルムの製造方法。  Furthermore, the cellulose mixed ester is melted at 180 to 230 ° C. to extrude the die force, and includes a melt film-forming step of melt-forming to obtain a cellulose mixed ester film. .
式（S— 1) 2. 5≤A+B≤3. 0  Formula (S— 1) 2. 5≤A + B≤3.0
式（S— 2) 0≤A≤2. 2  Formula (S—2) 0≤A≤2. 2
式（S— 3) 0. 8≤B≤3. 0  Formula (S—3) 0. 8≤B≤3.0
(式中、 Aはセルロースの水酸基に対するァセチル基の置換度を表し、 Bはセルロー スの水酸基に対する炭素数 3〜22のァシル基の置換度を表す。）  (In the formula, A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose, and B represents the degree of substitution of the acyl group having 3 to 22 carbon atoms with respect to the hydroxyl group of cellulose.)
[0008] (2) 前記微粒子が、 SiO、 ZnO、 TiO、 SnO、 Al O、 ZrO、 In O、 MgO、 BaO [0008] (2) The fine particles include SiO, ZnO, TiO, SnO, AlO, ZrO, InO, MgO, BaO.
2 2 2 2 3 2 2 3  2 2 2 2 3 2 2 3
、 MoO、 V Oの少なくとも一種力 選ばれることを特徴とする（1)に記載のセルロー At least one kind of force selected from MoO and V 2 O
2 2 5 2 2 5
ス混合エステルフィルムの製造方法。  A method for producing a mixed ester film.
[0009] (3) 前記セルロース混合エステル中のセルロースの水酸基に対して置換している炭 素数 3〜22のァシル基力 プロピオ-ル基およびプチリル基力 選択される 1以上の ァシル基を有することを特徴とする（1)または（2)に記載のセルロース混合エステル フィルムの製造方法。 [0009] (3) The acyl group having 3 to 22 carbon atoms substituted with respect to the hydroxyl group of cellulose in the cellulose mixed ester Propyl group and petityl group having at least one selected acyl group (1) or cellulose mixed ester according to (2) A method for producing a film.
[0010] (4) 前記溶融製膜工程において溶融製膜されたフィルムを、少なくとも 1方向にー1 0%〜50%延伸する延伸工程を有することを特徴とする（1)〜（3)のいずれかに記 載のセルロース混合エステルフィルムの製造方法。  [0010] (4) The method according to any one of (1) to (3), further comprising a stretching step of stretching the film that has been melt-formed in the melt-casting step in at least one direction by −10% to 50% The manufacturing method of the cellulose mixed ester film as described in any one.
[0011] (5) セルロース混合エステルを溶融製膜した膜厚 20 μ m〜200 μ mのセルロース 混合エステルフィルムであって、  [0011] (5) A cellulose mixed ester film having a film thickness of 20 μm to 200 μm formed by melt-forming a cellulose mixed ester,
前記セルロース混合エステル力 下記式 ー1)〜（3— 3)を満たし、且つ、平均一 次粒子サイズが 0. 005 μ m〜2 μ mである微粒子を前記セルロース混合エステルに 対して 0. 005〜1. 0質量％含有するとともに、フエノール系安定剤、リン系安定剤、 チォエーテル系安定剤、スズ系安定剤およびアミン系安定剤からなる群より選択され る 1種類以上の安定剤をセルロース混合エステルに対して 0. 01〜3質量％含有して おり、  Cellulose mixed ester force Fine particles satisfying the following formulas (1) to (3-3) and having an average primary particle size of 0.005 μm to 2 μm are added to the cellulose mixed ester to 0.005. ˜1.0% by mass and mixed with one or more stabilizers selected from the group consisting of phenol stabilizers, phosphorus stabilizers, thioether stabilizers, tin stabilizers and amine stabilizers Contained in an amount of 0.01 to 3% by mass relative to the ester,
更に、前記セルロース混合エステルを 180〜230°Cで溶融してダイ力も押し出し、 溶融製膜されて形成されることを特徴とするセルロース混合エステルフィルム。  Further, the cellulose mixed ester film is formed by melting the cellulose mixed ester at 180 to 230 ° C., extruding the die force, and forming a melt.
式（S— 1) 2. 5≤A+B≤3. 0  Formula (S— 1) 2. 5≤A + B≤3.0
式（S— 2) 0≤A≤2. 2  Formula (S—2) 0≤A≤2. 2
式（S— 3) 0. 8≤B≤3. 0  Formula (S—3) 0. 8≤B≤3.0
(式中、 Aはセルロースの水酸基に対するァセチル基の置換度を表し、 Bはセルロー スの水酸基に対する炭素数 3〜22のァシル基の置換度を表す。）  (In the formula, A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose, and B represents the degree of substitution of the acyl group having 3 to 22 carbon atoms with respect to the hydroxyl group of cellulose.)
[0012] (6) 正面レターデーシヨン (Re)が、 0〜： LOnmであり、且つ、厚さ方向のレターデー シヨン (Rth)の絶対値が 0〜60nmであることを特徴とする（5)に記載のセルロース混 合エステルフィルム。 (6) The front letter decision (Re) is 0 to: LOnm, and the absolute value of the thickness direction letter decision (Rth) is 0 to 60 nm (5) Cellulose-mixed ester film described in 1.
[0013] (7) ヘイズが 0. 1〜1. 2%であり、可視光の透過率が 91%以上であり、 25°C *相対 湿度 60%環境下で波長 590nmにおける面内方向の固有複屈折が 0〜0. 001であ り、厚さ方向の固有複屈折の絶対値が 0〜0. 003であることを特徴とする（5)または（ 6)に記載のセルロース混合エステルフィルム。  [0013] (7) Haze is 0.1 to 1.2%, visible light transmittance is 91% or more, and inherent in the in-plane direction at a wavelength of 590nm under an environment of 25 ° C * relative humidity 60% The cellulose mixed ester film according to (5) or (6), wherein birefringence is 0 to 0.001, and the absolute value of intrinsic birefringence in the thickness direction is 0 to 0.003.
[0014] (8) 波長 400nmおよび 700nmにおけるそれぞれの正面レターデーシヨン (Re)お よび厚さ方向のレターデーシヨン (Rth)が下記式 (A— 1)および (A— 2)を満たすこ とを特徴とする（5)〜（7)の 、ずれ力 1項に記載のセルロース混合エステルフィルム。 式 (A— 1) 0≤ I Re (700) -Re (400) | ≤15nm [8] (8) Respective front face lettering (Re) and thickness direction lettering (Rth) at wavelengths of 400 nm and 700 nm satisfy the following formulas (A— 1) and (A— 2). The cellulose mixed ester film according to item 1 of (5) to (7), wherein: Formula (A— 1) 0≤ I Re (700) -Re (400) | ≤15nm
式 (A— 2) 0≤ I Rth(700) -Rth (400) | ≤35nm  Formula (A— 2) 0≤ I Rth (700) -Rth (400) | ≤35nm
(式中、 Re (400)および Re (700)は、波長 400nmおよび 700nmにおける正面レ ターデーシヨン (Re)を表し、 Rth(400)および Rth (700)は、波長 400nmおよび 70 Onmにおける厚さ方向のレターデーシヨン (Rth)を表す。）  (Where Re (400) and Re (700) represent frontal retardation (Re) at wavelengths of 400 nm and 700 nm, and Rth (400) and Rth (700) are thickness-wise at wavelengths of 400 nm and 70 Onm. Represents letter decision (Rth).)
[0015] (9) 前記溶融製膜工程において、溶融押出された前記セルロース混合エステルと 前記微粒子との溶融混合物 (メルト）をキャスティングドラム上で固化させ、キャスティ ングドラム上に形成されたセルロース混合エステルフィルムを剥離し、 -ップロールで 張力カットし、さらに巻き取り時の張力を 0. 01kgZcm2〜10kgZcm2として前記セ ルロース混合エステルを巻き取ることを特徴とする（1)〜 (4)に記載のセルロース混 合エステルフィルムの製造方法。 [0015] (9) A cellulose mixed ester film formed on a casting drum by solidifying a molten mixture (melt) of the melt-extruded cellulose mixed ester and the fine particles in the melt film-forming step on a casting drum. The cellulose according to any one of (1) to (4), wherein the cellulose mixed ester is wound up with the tension being cut with a -roll, and the tension at the time of winding being 0.01 kgZcm 2 to 10 kgZcm 2 A method for producing a mixed ester film.
[0016] (10) 前記溶融製膜工程は、前記溶融混合物をキャスティングドラム上で固化する 際、（Tg + 30°C)力 Tgの間の温度（ここで Tgはセルロース混合エステルフィルムの ガラス転移温度を示す。 )で冷却を 10°CZ秒〜 100°CZ秒の速度（固化速度)で行う ことを特徴とする（1)〜 (4)または（9)に記載のセルロース混合エステルフィルムの製 造方法。  [0016] (10) In the melt film-forming step, when the molten mixture is solidified on a casting drum, a temperature between (Tg + 30 ° C) force Tg (where Tg is the glass transition of the cellulose mixed ester film) (1) to (4) or (9), wherein cooling is performed at a rate of 10 ° CZ seconds to 100 ° CZ seconds (solidification rate). Manufacturing method.
[0017] (11) 前記溶融製膜工程において、前記セルロース混合エステルと前記微粒子との 溶融混合物を、圧縮比 2〜15のスクリューを用いて 180°C〜230°Cで溶融した後、ダ イカ キャスティングドラム上に押し出すことを特徴とする（1)〜 (4)または（10)に記 載のセルロース混合エステルフィルムの製造方法。  [0017] (11) In the melt film-forming step, the molten mixture of the cellulose mixed ester and the fine particles is melted at 180 ° C to 230 ° C using a screw having a compression ratio of 2 to 15, and then the die. The method for producing a cellulose mixed ester film according to any one of (1) to (4) or (10), wherein the cellulose mixed ester film is extruded onto a casting drum.
[0018] (12) 前記溶融製膜工程において、ダイカゝら前記セルロース混合エステルを押し出 した後、 Tgから (Tg— 20°C)の間の温度で冷却を 0. 1°CZ秒〜 20°CZ秒の速度で 行うことを特徴とする（10)または（11)に記載のセルロース混合エステルフィルムの 製造方法。  [0018] (12) In the melt film-forming step, after extruding the cellulose mixed ester from Daika et al., Cooling is performed at a temperature between Tg and (Tg—20 ° C) for 0.1 ° CZ seconds to 20 ° C. The method for producing a cellulose mixed ester film according to (10) or (11), wherein the method is performed at a rate of ° CZ seconds.
[0019] (13) (9)〜（12)のいずれかに記載のセルロース混合エステルフィルムの製造方 法により製造したことを特徴とするセルロース混合エステルフィルム。  [0019] (13) A cellulose mixed ester film produced by the method for producing a cellulose mixed ester film according to any one of (9) to (12).
[0020] (14) 厚みムラが 0〜5 /ζ πιであることを特徴とする（13)に記載のセルロース混合ェ ステノレフイノレム。 [0020] (14) The cellulose mixture according to (13), wherein the thickness unevenness is 0 to 5 / ζ πι. Steno refinolem.
[0021] (15)  [0021] (15)
フィルム表面の水の接触角（25°CZ相対湿度 60%)が 45° 以下であることを特徴 とする（5)〜（8)あるいは（13)または（14)の!、ずれかに記載のセルロース混合エス テルフィルム。  The contact angle of water on the film surface (25 ° CZ relative humidity 60%) is 45 ° or less. (5) to (8) or (13) or (14)! Cellulose mixed ester film.
[0022] (16) 前記セルロース混合エステルが下記式 (S— 4)〜（S— 6)を満足することを特 徴とする（13)〜（15)のいずれか一項に記載のセルロース混合エステルフィルム。  [0022] (16) The cellulose mixture according to any one of (13) to (15), wherein the cellulose mixed ester satisfies the following formulas (S-4) to (S-6): Ester film.
式（S—4) 2. 6≤A+B'≤3. 0  Formula (S—4) 2. 6≤A + B'≤3.0
式（S— 5) 0≤A≤1. 8  Formula (S—5) 0≤A≤1.8
式（S— 6) 1. 0≤B'≤3. 0  Formula (S—6) 1. 0≤B'≤3.0
(式中、 Aはセルロースの水酸基に対するァセチル基の置換度を表し、 B'はセル口 ースの水酸基に対するプロピオニル基またはプチリル基の置換度の総和を表す。 ) (17) 前記セルロース混合エステルフィルムの動的および静的キシミ値が共に 0. 2 〜1. 5であり、前記セルロース混合エステルフィルム中に存在する前記微粒子の平 均二次粒子サイズが 0. 01 m〜5 μ mであることを特徴とする（5)〜（8)または（13 )〜（16)のいずれか 1項に記載のセルロース混合エステルフィルム。  (In the formula, A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose, and B ′ represents the sum of the degree of substitution of propionyl group or petityl group with respect to the hydroxyl group of cell mouth.) (17) The cellulose mixed ester film Both the dynamic and static kimimi values of the particles are 0.2 to 1.5, and the average secondary particle size of the fine particles present in the cellulose mixed ester film is 0.01 m to 5 μm. The cellulose mixed ester film according to any one of (5) to (8) or (13) to (16).
[0023] (18) 偏光膜に（5)〜（8)または（13)〜（16)のいずれかに記載のセルロース混合 エステルフィルムを少なくとも 1層積層したことを特徴とする偏光板。  (18) A polarizing plate comprising at least one layer of the cellulose mixed ester film according to any one of (5) to (8) or (13) to (16) laminated on a polarizing film.
[0024] (19) 前記偏光膜が長手方向に対して実質的に 45° の方向にテンター延伸され たことを特徴とする（18)に記載の偏光板。  (19) The polarizing plate according to (18), wherein the polarizing film is tenter-stretched in a direction substantially 45 ° with respect to the longitudinal direction.
[0025] (20) (5)〜（8)または（13)〜（16)のいずれかに記載のセルロース混合エステル フィルムを基材に用いたことを特徴とする光学補償フィルム。  [0025] (20) An optical compensation film comprising the cellulose mixed ester film according to any one of (5) to (8) or (13) to (16) as a base material.
[0026] (21) (5)〜（8)または（13)〜（16)のいずれかに記載のセルロース混合エステル フィルムを基材に用いたことを特徴とする反射防止フィルム。  [0026] (21) An antireflection film comprising the cellulose mixed ester film according to any one of (5) to (8) or (13) to (16) as a base material.
(22) (18)または（19)に記載の偏光板、（20)に記載の光学補償フィルム、および 、 (21)に記載の反射防止フィルムの少なくとも一つを用いたことを特徴とする液晶表 示装置。  (22) A liquid crystal using at least one of the polarizing plate according to (18) or (19), the optical compensation film according to (20), and the antireflection film according to (21) Display device.
発明の効果 [0027] 本発明によれば、セルロース混合エステルの製造時のハンドリング性を改良し、表 面欠陥 (傷付き）を大幅に軽減し、液晶表示装置に組み込んだときに発生する表示 画面での異物故障や経時による視認性の変化を改善することができるセルロース混 合エステルフィルムの製造方法および該製造方法によって製造されたセルロース混 合エステルフィルムを提供することができる。 The invention's effect [0027] According to the present invention, the handling property during the production of the cellulose mixed ester is improved, the surface defects (scratches) are greatly reduced, and the foreign matter on the display screen generated when the liquid crystal display device is incorporated. It is possible to provide a method for producing a cellulose mixed ester film capable of improving a change in visibility due to failure or aging, and a cellulose mixed ester film produced by the production method.
本発明のセルロース混合エステルフィルムにより、経時での耐候性、特に高温環境 下における優れた耐久性を有する光学用途のフィルムを提供することができる。 本発明のセルロース混合エステルフィルムを組み込んで液晶表示装置を製造すれ ば、表示ムラや湿度、あるいは画像の色による光学特性の変化を抑制することができ る。  The cellulose mixed ester film of the present invention can provide a film for optical use having excellent weather resistance over time, particularly excellent durability under a high temperature environment. If a liquid crystal display device is manufactured by incorporating the cellulose mixed ester film of the present invention, it is possible to suppress changes in optical characteristics due to display unevenness, humidity, or image color.
図面の簡単な説明  Brief Description of Drawings
[0028] 図 1は、押出機の構造を示す断面図である。図中、 22は押出機、 32はシリンダー、 40は供給口、 Aは供給部、 Bは圧縮部、 Cは計量部である。  FIG. 1 is a cross-sectional view showing the structure of the extruder. In the figure, 22 is an extruder, 32 is a cylinder, 40 is a supply port, A is a supply section, B is a compression section, and C is a weighing section.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0029] 以下において、本発明のセルロース混合エステルフィルムの製造方法および該製 造方法にぉ 、て製造されたセルロース混合エステルフィルムつ 、て詳細に説明する 。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなさ れることがあるが、本発明はそのような実施態様に限定されるものではない。なお、本 明細書にお 1ヽて「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を 下限値および上限値として含む範囲を意味する。  [0029] Hereinafter, the method for producing a cellulose mixed ester film of the present invention and the cellulose mixed ester film produced by the production method will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
[0030] 《セルロース混合エステルフィルムの製造方法》  <Method for producing cellulose mixed ester film>
本発明のセルロース混合エステルフィルムの製造方法 (以下、「本発明の製造方法 」と称する場合がある。）は、セルロース混合エステルを溶融製膜して膜厚 20〜200 /z mのセルロース混合エステルフィルムを製造するセルロース混合エステルフィルム の製造方法であって、  The method for producing a cellulose mixed ester film of the present invention (hereinafter sometimes referred to as “the production method of the present invention”) is a cellulose mixed ester film having a film thickness of 20 to 200 / zm by melt-forming a cellulose mixed ester. A method for producing a cellulose mixed ester film comprising:
前記セルロース混合エステル力 下記式 ー1)〜（3— 3)を満たし、且つ、平均一 次粒子サイズが 0. 005 μ m〜2 μ mである微粒子を前記セルロース混合エステルに 対して 0. 005〜1. 0質量％含有するとともに、フエノール系安定剤、リン系安定剤、 チォエーテル系安定剤、スズ系安定剤およびアミン系安定剤からなる群より選択され る 1種類以上の安定剤をセルロース混合エステルに対して 0. 01〜3質量％含有して おり、 Cellulose mixed ester force Fine particles satisfying the following formulas (1) to (3-3) and having an average primary particle size of 0.005 μm to 2 μm are added to the cellulose mixed ester to 0.005. ~ 1.0% by mass, phenolic stabilizer, phosphorus stabilizer, Containing 0.01 to 3% by mass of one or more stabilizers selected from the group consisting of thioether stabilizers, tin stabilizers and amine stabilizers, based on the cellulose mixed ester;
更に、前記セルロース混合エステルを 180〜230°Cで溶融してダイ力も押し出し、 溶融製膜してセルロース混合エステルフィルムを得る溶融製膜工程を含むことを特 徴とする。  Further, the present invention is characterized in that it includes a melt film forming step of melting the cellulose mixed ester at 180 to 230 ° C. to extrude the die force to form a cellulose mixed ester film by melt film formation.
式（S— 1) 2. 5≤A+B≤3. 0  Formula (S— 1) 2. 5≤A + B≤3.0
式（S— 2) 0≤A≤2. 2  Formula (S—2) 0≤A≤2. 2
式（S— 3) 0. 8≤B≤3. 0  Formula (S—3) 0. 8≤B≤3.0
(式中、 Aはセルロースの水酸基に対するァセチル基の置換度を表し、 Bはセルロー スの水酸基に対する炭素数 3〜22のァシル基の置換度を表す。）  (In the formula, A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose, and B represents the degree of substitution of the acyl group having 3 to 22 carbon atoms with respect to the hydroxyl group of cellulose.)
[0031] (セルロース混合エステル） [0031] (Cellulose mixed ester)
本発明の製造方法で用いられるセルロース混合エステルは下記式 (S— 1)〜（S— 3)を満足する。  The cellulose mixed ester used in the production method of the present invention satisfies the following formulas (S-1) to (S-3).
式（S— 1) 2. 5≤A+B≤3. 0  Formula (S— 1) 2. 5≤A + B≤3.0
式（S— 2) 0≤A≤2. 2  Formula (S—2) 0≤A≤2. 2
式（S— 3) 0. 8≤B≤3. 0  Formula (S—3) 0. 8≤B≤3.0
(式中、 Aはセルロースの水酸基に対するァセチル基の置換度を表し、 Bはセルロー スの水酸基に対する炭素数 3〜22のァシル基の置換度を表す。）  (In the formula, A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose, and B represents the degree of substitution of the acyl group having 3 to 22 carbon atoms with respect to the hydroxyl group of cellulose.)
[0032] セルロースを構成する、ベータ（ j8 )—1, 4結合しているグルコース単位は、 2位、 3 位および 6位に遊離の水酸基を有している。セルロース混合エステルは、これらの水 酸基の一部または全部をエステル化した重合体 (ポリマー）である。ァシル置換度は 、 2位、 3位および 6位のそれぞれについて、セルロースがエステル化している割合（1 00%のエステルイ匕は置換度 1)の合計を意味する。本発明において、 A+Bはより好 ましくは 2. 6≤A+B≤3. 0であり、さらに好ましくは 2. 67≤A+B≤2. 97である。 また、 Aは、好ましくは 0≤A≤1. 8であり、 Bは 1. 0≤B≤2. 97が好ましぐさらには 1. 2≤B≤2. 97力 S好ましい。本発明においては、セルロースの 2位、 3位および 6位 の水酸基の置換度は特に限定されな ヽが、セルロース混合エステルの 6位の置換度 が好ましくは 0. 7以上であり、さらに好ましくは 0. 8以上であり、特に好ましくは 0. 85 以上であり、特に 0. 90以上が好ましい。これによりセルロース混合エステルの溶解 性、耐熱性を向上させることができる。 [0032] Glucose units in cellulose that are bonded to beta (j8) -1, 4 have free hydroxyl groups at the 2nd, 3rd and 6th positions. The cellulose mixed ester is a polymer obtained by esterifying some or all of these hydroxyl groups. The degree of acyl substitution means the total of the ratios of esterification of cellulose for each of the 2nd, 3rd and 6th positions (100% esterification is 1 substitution degree). In the present invention, A + B is more preferably 2.6≤A + B≤3.0, and more preferably 2.67≤A + B≤2.97. Also, A is preferably 0≤A≤1.8 and B is preferably 1.0≤B≤2. 97 or even 1.2≤B≤2. 97 force S. In the present invention, the substitution degree of the hydroxyl groups at the 2nd, 3rd and 6th positions of the cellulose is not particularly limited. However, the substitution degree at the 6th position of the cellulose mixed ester is not limited. Is preferably at least 0.7, more preferably at least 0.8, particularly preferably at least 0.85, particularly preferably at least 0.90. Thereby, the solubility and heat resistance of the cellulose mixed ester can be improved.
[0033] 次に本発明のセルロース混合エステルの置換基 Bで表される炭素数 3〜22のァシ ル基は、脂肪族ァシル基でも芳香族ァシル基のいずれであってもよい。本発明のセ ルロース混合エステルのァシル基が脂肪族ァシル基である場合、炭素数は 3〜18で あることが好ましぐ炭素数は 3〜12であることがさらに好ましぐ炭素数は 3〜8であ ることが特に好ましい。これらの脂肪族ァシル基の例としては、アルキルカルボ-ル基 、ァルケ-ルカルポ-ル基、あるいはアルキ-ルカルボ-ル基などを挙げることがで きる。ァシル基が芳香族ァシル基である場合、炭素数は 6〜22であることが好ましぐ 炭素数は 6〜18であることがさらに好ましぐ炭素数は 6〜12であることが特に好まし い。これらのァシル基は、それぞれさらに置換基を有していてもよい。 Next, the acyl group having 3 to 22 carbon atoms represented by the substituent B of the cellulose mixed ester of the present invention may be either an aliphatic acyl group or an aromatic acyl group. When the acyl group of the cellulose mixed ester of the present invention is an aliphatic acyl group, the number of carbon atoms is preferably 3-18, and more preferably 3-12. It is particularly preferred that it is ˜8. Examples of these aliphatic acyl groups include an alkyl carbo yl group, an alkaryl carbo ol group, an alkyl carbo ol group, and the like. When the acyl group is an aromatic acyl group, the carbon number is preferably 6-22. The carbon number is more preferably 6-18, and the carbon number is particularly preferably 6-12. Good. Each of these acyl groups may further have a substituent.
[0034] 好まし!/、ァシル基の例としては、プロピオ-ル基、ブチリル基、ペンタノィル基、へキ サノィル基、ヘプタノィル基、オタタノィル基、デカノィル基、ドデカノィル基、トリデカ ノィル基、テトラデカノィル基、へキサデカノィル基、ォクタデカノィル基、イソプチリル 基、ピバロイル基、シクロへキサンカルボ-ル基、ォレオイル基、ベンゾィル基、ナフ タレンカルボニル基、フタロイル基、シンナモイル基などを挙げることができる。これら の中でも、さらに好ましいものは、プロピオ-ル基、ブチリル基、ドデカノィル基、オタ タデカノィル基、ビバロイル基、ォレオイル基、ベンゾィル基、ナフチルカルボニル基 、シンナモイル基などである。 [0034] Preferred examples of the acyl group include propiol group, butyryl group, pentanoyl group, hexanol group, heptanol group, otatanyl group, decanol group, dodecanol group, tridecanol group, tetradecanol group, Examples include a hexadecanol group, an octadecanol group, an isoptyryl group, a pivaloyl group, a cyclohexanecarbol group, an oleoyl group, a benzoyl group, a naphthalenecarbonyl group, a phthaloyl group, and a cinnamoyl group. Among these, more preferred are propiol group, butyryl group, dodecanol group, otadecanoyl group, bivaloyl group, oleoyl group, benzoyl group, naphthylcarbonyl group, cinnamoyl group and the like.
[0035] 本発明のセルロース混合エステルのエステルを構成するァシル基は、好ましくは炭 素原子数が 6以下の脂肪族ァシル基であり、ァセチル基、プロピオニル基、プチリル 基、ペンタノィル基およびへキサノィル基力 なる群より選択されるァシル基が好まし い。より好ましいのは、ァセチル基、プロピオ-ル基、ブチリル基およびペンタノィル 基力 なる群より選択されるァシル基であり、さらに好ましいのはァセチル基、プロピ ォニル基およびプチリル基力もなる群より選択されるァシル基である。本発明のセル ロース混合エステルのエステルを構成するァシル基は、単一種であってもよいし、複 数種であってもよい。 [0036] さらに、本発明で使用するセルロース混合エステルは、下記式 (S— 4)〜（S— 6)を 満足することが好ましい。 [0035] The acyl group constituting the ester of the mixed cellulose ester of the present invention is preferably an aliphatic acyl group having 6 or less carbon atoms, and includes an acetyl group, a propionyl group, a pentyl group, a pentanoyl group, and a hexanol group. The acyl group selected from the group of forces is preferred. More preferred is a acyl group selected from the group consisting of acetyl group, propiol group, butyryl group and pentanoyl group, and more preferred is selected from the group consisting of acetyl group, propionyl group and petityl group. Is an acyl group. The acyl group constituting the ester of the cellulose mixed ester of the present invention may be a single species or a plurality of species. Furthermore, the cellulose mixed ester used in the present invention preferably satisfies the following formulas (S-4) to (S-6).
式（S—4) 2. 6≤A+B'≤3. 0  Formula (S—4) 2. 6≤A + B'≤3.0
式（S— 5) 0≤A≤1. 8  Formula (S—5) 0≤A≤1.8
式（S— 6) 1. 0≤B'≤3. 0  Formula (S—6) 1. 0≤B'≤3.0
(式中、 Aはセルロースの水酸基に対するァセチル基の置換度を表し、 B'はセル口 ースの水酸基に対するプロピオニル基、プチリル基の置換度の総和を表す。 )  (In the formula, A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose, and B ′ represents the total degree of substitution of the propionyl group and petityl group with respect to the hydroxyl group of the cell mouth.)
[0037] また、より好ましくは、本発明で使用するセルロース混合エステル力 2. 6≤A+B， ≤3. 0、0≤A≤1. 4、および 1. 0≤B'≤ 3を満足することが好ましい。特に、本発 明で使用するセルロース混合エステル力 2. 7≤A+B'≤3. 0、 0≤A≤1. 0およ び 1. 3≤B'≤ 3を満足することが好ましい。このようにァセチル基の含有率を低くし、 プロピオ-ル基、ブチリル基の含有率を多くすることによって、フィルム化したときの温 度、湿度に対する光学特性変化を抑制することができる。 [0037] More preferably, the cellulose mixed ester power used in the present invention satisfies 2.6≤A + B, ≤3.0, 0≤A≤1.4, and 1.0≤B'≤3 It is preferable to do. In particular, it is preferable that the cellulose mixed ester strength used in the present invention satisfies 2.7≤A + B'≤3.0, 0≤A≤1.0 and 1.3≤B'≤3. Thus, by reducing the content of the acetyl group and increasing the content of the propiol group and butyryl group, it is possible to suppress changes in optical properties with respect to temperature and humidity when the film is formed.
[0038] (セルロース混合エステルの製造方法） [0038] (Method for producing cellulose mixed ester)
次に、本発明のセルロース混合エステルの製造方法について説明する。本発明の セルロース混合エステルのさらに詳細な原料綿や合成方法にっ ヽては、発明協会公 開技報 (公技番号 2001— 1745、 2001年 3月 15日発行、発明協会） 7〜 12頁に記 載されている。セルロース原料としては、広葉樹パルプ、針葉樹パルプ、綿花リンタ 一由来のものが好ましく用いられる。セルロース原料としては、 a セルロース含量 力 S92質量％〜99. 9質量％の高純度のものを用いることが好ましい。セルロース原 料がシート状や塊状である場合は、あら力じめ解砕しておくことが好ましぐセルロー スの形態は微細粉末力 羽毛状になるまで解砕が進行して 、ることが好ま 、。  Next, the manufacturing method of the cellulose mixed ester of this invention is demonstrated. For more detailed raw material cotton and synthesis method of the cellulose mixed ester of the present invention, see the Japan Institute of Technology (Technical Number 2001-1745, March 15, 2001, Japan Society of Invention and Innovation) 7-12 It is described in. As the cellulose raw material, those derived from hardwood pulp, softwood pulp and cotton linter are preferably used. As a cellulose raw material, it is preferable to use a high-purity material having a cellulose content force of S92 mass% to 99.9 mass%. When the cellulose raw material is in the form of a sheet or a lump, it is preferable to pulverize it. The cellulosic form is fine powder force. Favored ,.
[0039] セルロース原料はァシルイ匕に先立って、活性化剤と接触させる処理 (活性化）を行 なっておくことが好ましい。前記活性化剤としては、カルボン酸または水を用いること ができる力 水を用いた場合には、活性ィ匕の後に酸無水物を過剰に添加して脱水を 行ったり、水を置換するためにカルボン酸で洗浄したり、ァシル化の条件を調節した りすると ヽつた工程を含むことが好まし ヽ。活性化剤は!ヽかなる温度に調節して添カロ してもよく、添加方法としては噴霧、滴下、浸漬などの方法力 選択することができる 。活性化剤として好ましいカルボン酸は、炭素数 2〜7のカルボン酸 (例えば、酢酸、 プロピオン酸、酪酸、 2—メチルプロピオン酸、吉草酸、 3—メチル酪酸、 2—メチル酪 酸、 2, 2—ジメチルプロピオン酸（ピバル酸）、へキサン酸、 2—メチル吉草酸、 3—メ チル吉草酸、 4ーメチル吉草酸、 2, 2—ジメチル酪酸、 2, 3—ジメチル酪酸、 3, 3— ジメチル酪酸、シクロペンタンカルボン酸、ヘプタン酸、シクロへキサンカルボン酸、 安息香酸など)であり、より好ましくは、酢酸、プロピオン酸、または酪酸である。活性 化の際はさらに硫酸などをセルロースに対して 0. 1質量％〜10質量％添加してもよ い。 [0039] The cellulose raw material is preferably subjected to a treatment (activation) in contact with an activator prior to the acylation. As the activator, carboxylic acid or water that can use water is used. In order to perform dehydration by adding an excess of acid anhydride after the activation, or to replace water It is preferable to include two steps when washing with carboxylic acid and adjusting the conditions of acylation. The activator may be adjusted to a very high temperature and added. . Preferred carboxylic acids as activators are carboxylic acids having 2 to 7 carbon atoms (eg acetic acid, propionic acid, butyric acid, 2-methylpropionic acid, valeric acid, 3-methylbutyric acid, 2-methylbutyric acid, 2, 2 —Dimethylpropionic acid (pivalic acid), hexanoic acid, 2-methylvaleric acid, 3-methylvaleric acid, 4-methylvaleric acid, 2,2-dimethylbutyric acid, 2,3-dimethylbutyric acid, 3,3-dimethyl Butyric acid, cyclopentanecarboxylic acid, heptanoic acid, cyclohexanecarboxylic acid, benzoic acid, etc.), more preferably acetic acid, propionic acid, or butyric acid. In the activation, sulfuric acid or the like may be added in an amount of 0.1% by mass to 10% by mass with respect to cellulose.
[0040] 活性化剤の添カ卩量は、セルロース質量に対して 0.05〜： LOO質量倍であることが好 ましぐ 0.1〜20質量倍であることがさらに好ましぐ 0.3〜20質量倍であることが特に 好ましい。活性ィ匕の時間は 20分〜 72時間が好ましぐさらに好ましくは 30分〜 24時 間、特に好ましくは 30分〜 12時間である。また、活性ィ匕の温度は 0°C〜90°Cが好ま しぐ 15°C〜80°Cがさらに好ましぐ 20°C〜60°Cが特に好ましい。セルロースの活性 化の工程は加圧または減圧条件下で行なうこともできる。また、加熱の手段として、マ イク口波や赤外線などの電磁波を用いてもょ 、。  [0040] The amount of the additive added to the activator is 0.05 to: LOO mass times, preferably 0.1 to 20 times mass, and more preferably 0.3 to 20 times mass with respect to the cellulose mass. It is particularly preferred. The duration of the activity is preferably 20 minutes to 72 hours, more preferably 30 minutes to 24 hours, and particularly preferably 30 minutes to 12 hours. Further, the temperature of the active liquid is preferably 0 ° C to 90 ° C, more preferably 15 ° C to 80 ° C, and particularly preferably 20 ° C to 60 ° C. The step of activating cellulose can be performed under pressure or reduced pressure. Also, use electromagnetic waves such as microphone mouth waves and infrared rays as a means of heating.
[0041] 本発明におけるセルロース混合エステルを製造する方法においては、セルロース にカルボン酸の酸無水物を加え、ブレンステッド酸またはルイス酸を触媒として反応 させることで、セルロースの水酸基をァシルイ匕することが好ましい。本発明におけるセ ルロース混合エステルを得る方法としては、ァシル化剤として 2種のカルボン酸無水 物を混合または逐次添カ卩により反応させる方法； 2種のカルボン酸の混合酸無水物（ 例えば、酢酸'プロピオン酸混合酸無水物）を用いる方法;カルボン酸と別のカルボ ン酸の酸無水物（例えば、酢酸とプロピオン酸無水物）とを原料として反応系内で混 合酸無水物（例えば、酢酸'プロピオン酸混合酸無水物）を合成してセルロースと反 応させる方法;置換度が 3に満たないセルロース混合エステルをー且合成し、酸無水 物や酸ハライドを用いて残存する水酸基をさらにァシルイ匕する方法などを用いること ができる。  [0041] In the method for producing a cellulose mixed ester in the present invention, a hydroxyl group of cellulose can be acylated by adding an acid anhydride of carboxylic acid to cellulose and reacting with Bronsted acid or Lewis acid as a catalyst. preferable. In the present invention, the mixed cellulose ester can be obtained by mixing two carboxylic anhydrides as an acylating agent or reacting them by sequential addition; a mixed acid anhydride of two carboxylic acids (for example, acetic acid). 'Propionic acid mixed acid anhydrides' method; mixed acid anhydrides (for example, acetic acid and propionic acid anhydrides, for example, acetic acid and propionic acid anhydrides) as raw materials A method of synthesizing acetic acid (propionic acid mixed acid anhydride) and reacting with cellulose; a cellulose mixed ester having a degree of substitution of less than 3 is synthesized, and residual hydroxyl groups are further added using acid anhydride or acid halide. For example, a method for making a password can be used.
[0042] 前記カルボン酸の酸無水物として、好ましくはカルボン酸としての炭素数が 2〜7で あり、例えば、無水酢酸、プロピオン酸無水物、酪酸無水物、 2—メチルプロピオン酸 無水物、吉草酸無水物、 3 メチル酪酸無水物、 2 メチル酪酸無水物、 2, 2 ジメ チルプロピオン酸無水物（ピバル酸無水物）、へキサン酸無水物、 2—メチル吉草酸 無水物、 3 メチル吉草酸無水物、 4 メチル吉草酸無水物、 2, 2 ジメチル酪酸無 水物、 2, 3 ジメチル酪酸無水物、 3, 3 ジメチル酪酸無水物、シクロペンタンカル ボン酸無水物、ヘプタン酸無水物、シクロへキサンカルボン酸無水物、安息香酸無 水物などを挙げることができる。 [0042] The acid anhydride of the carboxylic acid preferably has 2 to 7 carbon atoms as the carboxylic acid. For example, acetic anhydride, propionic anhydride, butyric anhydride, 2-methylpropionic acid Anhydride, valeric anhydride, 3 methylbutyric anhydride, 2 methylbutyric anhydride, 2,2 dimethylpropionic anhydride (pivalic anhydride), hexanoic anhydride, 2-methylvaleric anhydride, 3 Methyl valeric acid anhydride, 4 Methyl valeric acid anhydride, 2, 2 Dimethyl butyric acid anhydrous, 2, 3 Dimethyl butyric acid anhydride, 3, 3 Dimethyl butyric acid anhydride, Cyclopentane carboxylic acid anhydride, Heptanoic acid anhydrous Products, cyclohexanecarboxylic anhydride, benzoic acid anhydrous, and the like.
[0043] より好ましくは、無水酢酸、プロピオン酸無水物、酪酸無水物、吉草酸無水物、へキ サン酸無水物、ヘプタン酸無水物などの無水物であり、特に好ましくは、無水酢酸、 プロピオン酸無水物、酪酸無水物である。 [0043] More preferred are acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride and the like, and particularly preferred are acetic anhydride, propion Acid anhydride and butyric anhydride.
セルロース混合エステルを調製する目的で、これらの酸無水物を併用して使用する ことが好ましく行われる。その混合比は目的とするセルロース混合エステルの置換比 に応じて決定することが好ましい。酸無水物は、セルロースに対して、通常は過剰当 量を添加することが好ましぐセルロースの水酸基に対して 1. 2〜50当量添加するこ と力 子ましく、 1. 5〜30当量添加することがより好ましぐ 2〜： LO当量添加することが 特に好ましい。  For the purpose of preparing a cellulose mixed ester, it is preferable to use these acid anhydrides in combination. The mixing ratio is preferably determined according to the substitution ratio of the target cellulose mixed ester. The acid anhydride should be added in an amount of 1.2 to 50 equivalents relative to the hydroxyl group of cellulose, which is usually preferred to be added in an excess amount relative to the cellulose, and 1.5 to 30 equivalents. It is more preferable to add 2-: It is particularly preferable to add LO equivalent.
[0044] 本発明におけるセルロース混合エステルの製造に用いるァシル化の触媒には、ブ レンステッド酸またはルイス酸を使用することが好まし ヽ。ブレンステッド酸およびルイ ス酸の定義については、例えば、「理ィ匕学辞典」第五版（2000年）に記載されている 。好ましいブレンステッド酸の例としては、硫酸、過塩素酸、リン酸、メタンスルホン酸 、ベンゼンスルホン酸、 p トルエンスルホン酸などを挙げることができる。好ましいル イス酸の例としては、塩化亜鉛、塩化スズ、塩ィ匕アンチモン、塩ィ匕マグネシウムなどを 挙げることができる。前記触媒としては、硫酸または過塩素酸がより好ましぐ硫酸が 特に好ましい。前記触媒の好ましい添加量は、セルロースに対して 0. 1〜30質量％ であり、より好ましくは 1〜15質量％であり、特に好ましくは 3〜12質量％である。  [0044] It is preferable to use a Bronsted acid or a Lewis acid as the catalyst for the acylation used in the production of the cellulose mixed ester in the present invention. The definitions of Bronsted acid and Lewis acid are described, for example, in “The Science Dictionary”, 5th edition (2000). Examples of preferable Bronsted acid include sulfuric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like. Preferred examples of the Lewis acid include zinc chloride, tin chloride, salt-antimony, salt-magnesium and the like. The catalyst is particularly preferably sulfuric acid, more preferably sulfuric acid or perchloric acid. A preferable addition amount of the catalyst is 0.1 to 30% by mass with respect to cellulose, more preferably 1 to 15% by mass, and particularly preferably 3 to 12% by mass.
[0045] セルロースのァシルイ匕を行なう際には、粘度、反応速度、攪拌性、ァシル置換比な どを調整する目的で、溶媒を添加してもよい。このような溶媒としては、ジクロロメタン 、クロ口ホルム、カルボン酸、アセトン、ェチルメチルケトン、トルエン、ジメチルスルホ キシド、スルホランなどを用いることもできる力 好ましくはカルボン酸であり、例えば、 炭素数 2〜7のカルボン酸（例えば、酢酸、プロピオン酸、酪酸、 2 メチルプロピオン 酸、吉草酸、 3 メチル酪酸、 2 メチル酪酸、 2, 2 ジメチルプロピオン酸（ピバル 酸）、へキサン酸、 2—メチル吉草酸、 3—メチル吉草酸、 4ーメチル吉草酸、 2, 2- ジメチル酪酸、 2, 3 ジメチル酪酸、 3, 3 ジメチル酪酸、シクロペンタンカルボン酸 )などを挙げることができ、好ましくは、酢酸、プロピオン酸、酪酸などを挙げることが できる。これらの溶媒は混合して用いてもよい。 [0045] When carrying out the acylation of cellulose, a solvent may be added for the purpose of adjusting the viscosity, the reaction rate, the stirring property, the acyl substitution ratio, and the like. As such a solvent, dichloromethane, chloroform, carboxylic acid, acetone, ethyl methyl ketone, toluene, dimethyl sulfoxide, sulfolane and the like can be used, preferably carboxylic acid. C2-C7 carboxylic acids (eg acetic acid, propionic acid, butyric acid, 2 methylpropionic acid, valeric acid, 3 methylbutyric acid, 2 methylbutyric acid, 2, 2 dimethylpropionic acid (pivalic acid), hexanoic acid, 2 -Methyl valeric acid, 3-methyl valeric acid, 4-methyl valeric acid, 2,2-dimethylbutyric acid, 2,3 dimethylbutyric acid, 3,3 dimethylbutyric acid, cyclopentanecarboxylic acid) and the like. Examples include acetic acid, propionic acid and butyric acid. These solvents may be used as a mixture.
[0046] セルロースのァシルイ匕を行なう際には、酸無水物および触媒、さらに、必要に応じ て溶媒を混合して力 セルロースと混合してもよぐまたこれらを別々に逐次セルロー スと混合してもよいが、通常は、酸無水物と触媒との混合物、または、酸無水物と触 媒と溶媒との混合物をァシル化剤として調製して力 セルロースと反応させることが好 ましい。ァシルイ匕の際の反応熱による反応容器内の温度上昇を抑制するために、ァ シル化剤は予め冷却しておくことが好ましい。冷却温度としては、 50°C〜20°Cが 好ましぐ—35°C〜10°Cがより好ましぐ 25°C〜5°Cが特に好ましい。ァシル化剤 は液状で添加しても、凍結させて結晶、フレーク、またはブロック状の固体として添カロ してちよい。 [0046] When carrying out cellulose acylation, an acid anhydride and a catalyst and, if necessary, a solvent may be mixed and mixed with force cellulose, or these may be separately mixed with cellulose one after another. However, it is usually preferable to prepare a mixture of an acid anhydride and a catalyst, or a mixture of an acid anhydride, a catalyst and a solvent as an acylating agent and react with force cellulose. It is preferable to cool the acylating agent in advance in order to suppress the temperature rise in the reaction vessel due to the heat of reaction during the acylation. The cooling temperature is preferably from 50 ° C to 20 ° C, more preferably from 35 ° C to 10 ° C, particularly preferably from 25 ° C to 5 ° C. The acylating agent may be added in liquid form or may be frozen and added as crystals, flakes or block solids.
[0047] 前記ァシル化剤はさらに、セルロースに対して一度に添加しても、分割して添加し てもよい。また、ァシル化剤に対してセルロースを一度に添加しても、分割して添加し てもよい。ァシル化剤を分割して添加する場合は、同一組成のァシル化剤を用いて も、複数の組成の異なるァシル化剤を用いてもよい。好ましい例としては、 1)酸無水 物と溶媒との混合物をまず添加し、次いで、触媒を添加する、 2)酸無水物および溶 媒と触媒の一部との混合物をまず添加し、次いで、触媒の残りと溶媒との混合物を添 加する、 3)酸無水物と溶媒との混合物をまず添加し、次いで、触媒と溶媒との混合 物を添加する、 4)溶媒をまず添加し、酸無水物と触媒との混合物あるいは酸無水物 と触媒と溶媒との混合物を添加する、などを挙げることができる。  [0047] The acylating agent may be added to the cellulose at once or dividedly. In addition, cellulose may be added to the acylating agent at once or dividedly. When the acylating agent is added in portions, the same acylating agent or a plurality of different acylating agents may be used. Preferred examples include: 1) a mixture of acid anhydride and solvent is added first, then the catalyst is added, 2) a mixture of acid anhydride and solvent and a portion of the catalyst is added first, then Add the remainder of the catalyst and the solvent mixture, 3) Add the acid anhydride and solvent mixture first, then add the catalyst and solvent mixture, 4) Add the solvent first and the acid For example, a mixture of an anhydride and a catalyst or a mixture of an acid anhydride, a catalyst, and a solvent can be added.
[0048] セルロースのァシル化は発熱反応である力 本発明におけるセルロース混合エステ ルを製造する方法にお!、ては、ァシル化の際の最高到達温度が 50°C〜50°Cで あることが好ましく重合度のコントロールが容易であり、好ましくは 30°C〜45°Cであ り、より好ましくは— 20°C〜40°Cであり、特に好ましくは— 20°C〜35°Cである。好ま しいァシルイ匕時間は 0. 5時間〜 24時間であり、 1時間〜 12時間がより好ましぐ 1. 5 時間〜 6時間が特に好ま U、。 [0048] The acylation of cellulose is an exothermic reaction. In the method for producing a cellulose mixed ester in the present invention, the maximum temperature reached during the acylation is 50 ° C to 50 ° C. The degree of polymerization is preferably easy to control, preferably 30 ° C to 45 ° C, more preferably -20 ° C to 40 ° C, and particularly preferably -20 ° C to 35 ° C. is there. Like New time is 0.5 hours to 24 hours, 1 hour to 12 hours is more preferred 1. 5 hours to 6 hours is especially preferred U ,.
[0049] 本発明に用いられるセルロース混合エステルを製造する方法にお!、ては、ァシル 化反応の後に、反応停止剤を加えることが好ましい。反応停止剤としては、酸無水物 を分解するものであればいかなるものでもよぐ好ましい例として、水、アルコール（例 えばエタノール、メタノール、プロパノール、イソプロピルアルコールなど）またはこれ らを含有する組成物などを挙げることができる。反応停止剤の添加に際しては、反応 装置の冷却能力を超える大きな発熱が生じて、セルロース混合エステルの重合度を 低下させる原因となったり、セルロース混合エステルが望まな 、形態で沈殿したりす る場合があるなどの不都合を避けるため、水やアルコールを直接添加するよりも、酢 酸、プロピオン酸、酪酸等のカルボン酸と水との混合物を添加することが好ましぐ力 ルボン酸としては酢酸が特に好ま 、。カルボン酸と水の組成比は任意の割合で用 いることができるが、水の含有量が 5質量％〜80質量％、さらには 10質量％〜60質 量％、特には 15質量％〜50質量％の範囲であることが好ましい。 [0049] In the method for producing the cellulose mixed ester used in the present invention, it is preferable to add a reaction terminator after the acylation reaction. As the reaction terminator, any one that can decompose an acid anhydride may be used. Preferred examples include water, alcohol (eg, ethanol, methanol, propanol, isopropyl alcohol, etc.) or a composition containing them. Can be mentioned. Upon addition of the reaction terminator, a large exotherm that exceeds the cooling capacity of the reaction apparatus may occur, which may cause the degree of polymerization of the cellulose mixed ester to decrease, or the cellulose mixed ester may precipitate in a desired form. In order to avoid inconveniences such as, it is preferable to add a mixture of carboxylic acid such as acetic acid, propionic acid, butyric acid and water rather than adding water or alcohol directly. Favored ,. The composition ratio of the carboxylic acid and water can be used at any ratio, but the water content is 5% to 80% by mass, further 10% to 60% by mass, especially 15% to 50%. It is preferably in the range of mass%.
[0050] 前記反応停止剤は、ァシル化の反応容器に添加しても、反応停止剤の容器に反 応物を添加してもよい。反応停止剤は 3分間〜 3時間かけて添加することが好ましい 。反応停止剤の添加時間は、より好ましくは 4分間〜 2時間であり、さらに好ましくは 5 分間〜 1時間であり、特に好ましくは 10分間〜 45分間である。反応停止剤を添加す る際には反応容器を冷却しても冷却しなくてもよいが、解重合を抑制する目的から、 反応容器を冷却して温度上昇を抑制することが好ましい。また、反応停止剤を冷却し ておくことも好ましい。 [0050] The reaction terminator may be added to the reaction vessel for the acylation, or a reactant may be added to the reaction terminator vessel. The reaction terminator is preferably added over 3 minutes to 3 hours. The addition time of the reaction terminator is more preferably 4 minutes to 2 hours, further preferably 5 minutes to 1 hour, and particularly preferably 10 minutes to 45 minutes. When adding the reaction terminator, the reaction vessel may or may not be cooled, but for the purpose of suppressing depolymerization, it is preferable to cool the reaction vessel to suppress the temperature rise. It is also preferable to cool the reaction terminator.
[0051] ァシル化の停止後に、系内に残存している過剰の無水カルボン酸の加水分解およ びエステルイ匕触媒の一部または全部の中和のために、中和剤（例えば、カルシウム、 マグネシウム、鉄、アルミニウムまたは亜鉛の炭酸塩、酢酸塩、水酸化物または酸ィ匕 物）またはその溶液を添加してもよい。前記中和剤の溶媒としては、水、アルコール（ 例えばエタノール、メタノール、プロパノール、イソプロピルアルコールなど）、カルボ ン酸（例えば、酢酸、プロピオン酸、酪酸など）、ケトン（例えば、アセトン、ェチルメチ ルケトンなど）、ジメチルスルホキシドなどの極性溶媒、およびこれらの混合溶媒を好 まし 、例として挙げることができる。 [0051] After the acylation is stopped, a neutralizing agent (for example, calcium, etc.) is used for hydrolysis of excess carboxylic anhydride remaining in the system and neutralization of part or all of the ester catalyst. Magnesium, iron, aluminum or zinc carbonates, acetates, hydroxides or oxides) or solutions thereof may be added. Solvents for the neutralizing agent include water, alcohols (eg, ethanol, methanol, propanol, isopropyl alcohol, etc.), carboxylic acids (eg, acetic acid, propionic acid, butyric acid, etc.), ketones (eg, acetone, ethyl methyl ketone, etc.). , Polar solvents such as dimethyl sulfoxide, and mixed solvents thereof. It can be given as an example.
[0052] このようにして得られるセルロース混合エステルは、セルロース水酸基の全置換度 がほぼ 3に近いものである力 所望の置換度のものを得る目的で、少量の触媒 (一般 には、残存する硫酸などのァシル化触媒）と水との存在下で、 20〜90°Cに数分〜数 日間保つことによりエステル結合を部分的に加水分解し、所望のァシル置換度を有 するセルロース混合エステルまで変化させること（ 、わゆる熟成）が一般的に行われ る。部分加水分解の過程でセルロースの硫酸エステルも加水分解されることから、加 水分解の条件を調節することにより、セルロースに結合した硫酸エステルの量を削減 することができる。  [0052] The cellulose mixed ester obtained in this way has a force that the total substitution degree of the cellulose hydroxyl group is almost close to 3. For the purpose of obtaining a desired substitution degree, a small amount of catalyst (generally, the residual amount of Cellulose mixed ester having a desired degree of acyl substitution by partially hydrolyzing the ester bond by maintaining at 20 to 90 ° C for several minutes to several days in the presence of water and an acylation catalyst such as sulfuric acid) It is generally performed to change to (a kind of maturation). Since cellulose sulfate is also hydrolyzed during the partial hydrolysis, the amount of sulfate bound to cellulose can be reduced by adjusting the hydrolysis conditions.
[0053] 所望のセルロース混合エステルが得られた時点で、系内に残存して 、る触媒を、上 述のような中和剤またはその溶液を用いて完全に中和し、部分加水分解を停止させ ることが好ましい。反応溶液に対して溶解性が低い塩を生成する中和剤（例えば、炭 酸マグネシウム、酢酸マグネシウムなど）を添加することにより、溶液中あるいはセル口 ースに結合した触媒 (例えば、硫酸エステル)を効果的に除去することも好ま 、。  [0053] When the desired cellulose mixed ester is obtained, the catalyst remaining in the system is completely neutralized with the neutralizing agent as described above or a solution thereof, and subjected to partial hydrolysis. It is preferable to stop. By adding a neutralizing agent (for example, magnesium carbonate, magnesium acetate, etc.) that generates a salt having low solubility in the reaction solution, a catalyst (for example, sulfate ester) bound to the solution or the cell mouth. Also preferred to remove effectively.
[0054] セルロース混合エステル中の未反応物、難溶解性塩、その他の異物などを除去ま たは削減する目的として、ァシルイ匕後の反応混合物のろ過を行なうことが好ましい。 ろ過は、エステル化の完了力も再沈殿までの間のいかなる工程において行ってもよ い。ろ過圧や取り扱い性の制御の目的から、ろ過に先立って適切な溶媒で希釈する ことも好ましい。ろ過の際には、そのろ材は特に限定されず、布、ガラスフィルター、セ ルロース系ろ紙、セルロース系布フィルター、金属フィルター、ポリマー系フィルター（ 例えば、ポリプロピレン製フィルター、ポリエチレンフィルター、ポリアミド系フィルター 、フッ素系フィルターなど）を挙げることができる。そのフィルター口径サイズは、 0. 1 〜500 μ m力 S好ましく、より好ましくは 2〜200 μ mであり、さらには 3〜60 μ mである  [0054] For the purpose of removing or reducing unreacted substances, poorly soluble salts, and other foreign substances in the cellulose mixed ester, it is preferable to filter the reaction mixture after saponification. Filtration may be performed at any stage between the completion of esterification and reprecipitation. For the purpose of controlling filtration pressure and handleability, it is also preferable to dilute with an appropriate solvent prior to filtration. During filtration, the filter medium is not particularly limited, and cloth, glass filter, cellulose filter paper, cellulose cloth filter, metal filter, polymer filter (for example, polypropylene filter, polyethylene filter, polyamide filter, fluorine filter) System filters). The filter aperture size is preferably 0.1 to 500 μm force S, more preferably 2 to 200 μm, and even more preferably 3 to 60 μm.
[0055] 得られたセルロース混合エステル溶液を、水もしくはカルボン酸（例えば、酢酸、プ ロピオン酸、酪酸など）水溶液のような貧溶媒中に混合するか、セルロース混合エス テル反応溶液中に、貧溶媒を混合することにより、セルロース混合エステルを再沈殿 させ、洗浄および安定化処理により目的のセルロース混合エステルを得ることができ る。再沈殿によって、精製効率の向上、分子量分布や見かけ密度の調節を図ること ができる。再沈殿は連続的に行っても、一定量ずつバッチ式で行ってもよい。セル口 ース混合エステル溶液の濃度および貧溶媒の組成をセルロース混合エステルの置 換様式あるいは重合度により調整することで、再沈殿したセルロース混合エステルの 形態や分子量分布を制御することも好まし ヽ。 [0055] The obtained cellulose mixed ester solution is mixed in a poor solvent such as water or an aqueous solution of carboxylic acid (for example, acetic acid, propionic acid, butyric acid, etc.), or is mixed in a cellulose mixed ester reaction solution. By mixing the solvent, the cellulose mixed ester can be re-precipitated, and the desired cellulose mixed ester can be obtained by washing and stabilizing treatment. The By reprecipitation, purification efficiency can be improved and molecular weight distribution and apparent density can be adjusted. Reprecipitation may be carried out continuously or batchwise by a fixed amount. It is also preferable to control the morphology and molecular weight distribution of the re-precipitated cellulose mixed ester by adjusting the concentration of the cell mouth mixed ester solution and the composition of the poor solvent according to the replacement mode of the cellulose mixed ester or the degree of polymerization. .
[0056] また、生成したセルロース混合エステルは洗浄処理することが好ましい。洗浄には、 不純物を除去することができるものであればいかなるものでもよいが、通常は水また は温水が用いられる。洗浄水の温度は、好ましくは 5°C〜100°Cであり、さらに好まし くは 15°C〜90°Cであり、特に好ましくは 30°C〜80°Cである。洗浄処理はろ過と洗浄 液の交換を繰り返すいわゆるバッチ式で行っても、連続洗浄装置を用いて行ってもよ い。再沈殿および洗浄の工程で発生した廃液を再沈殿の貧溶媒として再利用したり 、蒸留などの手段によりカルボン酸などの溶媒を回収して再利用することも好ましい。 洗浄の進行はいかなる手段で追跡を行なってよいが、水素イオン濃度、イオンクロマ トグラフィー、電気伝導度、 ICP、元素分析、原子吸光スペクトルなどの方法を好まし い例として挙げることができる。処理により、セルロース混合エステル中のブレンステツ ド酸（硫酸、過塩素酸、トリフルォロ酢酸、 p—トルエンスルホン酸、メタンスルホン酸な ど）、中和剤（例えば、カルシウム、マグネシウム、鉄、アルミニウムまたは亜鉛の炭酸 塩、酢酸塩、水酸化物または酸化物）、中和剤と触媒との反応物、カルボン酸 (酢酸 、プロピオン酸、酪酸など）、中和剤とカルボン酸との反応物などを除去することがで き、セルロース混合エステルの安定性 (特に高温高湿度によるエステル結合の分解） を高めるために有効である。  [0056] The produced cellulose mixed ester is preferably washed. The cleaning can be performed with any material that can remove impurities, but usually water or warm water is used. The temperature of the washing water is preferably 5 ° C to 100 ° C, more preferably 15 ° C to 90 ° C, and particularly preferably 30 ° C to 80 ° C. The cleaning process may be performed in a so-called batch system in which filtration and replacement of the cleaning liquid are repeated, or may be performed using a continuous cleaning apparatus. It is also preferable to reuse the waste liquid generated in the reprecipitation and washing steps as a poor solvent for reprecipitation, or to recover and reuse a solvent such as carboxylic acid by means such as distillation. The progress of the cleaning may be traced by any means, but preferable examples include methods such as hydrogen ion concentration, ion chromatography, electrical conductivity, ICP, elemental analysis, and atomic absorption spectrum. Depending on the treatment, blended acid in cellulose mixed ester (sulfuric acid, perchloric acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, etc.), neutralizing agent (eg calcium, magnesium, iron, aluminum or zinc) Carbonate, acetate, hydroxide or oxide), reaction product of neutralizing agent and catalyst, carboxylic acid (acetic acid, propionic acid, butyric acid, etc.), reaction product of neutralizing agent and carboxylic acid, etc. Therefore, it is effective for improving the stability of the mixed ester of cellulose (especially, the decomposition of ester bond at high temperature and high humidity).
[0057] 温水処理による洗浄後のセルロース混合エステルは、安定性をさらに向上させたり 、カルボン酸臭を低下させるために、弱アルカリ（例えば、ナトリウム、カリウム、カルシ ゥム、マグネシウム、アルミニウムなどの炭酸塩、炭酸水素塩、水酸化物、酸化物など )の水溶液などで処理することも好ましい。残存不純物の量は、洗浄液の量、洗浄の 温度、時間、攪拌方法、洗浄容器の形態、安定化剤の組成や濃度により制御できる  [0057] The cellulose mixed ester after washing by hot water treatment has a weak alkali (for example, carbonic acid such as sodium, potassium, calcium, magnesium, aluminum, etc.) in order to further improve the stability or reduce the carboxylic acid odor. It is also preferable to treat with an aqueous solution of a salt, bicarbonate, hydroxide, oxide or the like. The amount of residual impurities can be controlled by the amount of cleaning liquid, cleaning temperature, time, stirring method, shape of cleaning container, composition and concentration of stabilizer.
[0058] 本発明にお 、てセルロース混合エステルの含水率を好まし 、量に調整するために は、セルロース混合エステルを乾燥することが好ましい。乾燥の方法については、目 的とする含水率が得られるのであれば特に限定されないが、加熱、送風、減圧、攪拌 などの手段を単独または組み合わせで用いることで効率的に行うことが好まし 、。乾 燥温度として 0〜200°Cが好ましぐさらに好ましくは 40〜180°Cであり、特に好ましく は 50〜160°Cである。この際、セルロース混合エステルのガラス転移点 (Tg)よりも低 い温度で乾燥することが好ましぐ Tgより 10°C以上低い温度で乾燥することがさらに 好ましい。乾燥によって得られる本発明におけるセルロース混合エステルは、その含 水率が 2質量％以下であることが好ましぐ 1質量％以下であることがさらに好ましぐ 0. 5質量％以下であることが特に好ましい。 [0058] In the present invention, the water content of the cellulose mixed ester is preferred and the amount is adjusted. It is preferable to dry the cellulose mixed ester. The drying method is not particularly limited as long as the desired moisture content can be obtained, but it is preferable that the drying method be carried out efficiently by using means such as heating, air blowing, decompression and stirring alone or in combination. . The drying temperature is preferably 0 to 200 ° C, more preferably 40 to 180 ° C, and particularly preferably 50 to 160 ° C. At this time, drying at a temperature lower than the glass transition point (Tg) of the cellulose mixed ester is preferable. Drying at a temperature lower by 10 ° C. or more than Tg is more preferable. The cellulose mixed ester in the present invention obtained by drying preferably has a water content of 2% by mass or less, more preferably 1% by mass or less, and 0.5% by mass or less. Particularly preferred.
[0059] セルロース混合エステルをフィルム製造の原料として用いる場合、粒子状または粉 末状であることが好ましい。乾燥後のセルロース混合エステルは、粒子サイズの均一 化や取り扱い性の改善のために、粉砕や篩がけを行ってもよい。セルロース混合エス テルが粒子状であるとき、使用する粒子の 90質量％以上は、 0. 5mn！〜 5mmの粒 子サイズを有することが好ましい。また、使用する粒子の 50質量％以上が lmn！〜 4 mmの粒子サイズを有することが好ましい。セルロース混合エステル粒子は、なるべく 球形に近 ヽ形状を有することが好ま Uヽ。  [0059] When cellulose mixed ester is used as a raw material for film production, it is preferably in the form of particles or powder. The cellulose mixed ester after drying may be pulverized or sieved in order to make the particle size uniform and improve the handleability. When the cellulose mixed ester is in the form of particles, 90% by mass or more of the particles used is 0.5mn! It preferably has a particle size of ~ 5mm. Also, more than 50% by mass of the particles used are lmn! Preferably it has a particle size of ~ 4 mm. It is preferable that the cellulose mixed ester particles have a nearly spherical shape as much as possible.
[0060] 本発明で好ましく用いられるセルロース混合エステルの重合度は、平均重合度 100 〜700であり、好ましく ίま 120〜550であり、さら【こ好ましく ίま 120〜400であり、特【こ 好ましくは平均重合度 130〜350である。平均重合度は、宇田らの極限粘度法 (宇 田和夫、斉藤秀夫、繊維学会誌、第 18卷第 1号、 105〜120頁、 1962年）に記載さ れるように、ゲル浸透クロマトグラフィー（GPC)による分子量分布測定などの方法に より測定できる。さらに特開平 9— 95538号公報に詳細に記載されている。  [0060] The polymerization degree of the cellulose mixed ester preferably used in the present invention is an average polymerization degree of 100 to 700, preferably 120 to 550, more preferably 120 to 400, and The average degree of polymerization is preferably 130 to 350. The average degree of polymerization was determined by gel permeation chromatography (Uda et al., Kazuo Uda, Hideo Saito, Journal of Textile Science, 18th No. 1, pages 105-120, 1962). It can be measured by methods such as molecular weight distribution measurement by GPC). Further details are described in JP-A-9-95538.
これらのセルロース混合エステルは 1種類のみを用いてもよぐ 2種以上混合してもよ い。このような重合度の調整は低分子量成分を除去することでも達成できる。低分子 成分の除去は、セルロース混合エステルを適当な有機溶媒で洗浄することにより実 施できる。また、本発明におけるセルロース混合エステルは、セルロース混合エステ ル以外の高分子成分を適宜混合したものでもよ!/ヽ。混合される高分子成分はセル口 ース混合エステルと相溶性に優れるものが好ましぐフィルムにしたときの透過率が 8 0%以上、さらに好ましくは 90%以上、さらに好ましくは 92%以上であることが好まし い。 These cellulose mixed esters may be used alone or in combination of two or more. Such adjustment of the degree of polymerization can also be achieved by removing low molecular weight components. Removal of low molecular weight components can be performed by washing the cellulose mixed ester with an appropriate organic solvent. In addition, the cellulose mixed ester in the present invention may be one obtained by appropriately mixing polymer components other than the cellulose mixed ester! / ヽ. The polymer component to be mixed is excellent in compatibility with the cell mouth mixed ester, but has a transmittance of 8 when the film is preferred. It is preferably 0% or more, more preferably 90% or more, and still more preferably 92% or more.
[0061] 本発明で用いられるセルロース混合エステルは、重量平均分子量 MwZ数平均分 子量 Mn比が 1. 5〜5. 5のものが好ましく用いられ、特に好ましくは 1. 5〜5. 0であ り、さら〖こ好ましくは 2. 0〜4. 5であり、さら〖こ好ましくは 2. 0〜4. 0のセノレロース混合 エステルが好ましく用いられる。セルロース混合エステルはペレツトイ匕することが好ま しぐ好ましいペレットの大きさは lmm3〜 10cm3であり、より好ましくは 5mm3〜5cm3 、さらに好ましくは 10mm3〜3cm3である。この後、上述の条件で乾燥する。得られた セルロース混合エステルは、その保存は環境による影響を受けに《するために、低 温暗所で保存する事が望ましい。さらに、保管用としてアルミニウムなどの防止素材 で作製された防湿袋や、 SUS製ドラムあるいはコンテナに保存する事がさらに好まし い。 [0061] The cellulose mixed ester used in the present invention is preferably one having a weight average molecular weight MwZ number average molecular weight Mn ratio of 1.5 to 5.5, particularly preferably 1.5 to 5.0. More preferably, it is 2.0 to 4.5, and a selenorose mixed ester of 2.0 to 4.0 is preferably used. Cellulose mixed ester is the size of the signaling preferred pellet preferred to Peretsutoi spoon is lmm 3 ~ 10cm 3, more preferably 5 mm 3 to 5 cm 3, more preferably from 10mm 3 ~3cm 3. Then, it dries on the above-mentioned conditions. It is desirable to store the obtained cellulose mixed ester in a low-temperature dark place so that the storage is influenced by the environment. Furthermore, it is more preferable to store it in a moisture-proof bag made of a prevention material such as aluminum, a SUS drum, or a container for storage.
[0062] その他、 6位置換度の大き!/、セルロース混合エステルの合成につ!、ては、特開平 1 1— 5851号、特開 2002— 212338号ゃ特開 2002— 338601号各公報などに記載 がある。セルロース混合エステルの他の合成法としては、塩基 (水酸化ナトリウム、水 酸ィ匕カリウム、水酸化バリウム、炭酸ナトリウム、ピリジン、トリェチルァミン、 tert—ブト キシカリウム、ナトリウムメトキシド、ナトリウムエトキシドなど）の存在下に、カルボン酸 無水物やカルボン酸ハライドと反応させる方法や、ァシル化剤として混合酸無水物（ カルボン酸'トリフルォロ酢酸混合無水物、カルボン酸'メタンスルホン酸混合無水物 など）を用いる方法も用いることができ、特に後者の方法は、炭素数の多いァシル基 や、カルボン酸無水物 酢酸 硫酸触媒による液相ァシルイ匕法が困難なァシル基 を導入する際には有効である。  [0062] In addition, the degree of substitution at the 6-position is great! / For the synthesis of cellulose mixed esters! For example, JP-A-11-5851, JP-A-2002-212338, JP-A-2002-338601, etc. There is a description. Other synthetic methods for cellulose mixed esters include bases (sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, pyridine, triethylamine, tert-butoxy potassium, sodium methoxide, sodium ethoxide, etc.). A method of reacting with a carboxylic acid anhydride or a carboxylic acid halide in the presence, or a method using a mixed acid anhydride (such as carboxylic acid 'trifluoroacetic acid mixed anhydride, carboxylic acid' methanesulfonic acid mixed anhydride) as an acylating agent In particular, the latter method is effective when introducing an acyl group having a large number of carbon atoms or an acyl group in which liquid phase acylation using a carboxylic anhydride, acetic acid or sulfuric acid catalyst is difficult.
[0063] (添加剤）  [0063] (Additive)
本発明のセルロース混合エステルは、微粒子と安定剤を含有するものであり、その 他に必要に応じてさらに種々の添加剤を溶融液の調製前力 調製後のいずれの段 階で添加してもよい。本発明における微粒子や安定剤以外の添加剤としては、紫外 線吸収剤、カルシウム、マグネシウムなど 2族金属の塩などの熱安定剤、帯電防止剤 、難燃剤、滑剤、油剤などが挙げられる。 [0064] (微粒子） The cellulose mixed ester of the present invention contains fine particles and a stabilizer, and other various additives may be added at any stage after preparation of the melt pre-preparation force as necessary. Good. Examples of additives other than fine particles and stabilizers in the present invention include heat stabilizers such as ultraviolet absorbers, salts of Group 2 metals such as calcium and magnesium, antistatic agents, flame retardants, lubricants, and oils. [0064] (Fine particles)
本発明におけるセルロース混合エステルは、平均一次粒子サイズが 0. 005 μ m~ 2 mである微粒子をセルロース混合エステルに対して、 0. 005〜1. 0質量0 /0を含 有する。該微粒子としては、無機化合物の微粒子または有機化合物の微粒子が挙 げられ、いずれでもよい。 Cellulose mixed ester in the present invention, relative to the average primary particle size of 0. 005 μ m ~ fine particles cellulose mixed ester is 2 m, and containing not from 0.005 to 1.0 mass 0/0. Examples of the fine particles include inorganic compound fine particles and organic compound fine particles, and any of them may be used.
[0065] 前記無機化合物としては、 SiO、 ZnO、 TiO、 SnO、 Al O、 ZrO、 In O、 MgO [0065] Examples of the inorganic compound include SiO, ZnO, TiO, SnO, AlO, ZrO, InO, and MgO.
2 2 2 2 3 2 2 3 2 2 2 2 3 2 2 3
、 BaO、 MoO、 V O、タルク、クレイ、焼成カオリン、焼成ケィ酸カルシウム、水和ケ BaO, MoO, V 2 O, talc, clay, calcined kaolin, calcined calcium silicate, hydrated kettle
2 2 5  2 2 5
ィ酸カルシウム、ケィ酸アルミニウム、ケィ酸マグネシウムおよびリン酸カルシウム等が 挙げられる。好ましぐ SiO、 ZnO、 TiO、 SnO、 Al O、 ZrO、 In O、 MgO、 BaO  Examples thereof include calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate. Preferred SiO, ZnO, TiO, SnO, Al O, ZrO, In O, MgO, BaO
2 2 2 2 3 2 2 3  2 2 2 2 3 2 2 3
、 MoO、および V Oの少なくとも 1種が好ましぐさらに好ましくは SiO、 TiO、 SnO At least one of Mo, MoO, and V 2 O is preferred, more preferably SiO, TiO, SnO
2 2 5 2 22 2 5 2 2
、 Al O、 ZrOである。 Al O, ZrO.
2 2 3 2  2 2 3 2
[0066] 前記 SiOの微粒子としては、例えば、ァエロジノレ R972、 R972V、 R974、 R812、  [0066] Examples of the SiO fine particles include Aerozinole R972, R972V, R974, R812,
2  2
200、 200V, 300、 R202、 OX50、 TT600 (以上、 日本ァエロジル (株）製）等の巿 販品が使用できる。また、前記 ZrOの微粒子としては、例えば、ァエロジル R976お  Commercial products such as 200, 200V, 300, R202, OX50, TT600 (above, Nippon Aerosil Co., Ltd.) can be used. Examples of the ZrO fine particles include Aerosil R976 and
2  2
よび R811 (以上、 日本ァエロジル (株)製)等の市販品が使用できる。  And commercial products such as R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.
[0067] 次に、本発明で使用されうる有機化合物の微粒子としては、例えばシリコーン榭脂 、弗素榭脂およびアクリル榭脂等のポリマーが好ましぐシリコーン榭脂が特に好まし い。前記シリコーン榭脂としては、三次元の網状構造を有するものが好ましぐ例えば トスノ ール 103、同 105、同 108、同 120、同 145、同 3120および同 240 (以上、東 芝シリコーン (株)製)等の商品名を有する市販品を使用できる。 [0067] Next, as the fine particles of the organic compound that can be used in the present invention, for example, a silicone resin in which a polymer such as a silicone resin, a fluorine resin, and an acrylic resin is preferable is particularly preferable. As the silicone resin, those having a three-dimensional network structure are preferable. For example, Tosnor 103, 105, 108, 120, 145, 3120 and 240 (above, Toshiba Silicone Co., Ltd. A commercial product having a trade name such as) can be used.
[0068] 本発明におけるセルロース混合エステルに含まれる微粒子の平均一次粒子サイズ としては、ヘイズを低く抑えるという観点から平均一次粒子サイズが 0. 005 μ m~2 μ mであり、好ましくは平均一次粒子サイズが 0. 005 μ m〜0. 5 μ mであり、特に好 ましくは平均一次粒子サイズが 0. 005 μ m〜0. 1 μ mである。ここで、微粒子の平均 一次粒子サイズの測定は、セルロース混合エステルフィルムを透過型電子顕微鏡 ( 倍率 50万〜 100万倍)で粒子の観察を行い、粒子 100個を観察し、その平均値をも つて平均一次粒子サイズとした。 [0068] The average primary particle size of the fine particles contained in the cellulose mixed ester in the present invention is 0.005 μm to 2 μm from the viewpoint of keeping haze low, and preferably the average primary particle. The size is from 0.005 μm to 0.5 μm, particularly preferably the average primary particle size is from 0.005 μm to 0.1 μm. Here, the average primary particle size of the fine particles was measured by observing the particles of the cellulose mixed ester film with a transmission electron microscope (magnification 500,000 to 1,000,000 times), observing 100 particles, and measuring the average value. Therefore, the average primary particle size was used.
[0069] これら微粒子のセルロース混合エステルへの添加方法は、常法によって混練する などにより行うことができるが、特に好ましくは予め溶媒に分散した微粒子とセルロー ス混合エステルとを混合分散させた後、溶媒を揮発させた固形物とし、これをセル口 ース混合エステル溶融物の製造過程で用いることが均一な溶融物が得られる点で好 ましい。なお、フィルム中に微粒子を均一に分散させるためには、混練機中やあるい は製膜時のダイ中でのシェア一により、前記微粒子が粉体力 微粒子化され微細分 散化される工程を含むことが好ましい。なお、微粒子と共に必要に応じてその他の機 能性素材 (例えば可塑剤および Zまたは紫外線吸収剤)を同時に溶媒に溶解して分 散し、混合して使用してもよい。 [0069] The method of adding these fine particles to the cellulose mixed ester is kneaded by a conventional method. However, it is particularly preferable to mix and disperse the fine particles dispersed in the solvent in advance and the cellulose mixed ester, and then form a solid in which the solvent has been volatilized. It is preferable to use in the production process because a uniform melt can be obtained. In order to uniformly disperse the fine particles in the film, a process in which the fine particles are made into fine powder particles and finely dispersed by a share in the kneader or in the die during film formation is performed. It is preferable to include. In addition to the fine particles, other functional materials (for example, a plasticizer and Z or an ultraviolet absorber) may be simultaneously dissolved in a solvent, dispersed, and mixed as necessary.
[0070] また、本発明の製造方法により最終的に得られたセルロース混合エステルフィルム 中での微粒子の平均二次粒子サイズは 0. 01〜5 /ζ πιであることが好ましぐ平均二 次粒子サイズが 0. 02〜3 mであることがより好ましぐ平均二次粒子サイズが 0. 0 2〜1 μ mであることが特に好ましい。ここで、前記微粒子の平均二次粒子サイズの測 定は、セルロース混合エステルフィルムを透過型電子顕微鏡 (倍率 10万〜 100万倍 )で粒子の観察を行! \粒子 100個を観察しその平均値をもって平均二次粒子サイ ズとした。  [0070] The average secondary particle size of the fine particles in the cellulose mixed ester film finally obtained by the production method of the present invention is preferably 0.01 to 5 / ζ πι. It is particularly preferred that the average secondary particle size is more preferably 0.02 to 1 μm, more preferably a particle size of 0.02 to 3 m. Here, the average secondary particle size of the fine particles was measured by observing the particles in the cellulose mixed ester film with a transmission electron microscope (magnification 100,000 to 1,000,000 times)! The value was taken as the average secondary particle size.
[0071] さらに、無機化合物から成る微粒子は、セルロース混合エステルフィルム中で安定 に存在させるために表面処理をすることが好ましい。無機微粒子は、表面処理を施し て用いることも好ましい。表面処理法としては、カップリング剤を使用する化学的表面 処理と、プラズマ放電処理やコロナ放電処理のような物理的表面処理とがあるが、本 発明においてはカップリング剤の使用が好ましい。前記カップリング剤としては、オル ガノアルコキシ金属化合物（例、シランカップリング剤、チタンカップリング剤等）が好 ましく用いられる。微粒子として無機微粒子を用いた場合 (特に SiOを用いた場合）  [0071] Furthermore, it is preferable that the fine particles comprising an inorganic compound are subjected to a surface treatment in order to stably exist in the cellulose mixed ester film. The inorganic fine particles are preferably used after being subjected to a surface treatment. Surface treatment methods include chemical surface treatment using a coupling agent and physical surface treatment such as plasma discharge treatment and corona discharge treatment. In the present invention, the use of a coupling agent is preferred. As the coupling agent, an organoalkoxy metal compound (eg, silane coupling agent, titanium coupling agent, etc.) is preferably used. When inorganic fine particles are used as fine particles (especially when SiO is used)
2  2
ではシランカップリング剤による処理が特に有効である。前記シランカップリング剤と しては下記一般式（11)で表されるオルガノシラン化合物が使用可能である。前記力 ップリング剤の使用量は特に限定されないが、好ましくは無機微粒子に対して、 0. 0 05〜5質量％使用することが推奨され、さらには 0. 01〜3質量％が好ましい。  Then, the treatment with a silane coupling agent is particularly effective. As the silane coupling agent, an organosilane compound represented by the following general formula (11) can be used. The amount of the force coupling agent to be used is not particularly limited, but preferably 0.05 to 5% by mass, more preferably 0.01 to 3% by mass, based on the inorganic fine particles.
[0072] R Si(OR' ) 般式（11) [0072] R Si (OR ') General formula (11)
(4  (Four
(式中、 R、 R'は、それぞれ独立に、水素原子、アルキル基、ァリール基、ァリル基、 フルォロアルキル基を表す。なお、前記アルキル基は、官能基として、エポキシ基、 アミノ基、アクリル基、イソシァネート基、および Zまたはメルカプト基を有していてもよ い。 Xは 0〜3の整数であり、好ましくは 0〜2の整数である。 ) (In the formula, R and R ′ each independently represents a hydrogen atom, an alkyl group, an aryl group, a aryl group, Represents a fluoroalkyl group. The alkyl group may have an epoxy group, amino group, acrylic group, isocyanate group, and Z or mercapto group as a functional group. X is an integer of 0 to 3, preferably an integer of 0 to 2. )
[0073] 前記一般式（11)で表されるオルガノシランの具体例としては下記のものを挙げるこ とができる力 本発明はこれらの例示に限定されるものではない。 [0073] Specific examples of the organosilane represented by the general formula (11) can include the following: The present invention is not limited to these examples.
一般式（11)において x=0の場合:テトラメトキシシラン、テトラエトキシシラン、テトラ イソプロボキシシラン、テトラー n—ブトキシシラン等； When x = 0 in general formula (11): tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra- n -butoxysilane, etc .;
x= lの場合:メチルトリメトキシシラン、メチルトリエトキシシラン、ェチルトリメトキシシ ラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、フエニルトリメトキシシラン、フ ェ-ルトリエトキシシラン、 CF CH CH Si (OCH )  When x = l: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, CF CH CH Si (OCH)
3 2 2 3 3、 CF (CF ) CH CH Si(OCH  3 2 2 3 3, CF (CF) CH CH Si (OCH
3 2 5 2 2 3 3 2 5 2 2 3
)、 γーグリシドキシプロピルトリメトキシシラン、 γ—グリシドキシプロピノレトリエトキシ), Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropinoletriethoxy
3 Three
シラン、 γ —ァミノプロピルトリメトキシシラン、 γ —トリメトキシシリルプロピルイソシァネ ート、 γ—メルカプトプロピルトリメトキシシラン、 γ—メタクリロキシプロピルトリメトキシ シラン、 y—アタリロキシプロピルトリメトキシシラン等；  Silane, γ-aminopropyltrimethoxysilane, γ-trimethoxysilylpropylisocyanate, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, y-attaryloxypropyltrimethoxysilane, etc .;
x= 2の場合：ジメチノレジメトキシシラン、ジメチノレジェトキシシラン、 γ—グリシドキシ プロピルメチルジメトキシシラン、 γ—ァミノプロピルメチルトリエトキシシラン、 γ—メ ルカプトプロピルメチルジメトキシシラン、 γ—メタクリロキシプロピルメチルジメトキシ シラン等が挙げられる。  When x = 2: dimethylenoresimethoxysilane, dimethylenoletoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-methacryloxypropyl And methyldimethoxysilane.
[0074] また、硬化膜の硬さおよび脆性の調節や官能基導入の目的で、異なる 2種以上の オルガノシランを組み合わせて用いることもできる。  [0074] For the purpose of adjusting the hardness and brittleness of the cured film and introducing functional groups, two or more different organosilanes may be used in combination.
[0075] 前記カップリング剤は、微粒子への直接処理方法とインテグラルブレンド法とによつ て処理される。前記直接法は乾式法とスラリー法とスプレー法とに大きく分類される。 直接処理方法で得られた微粒子はバインダー中に添加され微粒子の表面に確実に カップリング剤が修飾できる点で優れて ヽる。その中で乾式法は微粒子にシランカツ プリング剤のアルコール水溶液、有機溶剤または水溶液中で均一に分散させた後乾 燥して実施するものであり一般的である。ヘンシェルミキサー、スーパーミキサー、レ ディミキサー、 V型プレンダー、オープン-一ダ一等の攪拌機を使用するのが好まし い。これらの攪拌機の中でも特にオープン-一ダ一が好ましい。微粒子と少量の水、 または水を含有する有機溶剤そしてカップリング剤を混合しオープン-一ダ一で攪 拌して水を除去したさらに微細分散するのが好ましい。 [0075] The coupling agent is treated by a direct treatment method for fine particles and an integral blend method. The direct method is roughly classified into a dry method, a slurry method, and a spray method. Fine particles obtained by the direct treatment method are excellent in that they can be added to the binder and the coupling agent can be reliably modified on the surface of the fine particles. Among them, the dry method is generally carried out by uniformly dispersing fine particles in an alcohol aqueous solution, organic solvent or aqueous solution of a silane coupling agent, followed by drying. It is preferable to use a Henschel mixer, a super mixer, a ready mixer, a V-type blender, an open-agitator or the like. Among these agitators, open-one is particularly preferable. Fine particles and a small amount of water, Alternatively, it is preferable that the organic solvent containing water and the coupling agent are mixed and stirred in an open-head manner to remove water and further finely dispersed.
[0076] また、スラリー法は微粒子の製造において微粒子をスラリー化する工程がある場合 にそのスラリー中にカップリング剤を添加する方法であり、製造工程で処理できる利 点を有する。また、スプレー法は微粒子の乾燥工程において微粒子にカップリング剤 を添加する方法であり、製造工程で処理できる利点を有するが処理の均一性に難点 がある。  [0076] In addition, the slurry method is a method of adding a coupling agent to the slurry when there is a step of slurrying the fine particles in the production of the fine particles, and has an advantage that it can be processed in the production process. The spray method is a method of adding a coupling agent to the fine particles in the fine particle drying step, and has an advantage that it can be treated in the production step, but has a problem in uniformity of treatment.
[0077] 前記インテグラルブレンド法にっ 、て述べると、インテグラルブレンド法は、カツプリ ング剤を微粒子とバインダーとの中に添加する方法であり、良く混練する必要がある が簡便な方法である。本発明における微粒子は、セルロース混合エステルに対して 0 . 005〜1. 0質量％を含有されることを特徴とする。前記微粒子の含有量は、好まし くは、 0. 01〜0. 8質量％であり、さらには 0. 02〜： L 0質量％が特に好ましい。  [0077] The integral blend method is described as follows. The integral blend method is a method of adding a coupling agent into fine particles and a binder, and it is a simple method that needs to be well kneaded. . The fine particles in the present invention are characterized by containing 0.005 to 1.0 mass% with respect to the cellulose mixed ester. The content of the fine particles is preferably 0.01 to 0.8% by mass, more preferably 0.02 to: L 0% by mass.
[0078] (安定剤）  [0078] (Stabilizer)
本発明におけるセルロース混合エステルは、 1種類以上の安定剤をセルロース混 合エステルに対して 0. 01〜3質量％含有する。本発明で用いられる安定剤としては 、フエノール系安定剤、リン系（フォスファイト系）安定剤、チォエーテル系安定剤、ス ズ系安定剤およびアミン系安定剤よりなる群から選択される 1種類以上の安定剤であ る。本発明においては、必要に応じて要求される性能を損なわない範囲内でこれら 以外の安定ィ匕作用を有する化合物を添加することができる。  The cellulose mixed ester in the present invention contains 0.01 to 3% by mass of one or more stabilizers with respect to the cellulose mixed ester. The stabilizer used in the present invention is one or more selected from the group consisting of a phenol stabilizer, a phosphorus (phosphite) stabilizer, a thioether stabilizer, a soot stabilizer and an amine stabilizer. It is a stabilizer. In the present invention, a compound having a stabilizing effect other than these can be added as long as the required performance is not impaired.
[0079] 上記リン系安定剤としては、特開 2004— 182979号公報の [0023]〜 [0039]に記 載の化合物をより好ましく用いることができる。亜リン酸エステル系安定剤の具体例と しては、特開昭 51— 70316号公報、特開平 10— 306175号公報、特開昭 57— 78 431号公報、特開昭 54— 157159号公報、特開昭 55— 13765号公報に記載の化 合物を挙げることができる。さらに、その他の安定剤としては、発明協会公開技報 (公 技番号 2001— 1745、 2001年 3月 15日発行、発明協会） 17頁〜 22頁に詳細に記 載されて!、る素材を好ましく用いることができる。  [0079] As the phosphorus stabilizer, compounds described in [0023] to [0039] of JP-A No. 2004-182979 can be used more preferably. Specific examples of the phosphite ester stabilizer include JP-A-51-70316, JP-A-10-306175, JP-A-57-78431, JP-A-54-157159. And compounds described in JP-A-55-13765. In addition, other stabilizers are described in detail on pages 17 to 22 of the Inventors Association Technical Report (Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Inventions)! It can be preferably used.
[0080] 上記フエノール系安定剤としては、公知の任意のフエノール系安定剤を使用するこ とができる。好ましいフエノール系安定剤としては、ヒンダードフエノール系安定剤が 挙げられる。ヒンダードフエノール系安定剤の例としては、例えば、 1, 3, 5 トリス（3 , 5 ジ— tert—ブチル—4 ヒドロキシベンジル）—s トリジアン— 2, 4, 6— (1H, 3H, 5H)トリオン、 1, 1, 3 トリス（2—メチル 4 ヒドロキシ一 5— tert—ブチルフ ェ -ル）ブタン、テトラキス〔メチレン（3, 5—ジ tert—ブチルー 4ーヒドロキシハイド ロシ ンナメート）〕メタン、および 3, 9 ビス {2—〔3—（3— tert—ブチルー 4ーヒドロ キシ 5 メチルフエ-ル）プロピオ-ルォキシ〕 1, 1 ジメチルェチル}ー2, 4, 8 , 10—テトラオキサスピロ〔5, 5〕ゥンデカン、 2, 6 ジ tert—ブチルー p クレゾ一 ル、 2, 2，ーメチレンビス（4ーメチルー 6—tert ブチルフエノール）、 2, 2'—メチレ ンビス（4ーェチルー 6— tert ブチルフエノール）、 4, 4'ーブチリデンビス（3—メチ ルー 6— tert ブチルフエノール）、 4, 4，ーチォビス（3—メチルー 6— tert ブチル フエノール）、テトラキス [メチレン（3, 5—ジ tert ブチルー 4ーヒドロキシフエ-一 ル）プロピオネート]メタン、 n—ォクタデシルー 3—（4，ーヒドロォキシ 3，， 5，ージー tert—ブチルーフエニール）プロピオネート、トリスー 3, 5—ジー tert—ブチルー 4 ヒドロキシフエ-ル）イソシァヌレート、 2, 6 ジ一 tert—ブチル 4—メチルフエノー ル、 n—ォクタデシル 3— (3，， 5，—ジ— tert—ブチル—4，—ヒドロキシフエ-ル）プ 口ピオネート、テトラキス [3—（3、 5—ジ tert ブチルー 4ーヒドロキシフエニール） プロピオ-ルォキシメチル]メタン、トリス [N— (3、 5—ジ— tert—ブチル—4—ヒドロ キシベンジル)イソシァヌレート、ブチリデン一 1, 1—ビス一（2—メチル 4 ヒドロキ シ 5— t—ブチルフエ-ル）、トリエチレングリコール ビス [3— (3— tert—ブチルー 4ーヒドロキシー5—メチルフエ-ル）プロピオネート]が挙げられる。高分子量多環ヒ ンダードフエノール系酸ィ匕防止剤がより好ましい。さらに好ましくは、 1, 1, 3 トリス（ 2—メチル 4 ヒドロキシ一 5— tert ブチルフエ-ル）ブタンである。これらは、住 友化学からスミライザ一 BHT、スミライザ一 BP— 76、スミライザ一 BBM— S、スミライ ザ一 GA— 80として、またチノく'スペシャルティ'ケミカルズ社から Irganox 1076、 Irg anox 1000、 Irganox 3114、 Irganox 245として市販されている。 [0080] As the phenol-based stabilizer, any known phenol-based stabilizer can be used. Preferred phenolic stabilizers include hindered phenolic stabilizers. Can be mentioned. Examples of hindered phenol stabilizers include, for example, 1, 3, 5 tris (3, 5 di-tert-butyl-4-hydroxybenzyl) -s tridian-2, 4, 6- (1H, 3H, 5H) Trione, 1, 1, 3 tris (2-methyl-4-hydroxy-1-5-tert-butylphenyl) butane, tetrakis [methylene (3,5-ditert-butyl-4-hydroxyhydracinnamate)] methane, and 3 , 9 Bis {2- [3- (3-tert-Butyl-4-hydroxy-5-methylphenol) propio-loxy] 1,1 dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane 2,6 di-tert-butyl-p-cresol, 2,2, -methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenbis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl 6-tert butyl fuel 4,4, -thiobis (3-methyl-6-tertbutylphenol), tetrakis [methylene (3,5-ditertbutyl-4-hydroxyphenol) propionate] methane, n-octadecyl-3- (4, hydroxy) 3, 5, 5-ji tert-butyl-phenyl) propionate, tris 3,5-di-tert-butyl 4-hydroxyphenol) isocyanurate, 2, 6 di-tert-butyl 4-methylphenol, n-octadecyl 3— (3,5, -di-tert-butyl-4, -hydroxyphenol) propionate, tetrakis [3- (3,5-ditertbutyl-4-hydroxyphenyl) propio-oxymethyl] methane, tris [N— (3,5-Di-tert-butyl-4-hydroxybenzyl) isocyanurate, butylidene 1,1-bis-1- (2-methyl 4-hydroxy 5—t— Butylphenol), triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenol) propionate]. High molecular weight polycyclic hindered phenolic anti-oxidants are more preferred. More preferred is 1,1,3 tris (2-methyl-4-hydroxy-5-tertbutylphenol) butane. These are Sumitomo Chemical's Sumitizer 1 BHT, Sumilizer 1 BP-76, Sumilizer 1 BBM- S, Sumizer 1 GA-80, and Chinoku 'Specialty' Chemicals, Inc. Irganox 1076, Irg anox 1000, Irganox 3114, Commercially available as Irganox 245.
上記リン系安定剤としては、従来公知の任意のリン系安定剤を用いることができる。 好ましいリン系安定剤の好ましい具体例としては、ビス（2, 6 ジ tert—ブチルー 4 —メチルフエ-ル）ペンタエリスリトール一ジ一ホスファイト、トリス（2, 4 ジ一 tert— ブチルフエ-ル）フォスファイト、ジステアリル'ペンタエリスリトール ジフォスファイト、 トリオクタデシル フォスファイト、トリノ-ルフエ-ル フォスファイト、トリフエ-ル フォ スフアイト、 9, 10 ジヒドロー 9 ォキサ · 10 フォスファ 'フエナンスレン 10—ォキ サイド、テトラキス（2, 4 ジ一 tert—ブチルフエ-ル） 4, 4'—ビフエ-レンジフォ スフアイトを挙げることができる。リン系安定剤の中では、亜リン酸エステル系酸化防 止剤がより好ましい。さらに好ましくは、ビス（2, 6 ジ一 tert ブチル 4—メチルフ 工 -ル）ペンタエリスリトール—ジ—ホスファイトである。これらは、旭電化からアデカタ ブ 1178、同 2112、同 PEP— 8、同 PEP— 24G、 PEP— 36G、同 HP— 10として、ま たクラリアント社から Sandostab P—EPQとして市販されており、入手可能である。 As the phosphorus stabilizer, any conventionally known phosphorus stabilizer can be used. Preferable specific examples of preferred phosphorus stabilizers include bis (2,6 di tert-butyl-4-methylphenol) pentaerythritol monodiphosphite, tris (2,4 di tert- Butylphenol) phosphite, distearyl 'pentaerythritol diphosphite, trioctadecyl phosphite, trinoyl phosphite, triphenyl phosphite, 9, 10 dihydro 9 oxa 10 phospha' phenanthrene 10-oxy Side, tetrakis (2,4 di-tert-butylphenol) 4,4'-biphenol-range phosphate. Among the phosphorus stabilizers, phosphite antioxidants are more preferable. More preferred is bis (2,6-di-tert-butyl 4-methyl propyl) pentaerythritol-di-phosphite. These are commercially available from Asahi Denka as Adekatab 1178, 2112, PEP-8, PEP-24G, PEP-36G, HP-10, and Sandostab P-EPQ from Clariant. It is.
[0082] 上記チォエーテル系安定剤としては、公知の任意のチォエーテル系安定剤を用い ることができる。好ましいチォエーテル系安定剤の具体例としては、テトラキス〔メチレ ン 3—（ドデシルチオ）プロピオネート〕メタン、 3, 3，一チォジプロピオン酸、ジラゥリ ル'チォジプロピオネート、ジステアリル.チォジプロピオネートが挙げられる。これら は、住友化学からスミライザ一 TPL、同 TPM、同 TPS、同 TDPとして市販されている [0082] As the thioether stabilizer, any known thioether stabilizer can be used. Specific examples of preferred thioether stabilizers include tetrakis [methylen-3- (dodecylthio) propionate] methane, 3,3,4 monodipropionic acid, dilauryl thiodipropionate, distearyl thiodipropionate. Can be mentioned. These are marketed by Sumitomo Chemical as Sumilizer I TPL, TPM, TPS, TDP.
[0083] 上記スズ系安定剤としては、公知の任意のスズ系安定剤を用いることができる。好ま しいスズ系安定剤の具体例としては、ォクチル錫マレエートポリマー、モノステアリル 錫トリス (イソォクチルチオグリコレート）、ジブチル錫ジラウレートが挙げられる。 [0083] As the tin-based stabilizer, any known tin-based stabilizer can be used. Specific examples of preferred tin-based stabilizers include octyl tin maleate polymer, monostearyl tin tris (isooctyl thioglycolate), and dibutyl tin dilaurate.
[0084] また、上記アミン系安定剤としては、公知の任意のアミン系安定剤を用いることがで きる。好ましいアミン系安定剤の具体例としては、 2, 2' メチレンビス〔4— (1, 1, 3, 3—テトラメチルブチル） 6— [ (2H ベンゾトリァゾールー 2 ィル）フエノール]〕、 テトラキス（2, 2, 6, 6—テトラメチル一 4 ピペリジル） 1, 2, 3, 4 ブタンテトラカル ボキシラート、フエ-ルー β ナフチルァミン、 Ν—Ν，ージ—sec ブチルー ρ—フエ -レンジァミン、 N— N，ージフエ-ルー p フエ-レンジァミン、 N フエ-ルー N，一 シクロへキシル p フエ-レンジァミン、 N—イソプロピル N，一フエニル—— p— フエ二レンジァミン、 4 -ベンゾィルォキシ 2— 2—6 - 6—テトラメチルピペラジン、 ビス（2— 2— 6— 6—テトラメチル一 4 ピぺリジン）セバケイト、ビス [(1, 2, 2, 6, 6、 —ペンタメチル— 4 ピベリジ-ル） 2— (3, 5 ジ— tert—ブチル—4 ヒドロキシべ ンジル） 2— n—ブチル マロネート、テトラキス（2、 2、 6、 6—テトラメチル一 4 ピ ベリジ-ル） 1, 2, 3, 4 ブタン—テ卜ラカルボキシレー卜、テ卜ラキス（1、 2、 2、 6、 6 ペンタメチルー 4ーピベリジ-ル） 1, 2, 3, 4 ブタンーテトラカルボキシレート、等 が挙げられる。これらは、旭電化からアデカスタブ LA— 57、同 LA—52、同 LA— 67 、同 LA— 62、同 LA— 77として、またチノく'スぺシャリティーケミカノレズ社から TINU VIN 765、同 144として市販されている。 [0084] As the amine stabilizer, any known amine stabilizer can be used. Specific examples of preferred amine stabilizers include 2,2 'methylenebis [4- (1, 1, 3, 3-tetramethylbutyl) 6-[(2H benzotriazole-2-yl) phenol]], tetrakis (2, 2, 6, 6—tetramethyl-4-piperidyl) 1, 2, 3, 4 butanetetracarboxylate, ferulic β naphthylamine, Ν—Ν, ジ -sec butyl-ρ-phee-rangeamamine, N— N, -diphenyl-p-phenylenediamine, N-phenyl-N, monocyclohexyl p-phenylenediamine, N-isopropyl N, monophenyl-- p-phenyldiamine, 4-benzoyloxy 2--2-6-6 —Tetramethylpiperazine, bis (2—2—6—6-tetramethyl-4-piperidine) sebacate, bis [(1, 2, 2, 6, 6, —pentamethyl—4 piperidyl) 2— (3 , 5 Di-tert-butyl-4 hydroxy 2) n-Butyl malonate, tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) 1, 2, 3, 4 butane-tetracarboxylate, tetrakis (1, 2, 2, 6, 6 pentamethyl-4-piberidyl) 1, 2, 3, 4 butane-tetracarboxylate, and the like. These are Asahi Denka's Adeka Stub LA-57, LA-52, LA-67, LA-62, LA-77, and TINU VIN 765, from Chinoku's Specialty Chemicals. It is marketed as 144.
[0085] 本発明に用いられる安定剤は、高分子量多環ヒンダードフエノール系酸ィ匕防止剤と リン酸エステル系酸ィ匕防止剤とを組み合わせたものであることが好まし 、。さらに好ま しくは、 1, 1, 3 トリス（2—メチル 4 ヒドロキシ一 5— tert—ブチルフエ-ル）ブタ ンとビス（2, 6 ジー tert ブチル 4 メチルフエ-ル）ペンタエリスリトールージー ホスファイトとを組み合わせたものである。 [0085] The stabilizer used in the present invention is preferably a combination of a high molecular weight polycyclic hindered phenolic acid oxidant and a phosphate ester type acid oxidant. More preferably, 1,1,3 tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane and bis (2,6-ditertbutyl-4-methylphenol) pentaerythritol phosphite are used. It is a combination.
本発明における安定剤の添加量は、セルロース混合エステルを基準として、 0. 01 〜3質量％である。より好ましくは、 0. 03〜2質量％である。さらに好ましくは、 0. 05 〜1. 5質量％である。安定剤の添加量が 0. 01質量％より少ない場合は、安定剤の 効果が得られに《着色が激しくなるという問題がある。また、安定剤の添加量が 3質 量％より多い場合は、面状が悪化するという問題がある。  The addition amount of the stabilizer in the present invention is 0.01 to 3% by mass based on the cellulose mixed ester. More preferably, the content is 0.03 to 2% by mass. More preferably, it is 0.05-1.5 mass%. When the added amount of the stabilizer is less than 0.01% by mass, the effect of the stabilizer is obtained, and there is a problem that the coloring becomes intense. In addition, when the amount of stabilizer added is more than 3% by mass, there is a problem that the surface condition deteriorates.
[0086] (その他の添加剤）  [0086] (Other additives)
本発明におけるセルロース混合エステルには、各調製工程において用途に応じた 種々の添加剤 (例えば、可塑剤、紫外線防止剤、劣化防止剤、微粒子、光学特性調 整剤など)を加えることができる。またその添加する時期は溶融物（ドープ)作製工程 にお 、て何れでも添加してもよ!/、が、溶融物作製工程 (ドープ調製工程)の最後の調 製工程に添加剤を添加し調製する工程を加えてもよい。  Various additives (for example, plasticizers, ultraviolet inhibitors, deterioration inhibitors, fine particles, optical property modifiers, etc.) according to the use can be added to the cellulose mixed ester in the present invention in each preparation step. In addition, it can be added at any time during the melt (dope) production process! However, an additive is added to the final preparation process of the melt production process (dope preparation process). A step of preparing may be added.
[0087] 本発明のセルロース混合エステルに可塑剤を添加すれば、セルロース混合エステ ルの結晶融解温度 (Tm)を下げることができる。本発明に用いる可塑剤の分子量は 特に限定されるものではなぐ低分量でもよく高分子量でもよい。可塑剤の種類として は、リン酸エステル類、アルキルフタリルアルキルグリコレート類、カルボン酸エステル 類、多価アルコールの脂肪酸エステル類などが挙げられる。それらの可塑剤の形状 としては固体でもよく油状物でもよい。すなわち、その融点や沸点において特に限定 されるものではない。溶融製膜を行なう場合は、不揮発性を有するものを特に好まし く使用することがでさる。 [0087] If a plasticizer is added to the cellulose mixed ester of the present invention, the crystal melting temperature (Tm) of the cellulose mixed ester can be lowered. The molecular weight of the plasticizer used in the present invention is not particularly limited, and may be a low molecular weight or a high molecular weight. Examples of the plasticizer include phosphate esters, alkylphthalylalkyl glycolates, carboxylic acid esters, and fatty acid esters of polyhydric alcohols. These plasticizers may be solid or oily. In other words, the melting point and boiling point are particularly limited Is not to be done. When performing melt film formation, it is particularly preferable to use a non-volatile material.
[0088] 上記リン酸エステルの具体例としては、例えばトリフエ-ルホスフェート、トリブチルホ スフエート、トリブトキシェチルホスフェート、トリクレジルホスフェート、トリオクチルホス フェート、トリナフチルホスフェート、トリキシリルォスフェート、トリスオルトービフエ-ル ホスフェート、クレジノレフエ-ノレホスフェート、オタチノレジフエ-ノレホスフェート、ビフエ -ルジフエ-ルホスフェート、 1, 4一フエ-レンーテトラフエ-ル燐酸エステル等を挙 げることができる。また特表平 6— 501040号公報の請求項 3〜7に記載のリン酸エス テル系可塑剤を用いることも好ましい。  [0088] Specific examples of the phosphate ester include, for example, triphenyl phosphate, tributyl phosphate, tribubutychetyl phosphate, tricresyl phosphate, trioctyl phosphate, trinaphthyl phosphate, trixylyl phosphate, trisulol. Examples include tobiphenol phosphate, credinorephenol-norephosphate, otachinoresphie-norephosphate, biphenyl-diphenyl phosphate, and 1,4-phenol-tetraphenyl phosphate. It is also preferable to use the phosphoric ester plasticizer described in claims 3 to 7 of JP-T-6-501040.
[0089] 上記アルキルフタリルアルキルグリコレート類としては、例えばメチルフタリルメチル グリコレート、ェチノレフタリノレエチノレグリコレート、プロピノレフタリノレプロピノレグリコレート [0089] Examples of the alkyl phthalyl alkyl glycolates include, for example, methyl phthalyl methyl glycolate, ethino retinalino ethinore glycolate, propino phthalino repropenore glycolate
、ブチルフタリルブチルダリコレート、ォクチルフタリルオタチルダリコレート、メチルフ タリルェチルダリコレート、ェチルフタリルメチルダリコレート、ェチルフタリルプロピル グリコレート、メチルフタリルブチルダリコレート、ェチルフタリルブチルダリコレート、ブ チルフタリルメチルダリコレート、ブチルフタリルェチルダリコレート、プロピルフタリル ブチルダリコレート、ブチルフタリルプロピルグリコレート、メチルフタリルォクチルグリ コレート、ェチルフタリルオタチルダリコレート、ォクチルフタリルメチルダリコレート、ォ クチルフタリルェチルダリコレート等が挙げられる。 , Butyl phthalyl butyl dallicolate, octyl phthalyl octyl dallicolate, methyl phthalyl ethyl dallicolate, ethyl phthalyl methyl dallicolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl dallicolate Butyl butyl alcoholate, butyl phthalyl methyl dalicolate, butyl phthalyl ethyl dalicolate, propyl phthalyl butyl dalicolate, butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl dalicolate, Examples include octyl phthalyl methyl dallicolate, octyl phthalyl ethyl dallicolate, and the like.
[0090] 上記カルボン酸エステルとしては、例えばジメチルフタレート、ジェチルフタレート、 ジブチルフタレート、ジォクチルフタレートおよびジェチルへキシルフタレート等のフ タル酸エステル類、およびクェン酸ァセチルトリメチル、クェン酸ァセチルトリエチル、 タエン酸ァセチルトリブチル等のクェン酸エステル類、ジメチルアジペート、ジブチル アジペート、ジイソブチルアジペート、ビス（2—ェチルへキシル）アジペート、ジィソデ シルアジペート、ビス（ブチルジグリコールアジペート）等のアジピン酸エステル類、テ トラオクチルビ口メリテート、トリオクチルトリメリテートなどの芳香族多価カルボン酸エス テル類、ジブチルアジペート、ジォクチルアジペート、ジブチルセバケート、ジォクチ ルセバケート、ジェチルァゼレート、ジブチルァゼレート、ジォクチルァゼレートなどの 脂肪族多価カルボン酸エステル類、グリセリントリアセテート、ジグリセリンテトラァセテ ート、ァセチル化グリセライド、モノダリセライド、ジグリセライドなどの多価アルコール の脂肪酸エステル類などを挙げることができる。またその他、ォレイン酸プチル、リシ ノール酸メチルァセチル、セバシン酸ジブチル、トリァセチン等を単独あるいは併用 するのが好ましい。 [0090] Examples of the carboxylic acid ester include phthalic acid esters such as dimethyl phthalate, jetyl phthalate, dibutyl phthalate, dioctyl phthalate and jetyl hexyl phthalate, Citrates such as acetytributyl butylate, adipates such as dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, disodecyl adipate, bis (butyl diglycol adipate), Aromatic polycarboxylic acid esters such as tetraoctylbi-mouth melitate and trioctyl trimellitate, dibutyl adipate, dioctyl adipate, dibutyl sebacate, dioctyl sebacate, jetty Aliphatic polycarboxylic esters such as lucerate, dibutyl azelate, dioctyl azelate, glycerin triacetate, diglycerin tetraacetate And fatty acid esters of polyhydric alcohols such as glycerides, acetylated glycerides, monodallylides, and diglycerides. In addition, it is preferable to use octyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, triacetin, etc. alone or in combination.
[0091] また、ポリエチレンアジペート、ポリブチレンアジペート、ポリエチレンサクシネート、 ポリブチレンサクシネートなどのダリコールと二塩基酸とからなる脂肪族ポリエステル 類、ポリ乳酸、ポリダリコール酸などのォキシカルボン酸力 なる脂肪族ポリエステル 類、ポリ力プロラタトン、ポリプロピオラタトン、ポリバレロラタトンなどのラタトン力もなる 脂肪族ポリエステル類、ポリビニルピロリドンなどのビニルポリマー類などの高分子量 系可塑剤も挙げられる。可塑剤には、これらを単独もしくは低分量可塑剤と併用して 使用することができる。  [0091] In addition, aliphatic polyesters composed of dalicol and dibasic acid such as polyethylene adipate, polybutylene adipate, polyethylene succinate, and polybutylene succinate, and aliphatic polyesters composed of oxycarboxylic acid such as polylactic acid and polydaricholic acid Also included are high molecular weight plasticizers such as aliphatic polyesters that also have rataton power, such as polystrength polylataton, polypropiolatatone, polyvalerolatatone, and vinyl polymers such as polyvinylpyrrolidone. These plasticizers can be used alone or in combination with a low-part plasticizer.
[0092] 上記多価アルコール系可塑剤は、セルロース脂肪酸エステルとの相溶性が良ぐま た熱可塑化効果が顕著に現れるグリセリンエステル、ジグリセリンエステルなどグリセ リン系のエステル化合物やポリエチレングリコールやポリプロピレングリコールなどの ポリアルキレングリコール、ポリアルキレングリコールの水酸基にァシル基が結合した 化合物などである。具体的なグリセリンエステルとして、グリセリンジアセテートステア レート、グリセリンジアセテートパルミテート、グリセリンジアセテートミスチレート、グリセ リンジアセテートラウレート、グリセリンジアセテート力プレート、グリセリンジアセテート ノナネート、グリセリンジアセテートオタタノエート、グリセリンジアセテートヘプタノエー ト、グリセリンジアセテートへキサノエート、グリセリンジアセテートペンタノエート、グリ セリンジアセテートォレート、グリセリンアセテートジカプレート、グリセリンアセテートジ ノナネート、グリセリンアセテートジォクタノエート、グリセリンアセテートジヘプタノエー ト、グリセリンアセテートジカプロエート、グリセリンアセテートジバレレート、グリセリンァ セテートジブチレート、グリセリンジプロピオネート力プレート、グリセリンジプロビオネ ートラウレート、グリセリンジプロピオネートミスチレート、グリセリンジプロピオネートパ ノレミテート、グリセリンジプロピオネートステアレート、グリセリンジプロピオネートォレー ト、グリセリントリブチレート、グリセリントリペンタノエート、グリセリンモノパルミテート、 グリセリンモノステアレート、グリセリンジステアレート、グリセリンプロピオネートラウレ ート、グリセリンォレートプロピオネートなどが挙げられるがこれに限定されず、これら を単独もしくは併用して使用することができる。この中でも、グリセリンジアセテート力 プリレート、グリセリンジアセテートペラルゴネート、グリセリンジアセテート力プレート、 グリセリンジアセテートラウレート、グリセリンジアセテートミリステート、グリセリンジァセ テートパノレミテート、グリセリンジアセテートステアレート、グリセリンジアセテートォレー トが好ましい。 [0092] The polyhydric alcohol plasticizer is a glycerin-based ester compound such as glycerin ester or diglycerin ester, polyethylene glycol or polypropylene glycol, which has good compatibility with cellulose fatty acid ester and a remarkable thermoplastic effect. Such as a polyalkylene glycol, a compound in which an acyl group is bonded to a hydroxyl group of the polyalkylene glycol. Specific glycerin esters include glycerin diacetate stearate, glycerin diacetate palmitate, glycerin diacetate myristate, glycerin diacetate laurate, glycerin diacetate force plate, glycerin diacetate nonanate, glycerin diacetate otanoate, glycerin Diacetate heptanoate, glycerol diacetate hexanoate, glycerol diacetate pentanoate, glycerol diacetate phosphate, glycerol acetate dicaprate, glycerol acetate dinonanoate, glycerol acetate dioctanoate, glycerol acetate diheptano Acetate, glycerol acetate dicaproate, glycerol acetate divalerate, glycerol acetate Dibutylate, glycerol dipropionate force plate, glycerol dipropionate laurate, glycerol dipropionate myristate, glycerol dipropionate panolemate, glycerol dipropionate stearate, glycerol dipropionate sulfate, glycerol tributyrate, glycerol Tripentanoate, glycerol monopalmitate, glycerol monostearate, glycerol distearate, glycerol propionate lauré But not limited to these, and these can be used alone or in combination. Among them, glycerin diacetate power prelate, glycerin diacetate pelargonate, glycerin diacetate power plate, glycerin diacetate laurate, glycerin diacetate myristate, glycerin diacetate panoleate, glycerin diacetate stearate, glycerin diacetate alcohol Is preferred.
上記ジグリセリンエステルの具体的な例としては、ジグリセリンテトラアセテート、ジグ リセリンテトラプロピオネート、ジグリセリンテトラプチレート、ジグリセリンテトラバレレー ト、ジグリセリンテトラへキサノエート、ジグリセリンテトラヘプタノエート、ジグリセリンテ トラカプリレート、ジグリセリンテトラペラルゴネート、ジグリセリンテトラ力プレート、ジグ リセリンテトララウレート、ジグリセリンテトラミスチレート、ジグリセリンテトラパルミテート 、ジグリセリントリアセテートプロピオネート、ジグリセリントリアセテートブチレート、ジグ リセリントリアセテートバレレート、ジグリセリントリアセテートへキサノエート、ジグリセリ ントリアセテートヘプタノエート、ジグリセリントリアセテートカプリレート、ジグリセリントリ アセテートペラルゴネート、ジグリセリントリアセテート力プレート、ジグリセリントリァセ テートラウレート、ジグリセリントリアセテートミスチレート、ジグリセリントリアセテートパ ノレミテート、ジグリセリントリアセテートステアレート、ジグリセリントリアセテートォレート 、ジグリセリンジアセテートジプロピオネート、ジグリセリンジアセテートジブチレート、 ジグリセリンジアセテートジバレレート、ジグリセリンジアセテートジへキサノエート、ジ グリセリンジアセテートジヘプタノエート、ジグリセリンジアセテートジカプリレート、ジグ リセリンジアセテートジペラノレゴネート、ジグリセリンジアセテートジカプレート、ジグリ セリンジアセテートジラウレート、ジグリセリンジアセテートジミスチレート、ジグリセリン ジアセテートジパノレミテート、ジグリセリンジアセテートジステアレート、ジグリセリンジ アセテートジ才レート、ジグリセリンアセテートトリプロピ才ネート、ジグリセリンァセテ一 トトリプチレート、ジグリセリンアセテートトリバレレート、ジグリセリンアセテートトリへキ サノエート、ジグリセリンアセテートトリヘプタノエート、ジグリセリンアセテートトリカプリ レート、ジグリセリンアセテートトリペラルゴネート、ジグリセリンアセテートトリ力プレート 、ジグリセリンアセテートトリラウレート、ジグリセリンアセテートトリミスチレート、ジグリセ リンアセテートトリパノレミテート、ジグリセリンアセテートトリステアレート、ジグリセリンァ セテートトリオレート、ジグリセリンラウレート、ジグリセリンステアレート、ジグリセリン力 プリレート、ジグリセリンミリステート、ジグリセリンォレートなどのジグリセリンの混酸ェ ステルなどが挙げられるがこれらに限定されず、これらを単独もしくは併用して使用す ることができる。この中でも、ジグリセリンテトラアセテート、ジグリセリンテトラプロピ才ネ ート、ジグリセリンテトラプチレート、ジグリセリンテトラカプリレート、ジグリセリンテトララ ゥレートが好ましい。 Specific examples of the diglycerin ester include diglycerin tetraacetate, diglycerin tetrapropionate, diglycerin tetrabutylate, diglycerin tetravalerate, diglycerin tetrahexanoate, diglycerin tetraheptanoate, Diglycerin Tetracaprylate, Diglycerin Tetrapelargonate, Diglycerin Tetrapulonate, Diglycerin Tetralaurate, Diglycerin Tetramyristate, Diglycerin Tetrapalmitate, Diglycerin Triacetate Propionate, Diglycerin Triacetate Butyrate, Diglycerin Triacetate valerate, diglycerin triacetate hexanoate, diglycerin triacetate heptanoate, diglycerin triacetate capri Rate, diglycerin triacetate pelargonate, diglycerin triacetate force plate, diglycerin triacetate laurate, diglycerin triacetate myristate, diglycerin triacetate phenolate, diglycerin triacetate stearate, diglycerin triacetate stearate, diglycerin di Acetate dipropionate, diglycerol diacetate dibutyrate, diglycerol diacetate divalerate, diglycerol diacetate dihexanoate, diglycerol diacetate diheptanoate, diglycerol diacetate dicaprylate, diglycerol diacetate di Peranolegonate, diglycerin diacetate dicaprate, diglycerin diacetate dilaurate, diglycerin di Cetate dimyristate, diglycerin diacetate dipanoremitate, diglycerin diacetate distearate, diglycerin diacetate ditalate, diglyceryl acetate tripropiate, diglyceryl acetate tritriptylate, diglyceryl acetate trybare Diglycerol acetate trihexanoate, Diglycerol acetate triheptanoate, Diglycerol acetate tricaprylate, Diglycerol acetate tripelargonate, Diglycerol acetate tri-force plate, Diglycerol acetate trilaurate, Diglycerol acetate tri Mistylate, Digrise Phosphoric acetate trypanolemitate, diglyceryl acetate tristearate, diglycerin acetate trioleate, diglycerin laurate, diglyceryl stearate, diglycerin power pre-late, diglycerin myristate, diglycerin zoleate mixed acid Examples include, but are not limited to, esters, and these can be used alone or in combination. Of these, diglycerin tetraacetate, diglycerin tetrapropyrate, diglycerin tetrapropylate, diglycerin tetracaprylate, and diglycerin tetralaurate are preferable.
[0094] 上記ポリアルキレングリコールの具体的な例としては、平均分子量が 200〜1000 のポリエチレングリコール、ポリプロピレングリコールなどが挙げられるがこれらに限定 されず、これらを単独もしくは併用して使用することができる。ポリアルキレングリコー ルの水酸基にァシル基が結合した化合物の具体的な例として、ポリオキシエチレンァ セテート、ポリオキシエチレンプロピオネート、ポリオキシエチレンブチレート、ポリオキ シエチレンバリレート、ポリオキシエチレン力プロエート、ポリオキシエチレンヘプタノ エート、ポリオキシエチレンオタタノエート、ポリオキシエチレンノナネート、ポリオキシ エチレン力プレート、ポリオキシエチレンラウレート、ポリオキシエチレンミリスチレート 、ポリオキシエチレンパルミテート、ポリオキシエチレンステアレート、ポリオキシェチレ ンォレート、ポリオキシエチレンリノレート、ポリオキシプロピレンアセテート、ポリオキシ プロピレンプロピオネート、ポリオキシプロピレンブチレート、ポリオキシプロピレンバリ レート、ポリオキシプロピレン力プロエート、ポリオキシプロピレンヘプタノエート、ポリ ォキシプロピレンオタタノエート、ポリオキシプロピレンノナネート、ポリオキシプロピレ ンカプレート、ポリオキシプロピレンラウレート、ポリオキシプロピレンミリスチレート、ポ リオキシプロピレンパルミテート、ポリオキシプロピレンステアレート、ポリオキシプロピ レンォレート、ポリオキシプロピレンリノレートなどが挙げられるがこられに限定されず 、これらを単独もしくは併用して使用することができる。  [0094] Specific examples of the polyalkylene glycol include, but are not limited to, polyethylene glycol and polypropylene glycol having an average molecular weight of 200 to 1000, and these can be used alone or in combination. . Specific examples of a compound in which an acyl group is bonded to a hydroxyl group of polyalkylene glycol include polyoxyethylene acetate, polyoxyethylene propionate, polyoxyethylene butyrate, polyoxyethylene valerate, and polyoxyethylene strength proate. , Polyoxyethylene heptanoate, polyoxyethylene otanoate, polyoxyethylene nonanoate, polyoxyethylene power plate, polyoxyethylene laurate, polyoxyethylene myristate, polyoxyethylene palmitate, polyoxyethylene stearate , Polyoxyethylene glycol, polyoxyethylene linoleate, polyoxypropylene acetate, polyoxypropylene propionate, polyoxypropylene butyrate, polyoxypropylene Pyrene Valerate, Polyoxypropylene Power Proate, Polyoxypropylene Heptanoate, Polyoxypropylene Otanoate, Polyoxypropylene Nonanate, Polyoxypropylene Plate, Polyoxypropylene Laurate, Polyoxypropylene Myristate, Poly Examples include, but are not limited to, reoxypropylene palmitate, polyoxypropylene stearate, polyoxypropylenelate, and polyoxypropylene linoleate, and these can be used alone or in combination.
[0095] 可塑剤の添加量は、セルロース混合エステルに対して 0〜20質量％が好ましぐよ り好ましくは 0〜18質量％、最も好ましくは 2〜 15質量％である。可塑剤の含有量が 20質量％より多い場合、セルロース混合エステルの熱流動性は良好になるもの、可 塑剤が溶融製膜したフィルムの表面にしみ出したり、また耐熱性であるガラス転移温 度 Tgが低下したりすることもある。 [0095] The addition amount of the plasticizer is preferably 0 to 20% by mass, more preferably 0 to 18% by mass, and most preferably 2 to 15% by mass with respect to the cellulose mixed ester. When the content of the plasticizer is more than 20% by mass, the thermal fluidity of the cellulose mixed ester is improved, the plasticizer oozes out on the surface of the melt-formed film, and the glass transition temperature is heat resistant. Degree Tg may decrease.
[0096] (劣化防止剤） [0096] (Deterioration inhibitor)
前記セルロース混合エステルフィルムには、劣化防止剤（例えば、酸化防止剤、過 酸化物分解剤、ラジカル禁止剤、金属不活性化剤、酸捕獲剤、ァミン)や紫外線防 止剤を添加してもよい。これらの劣化防止剤や紫外線防止剤については、特開昭 60 The cellulose mixed ester film may be added with a deterioration preventing agent (for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal deactivator, an acid scavenger, an amine) or an ultraviolet light inhibitor. Good. For these deterioration inhibitors and UV inhibitors, see JP-A-60.
— 235852号、特開平 3— 199201号、同 5— 1907073号、同 5— 194789号、同 5— 235852, JP-A-3-199201, 5-1907073, 5-194789, 5
— 271471号、同 6— 107854号、同 6— 118233号、同 6— 148430号、同 7— 110 56号、同 7— 11055号、同 7— 11056号、同 H 19号、同 8— 239509号、特 開 2000— 204173号の各公報に記載がある。これらの添加量は、調製する溶融物（ ドープ）の 0. 01〜1質量％であることが好ましぐ 0. 01-0. 2質量％であることがさ らに好ましい。添加量が 0. 01質量％未満であると、劣化防止剤の効果がほとんど認 められない。添加量が 1質量％を越えると、フィルム表面への劣化防止剤のブリード アウト (滲み出し)が認められる場合がある。特に好ましい劣化防止剤の例としては、 ブチル化ヒドロキシトルエン（BHT)を挙げることができる。 -271471, 6-107854, 6-118233, 6-148430, 7-11056, 7-11055, 7-11056, H19, 8-239509 No. 2000-204173. The addition amount of these is preferably 0.01 to 1% by mass of the melt (dope) to be prepared, and more preferably 0.01 to 0.2% by mass. When the addition amount is less than 0.01% by mass, the effect of the deterioration inhibitor is hardly recognized. If the added amount exceeds 1% by mass, bleed-out (bleeding) of the deterioration preventing agent to the film surface may be observed. As an example of a particularly preferred deterioration preventing agent, butylated hydroxytoluene (BHT) can be mentioned.
[0097] (紫外線吸収剤）  [0097] (Ultraviolet absorber)
本発明のセルロース混合エステルには、 1種または 2種以上の紫外線吸収剤を含 有させることが好ましい。前記紫外線吸収剤は、液晶の劣化防止の観点から、波長 3 80nm以下の紫外線の吸収能に優れ、かつ、液晶表示性の観点から、波長 400nm 以上の可視光の吸収が少ないものが好ましい。例えば、ォキシベンゾフエノン系化合 物、ベンゾトリアゾール系化合物、サリチル酸エステル系化合物、ベンゾフエノン系化 合物、シァノアクリレート系化合物、ニッケル錯塩系化合物などが挙げられる。特に好 まし 、紫外線吸収剤は、ベンゾトリアゾール系化合物やべンゾフエノン系化合物であ る。中でも、ベンゾトリアゾール系化合物は、セルロース混合エステルに対する不要な 着色が少ないことから、好ましい。  The cellulose mixed ester of the present invention preferably contains one or more ultraviolet absorbers. From the viewpoint of preventing deterioration of the liquid crystal, the ultraviolet absorber is preferably excellent in the ability to absorb ultraviolet rays having a wavelength of 380 nm or less, and from the viewpoint of liquid crystal display properties, the absorption of visible light having a wavelength of 400 nm or more is small. Examples thereof include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. Particularly preferably, the ultraviolet absorber is a benzotriazole compound or a benzophenone compound. Of these, benzotriazole compounds are preferred because they have less unnecessary coloration with respect to cellulose mixed esters.
[0098] 好ましい紫外線吸収剤としては、 2, 6 ジー tert—ブチルー p クレゾール、ペン タエリスリチルーテトラキス〔3— (3, 5—ジ— tert—ブチル—4—ヒドロキシフエ-ル） プロピオネート〕、トリエチレングリコール ビス〔3—（3— tert—ブチルー 5—メチル 4ーヒドロキシフエ-ル）プロピオネート〕、 1, 6 へキサンジオール ビス〔3—（3, 5 ジ— tert—ブチル—4 ヒドロキシフエ-ル）プロピオネート〕、 2, 4 ビス—（n— ォクチルチオ） 6—（4ーヒドロキシー 3, 5 ジー tert—ブチルァ-リノ） 1, 3, 5 トリァジン、 2, 2 チォージエチレンビス〔3—（3, 5 ジ tert—ブチノレー 4ーヒド ロキシフエ-ル）プロピオネート〕、ォクタデシルー 3— (3, 5—ジ一 tert—ブチル 4 —ヒドロキシフエ-ル）プロピオネート、 N, N，一へキサメチレンビス（3, 5—ジ一 tert —ブチルー 4 ヒドロキシ一ヒドロシンナミド）、 1, 3, 5 トリメチル 2, 4, 6 トリス（ 3, 5—ジ— tert—ブチル—4—ヒドロキシベンジル）ベンゼン、トリス—（3, 5—ジ— te rt—ブチル 4—ヒドロキシベンジル）一イソシァヌレイトなどが挙げられる。 [0098] Preferable ultraviolet absorbers include 2, 6 tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate], Triethylene glycol bis [3- (3-tert-butyl-5-methyl 4-hydroxyphenol) propionate], 1, 6 hexanediol bis [3- (3, 5 di-tert-butyl-4 hydroxyphenol) propionate], 2, 4 bis- (n-octylthio) 6- (4-hydroxy-3,5 di tert-butyl-lino) 1, 3, 5 triazine, 2, 2 Thiodiethylenebis [3- (3,5 di tert-butynole 4-hydroxyphenyl) propionate], Octadecyl 3- (3,5-di-tert-butyl 4-hydroxyphenol) propionate, N, N , Monohexamethylenebis (3,5-di-tert-butyl-4-hydroxy-monohydrocinnamide), 1,3,5 trimethyl 2,4,6 tris (3,5-di-tert-butyl-4-hydroxybenzyl) Examples thereof include benzene and tris- (3,5-di-te rt-butyl 4-hydroxybenzyl) monoisocyanurate.
[0099] 特に前記紫外線吸収剤としては、 2, 6 ジ tert—ブチルー p クレゾール、ペン タエリスリチルーテトラキス〔3— (3, 5—ジ— tert—ブチル—4—ヒドロキシフエ-ル） プロピオネート〕、トリエチレングリコール ビス〔3—（3— tert—ブチルー 5—メチル —4—ヒドロキシフエ-ル）プロピオネート〕が最も好ましい。また例えば、 N, N，一ビス 〔3— (3, 5—ジ tert—ブチルー 4ーヒドロキシフエ-ル）プロピオ-ル〕ヒドラジンな どのヒドラジン系の金属不活性剤ゃトリス（2, 4 ジ— tert—ブチルフエ-ル）フォス ファイトなどの燐系加工安定剤を併用してもよい。これらの化合物の添加量は、セル ロース混合エステルに対して質量割合で lppm〜 3. 0%が好ましぐ 10ppm〜2% 力 Sさらに好ましい。 [0099] In particular, as the ultraviolet absorber, 2, 6 di tert-butyl-p cresol, pentaerythrityl-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenol) propionate] Triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenol) propionate] is most preferred. Also, for example, hydrazine-based metal deactivators such as N, N, bis [3- (3,5-di-tert-butyl-4-hydroxyphenol) propiol] hydrazine are tris (2,4 di-tert- Phosphorus processing stabilizers such as butylphenol) phosphite may be used in combination. The addition amount of these compounds is preferably from 1 ppm to 3.0% by mass with respect to the cellulose mixed ester, and more preferably from 10 ppm to 2%.
[0100] これらの紫外線吸収剤は、市販品として下記のものがあり利用できる。ベンゾトリア ゾール系としては TINUBIN P (チノく'スペシャルティ'ケミカルズ社製）、 TINUBIN 23 4 (チバ'スペシャルティ ·ケミカルズ社製）、 TINUBIN 320 (チバ'スペシャルティ ·ケミ カルズ社製）、 TINUBIN 326 (チノく'スペシャルティ ·ケミカルズ社製）、 TINUBIN 327 (チバ'スペシャルティ ·ケミカルズ社製）、 TINUBIN 328 (チバ'スペシャルティ ·ケミカ ルズ社製）、スミソープ 340 (住友ィ匕学社製)などがある。また、ベンゾフエノン系紫外 線吸収剤としては、シーソーブ 100 (シプロ化成社製）、シーソーブ 101 (シプロ化成社 製）、シーソーブ 101S (シプロ化成社製）、シーソーブ 102 (シプロ化成社製）、シーソ ーブ 103 (シプロ化成社製）、アデカスタイプ LA— 51 (旭電化社製）、ケミソープ 111 (ケ ミプロ化成社製）、 UVINUL D-49 (BASF社製）などを挙げられる。  [0100] These ultraviolet absorbers are available as the following commercial products. As benzotriazoles, TINUBIN P (manufactured by Chinoku Specialty Chemicals), TINUBIN 23 4 (manufactured by Chiba Specialty Chemicals), TINUBIN 320 (manufactured by Chiba Specialty Chemicals), TINUBIN 326 (Chinoku) Specialty Chemicals), TINUBIN 327 (Ciba's Specialty Chemicals), TINUBIN 328 (Ciba's Specialty Chemicals), and Sumisorp 340 (Sumitomo Chemical Co., Ltd.). Also, benzophenone-based ultraviolet absorbers include Seasorb 100 (Cipro Kasei), Seasorb 101 (Cipro Kasei), Seasorb 101S (Cipro Kasei), Seasorb 102 (Cipro Kasei), Seasorb 103 (manufactured by Sipro Kasei Co., Ltd.), Adekas type LA-51 (manufactured by Asahi Denka Co., Ltd.), Chemisorp 111 (manufactured by Chemipro Kasei Co., Ltd.), UVINUL D-49 (manufactured by BASF) and the like.
また、ォキザリックアシッドァ-リド系紫外線吸収剤としては、 TINUBIN 312 (チバ' スペシャルティ ·ケミカルズ社製）や TINUBIN 315 (チノく'スペシャルティ ·ケミカルズ 社製）がある。更にサリチル酸系紫外線吸収剤としては、シーソーブ 201 (シプロ化成 社製)やシーソーブ 202 (シプロ化成社製）が上巿されており、シァノアクリレート系紫 外線吸収剤としてはシーソーブ 501 (シプロ化成社製）、 UVINUL N-539 (BASF社 製)がある。 In addition, as oxalic acid-based UV absorbers, TINUBIN 312 (Ciba ' Specialty Chemicals) and TINUBIN 315 (Chinoku's Specialty Chemicals). In addition, as a salicylic acid ultraviolet absorber, Seasorb 201 (manufactured by Sipro Kasei Co., Ltd.) and Seasorb 202 (manufactured by Sipro Kasei Co., Ltd.) are listed, and as a cyanoacrylate-based ultraviolet absorber, Seasorb 501 (manufactured by Sipro Kasei) ), UVINUL N-539 (manufactured by BASF).
[0101] (光学調整剤） [0101] (Optical adjusting agent)
本発明のセルロース混合エステルには、光学異方性をコントロールするための光学 調整剤（レターデーシヨンコントロール剤、特にレターデーシヨン上昇剤）を添加しても よい。本発明では、セルロース混合エステルフィルムのレターデーシヨンを調整する ため、少なくとも一個の芳香族環を有する芳香族化合物をレターデーシヨンコント口 ール剤として使用することが好ましい。芳香族化合物は、セルロース混合エステル 10 0質量部に対して、 0. 01〜20質量部の範囲で使用する。芳香族化合物は、セル口 一スァセレート 100質量部に対して、 0. 05〜15質量部の範囲で使用することが好ま しく、 0. 1〜10質量部の範囲で使用することがさらに好ましい。 2種類以上の芳香族 化合物を併用してもよい。芳香族化合物の芳香族環には、芳香族炭化水素環にカロ えて、芳香族性へテロ環を含む。  The cellulose mixed ester of the present invention may contain an optical adjusting agent (lettering control agent, particularly a letter raising agent) for controlling optical anisotropy. In the present invention, it is preferred to use an aromatic compound having at least one aromatic ring as a letter control agent in order to adjust the letter determination of the cellulose mixed ester film. The aromatic compound is used in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the cellulose mixed ester. The aromatic compound is preferably used in the range of 0.05 to 15 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass, with respect to 100 parts by mass of the cell mouth monosulfate. Two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound includes an aromatic heterocycle in addition to an aromatic hydrocarbon ring.
芳香族炭化水素環は、 6員環 (すなわち、ベンゼン環)であることが特に好ましい。 芳香族性へテロ環は一般に、不飽和へテロ環である。芳香族性へテロ環は、 5員環、 6員環または 7員環であることが好ましぐ 5員環または 6員環であることがさらに好まし い。芳香族性へテロ環は一般に、最多の二重結合を有する。ヘテロ環に含まれるへ テロ原子としては、窒素原子、酸素原子および硫黄原子が好ましぐ窒素原子が特に 好ましい。芳香族性へテロ環の例には、フラン環、チォフェン環、ピロール環、ォキサ ゾール環、イソォキサゾール環、チアゾール環、イソチアゾール環、イミダゾール環、 ピラゾール環、フラザン環、トリァゾール環、ピラン環、ピリジン環、ピリダジン環、ピリミ ジン環、ピラジン環および 1, 3, 5 トリァジン環が含まれる。  The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring). Aromatic heterocycles are generally unsaturated heterocycles. The aromatic heterocycle is preferably a 5-membered, 6-membered or 7-membered ring, more preferably a 5-membered or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As the hetero atom contained in the heterocycle, a nitrogen atom, particularly preferred is a nitrogen atom, an oxygen atom or a sulfur atom. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine Rings, pyridazine rings, pyrimidine rings, pyrazine rings and 1, 3, 5 triazine rings are included.
[0102] (フッ素原子を有する重合体 離型剤） [0102] (Polymer-containing polymer release agent)
本発明におけるセルロース混合エステルは、フッ素原子を有する重合体を含むこと が好ましい。前記フッ素原子を有する重合体は、離型剤としての作用を発現でき、低 分子量ィ匕合物であっても重合体であってもよ 、。 The cellulose mixed ester in the present invention preferably contains a polymer having a fluorine atom. The polymer having a fluorine atom can exhibit an action as a release agent and has a low It may be a molecular weight compound or a polymer.
前記フッ素原子を有する重合体としては、例えば、特開 2001— 269564号公報に 記載の重合体を挙げることができる。前記フッ素原子を有する重合体として好まし 、 ものは、フッ素化アルキル基含有エチレン性不飽和単量体 (単量体 A)を必須成分と して含有してなる単量体を重合せしめた重合体である。前記重合体に係わるフッ素 化アルキル基含有エチレン性不飽和単量体（単量体 A)としては、分子中にエチレン 性不飽和基とフッ素化アルキル基とを有する化合物であれば特に制限はな 、。好ま しくはアクリルエステル基およびその類縁基を含有するものが適しており、具体的に は下記一般式（1)で表されるフッ素化 (メタ）アタリレートが挙げられる。尚、（メタ)ァク リレートは、メタタリレート、アタリレート、フルォロアタリレート、塩素化アタリレートを総 称するものとする。  Examples of the polymer having a fluorine atom include the polymers described in JP-A-2001-269564. The polymer having a fluorine atom is preferably a polymer obtained by polymerizing a monomer containing an ethylenically unsaturated monomer (monomer A) containing a fluorinated alkyl group as an essential component. It is a coalescence. The fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) related to the polymer is not particularly limited as long as it is a compound having an ethylenically unsaturated group and a fluorinated alkyl group in the molecule. ,. Preferably, those containing an acrylic ester group and its related groups are suitable, and specific examples include fluorinated (meth) acrylates represented by the following general formula (1). Note that (meth) acrylate is a generic term for metatalylate, attalylate, fluoro acrylate, and chlorinated acrylate.
[0103] 一般式（1) CH =C (R1) -COO- (X) n-Rf [0103] General formula (1) CH = C (R 1 ) -COO- (X) n-Rf
2  2
(式中、 Rfは炭素数 1〜20のパーフロロアルキル基、または部分フッ素化アルキル 基であり、 Rfは直鎖状であっても分岐状であってもよぐまた酸素原子および Zまた は窒素原子を含む官能基を主鎖中に有するものであってもよい。 R1は H、フッ素ィ匕さ れていてもよいアルキル基、 Cほたは Fを表し、 Xは 2価の連結基を表し、 nは 0以上 の整数を表す。 ) (In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group, and Rf may be linear or branched, and may be an oxygen atom and Z or It may have a functional group containing a nitrogen atom in the main chain R 1 is H, an alkyl group which may be fluorinated, C or F, X is a divalent linkage Represents a group, and n represents an integer of 0 or more.)
[0104] Rfのパーフロロアルキル基の好ましい炭素数は 1〜18であり、より好ましくは 4〜18 であり、さらに好ましくは 6〜 14であり、最も好ましくは 6〜 12である。部分フッ素化ァ ルキル基は、その一部にパーフロロアルキル基を有するものが好ましぐそのパーフ ロロアルキル基の炭素数の好ましい範囲は前記と同じである。また、主鎖中に有して いてもよい酸素原子を含む官能基としては、 - so —c ( = o)—、窒素原子を含  [0104] The preferred carbon number of the perfluoroalkyl group of Rf is 1 to 18, more preferably 4 to 18, still more preferably 6 to 14, and most preferably 6 to 12. The partially fluorinated alkyl group preferably has a perfluoroalkyl group in part, and the preferred range of the carbon number of the perfluoroalkyl group is the same as described above. In addition, examples of the functional group containing an oxygen atom that may be present in the main chain include -so-c (= o)-and a nitrogen atom.
2  2
む官能基としては、 NH— N (CH ) N (C H ) N (C H )—などを  Examples of functional groups include NH—N (CH) N (C H) N (C H) —
3 2 5 3 7 挙げることができる。  3 2 5 3 7 Can be mentioned.
R1が採りうるフッ素化されていてもよいアルキル基は、無置換のアルキル基、パーフ ロロアルキル基、部分フッ素化アルキル基のいずれであってもよい。好ましいのは、 無置換のアルキル基および部分フッ素化アルキル基である。無置換のアルキル基と して好ましいのは、メチノレ基である。 [0105] Xが採りうる 2価の連結基として好ましいものは、一（CH ) ―、 -CH CH (OH) - ( The alkyl group which may be fluorinated for R 1 may be any of an unsubstituted alkyl group, a perfluoroalkyl group and a partially fluorinated alkyl group. Preference is given to unsubstituted alkyl groups and partially fluorinated alkyl groups. Preferred as an unsubstituted alkyl group is a methinore group. [0105] Preferred as the divalent linking group that X can take is one (CH)-, -CH CH (OH)-(
2 m 2  2 m 2
CH ) (CH ) N (R2) -SO (CH ) N (R2)—CO -、—CH (CH )CH) (CH) N (R 2 ) -SO (CH) N (R 2 ) —CO —, —CH (CH)
2 m 2 m 2 2 m 3 CH (CH CH ) -C (CH ) CH (CF ) C (CH ) (CF ) C (C 2 m 2 m 2 2 m 3 CH (CH CH) -C (CH) CH (CF) C (CH) (CF) C (C
2 3 3 2 3 3 3  2 3 3 2 3 3 3
F ) ―、また、一般式 (3)で表される素材もフッ素化アルキル基含有エチレン性不飽 F)-, and the material represented by the general formula (3) is also a fluorinated alkyl group-containing
3 2 3 2
和単量体 (A)として好ましい。 R2は水素または炭素数 1〜6アルキル基である。 Preferred as the sum monomer (A). R 2 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
nは 0以上の整数であり、 0〜25力 子ましく、 1〜15がより好ましぐ 1〜10が特に好 ましい。 nが 2以上であるとき、各 Xが表す連結基は同一であっても異なっていてもよ い。  n is an integer of 0 or more, 0 to 25 dynamics, 1 to 15 is more preferable, and 1 to 10 is particularly preferable. When n is 2 or more, the linking groups represented by each X may be the same or different.
[0106] フッ素化アルキル基含有エチレン性不飽和単量体 (単量体 A)は、 1種類だけを用 いても構わないし、 2種類以上を同時に用いても構わない。フッ素化アルキル基含有 エチレン性不飽和単量体 (単量体 A)におけるフッ素化アルキル基は、離型性 (剥離 性）の観点からは、その炭素数は 6〜18が特に好ましぐさらには 6〜14であり、特に は 6〜 12が好ましい。本発明において、フッ素化アルキル基含有エチレン性不飽和 単量体 (単量体 A)の重合体 (I)中への導入量に特に制限はないが、 10質量％以上 重合せしめることが好ましぐ 15質量％以上がより好ましぐ 20質量％以上の含有量 が好ましい。  [0106] The fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) may be used alone or in combination of two or more. The fluorinated alkyl group in the ethylenically unsaturated monomer (monomer A) containing a fluorinated alkyl group is particularly preferably 6 to 18 carbon atoms from the viewpoint of releasability (peelability). Is 6 to 14, particularly 6 to 12. In the present invention, the amount of the fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) introduced into the polymer (I) is not particularly limited, but it is preferably 10% by mass or more. More preferred is a content of 20% by mass or more.
[0107] さらに本発明においてはフッ素原子を有する重合体中に、ポリオキシアルキレン基 含有不飽和単量体 (単量体 B)を含有させることも可能である。ポリオキシアルキレン 基含有エチレン性不飽和単量体（単量体 B)としては、 1分子中にポリオキシアルキレ ン基とエチレン性不飽和基を有する化合物であれば特に制限はな 、。ォキシアルキ レン基としてはエチレンォキシド基および Zまたはプロピレンォキシド基が好ましい。 またその重合度は通常 1〜： L00であり、 5〜50が好ましい。エチレン性不飽和基とし ては、原料の入手性、各種コーティング組成物中の配合物に対する相溶性、そのよう な相溶性を制御することの容易性、あるいは重合反応性の観点から (メタ)アクリルェ ステル基およびその類縁基を含有するものが適して 、る。  Furthermore, in the present invention, a polyoxyalkylene group-containing unsaturated monomer (monomer B) can be contained in the polymer having a fluorine atom. The polyoxyalkylene group-containing ethylenically unsaturated monomer (monomer B) is not particularly limited as long as it is a compound having a polyoxyalkylene group and an ethylenically unsaturated group in one molecule. As the oxyalkylene group, an ethylene oxide group and a Z or propylene oxide group are preferable. The degree of polymerization is usually 1 to: L00, preferably 5 to 50. The ethylenically unsaturated group is a (meth) acrylic acid from the viewpoint of availability of raw materials, compatibility with formulations in various coating compositions, ease of controlling such compatibility, or polymerization reactivity. Those containing a stealth group and its related groups are suitable.
[0108] さらに、 1分子中に 2個以上の不飽和結合を有するエチレン性不飽和単量体 (単量 体 C)を含有させることも可能である。 1分子中に 2個以上の不飽和結合を有するェチ レン性不飽和単量体 (単量体 C)としては、特に制限はなぐ 目的とする配合物中の マトリックス榭脂、溶媒等の組成により適宜選択される。エチレン性不飽和基としては 原料の入手性、各種コーティング組成物中の配合物に対する相溶性、そのような相 溶性を制御することの容易性あるいは重合反応性の観点から (メタ)アクリルエステル 基およびその類縁基を含有するものが適して！/ヽる。 [0108] Further, an ethylenically unsaturated monomer (monomer C) having two or more unsaturated bonds can be contained in one molecule. Ethylene unsaturated monomer (monomer C) having two or more unsaturated bonds in one molecule is not particularly limited. It is appropriately selected depending on the composition of the matrix resin, solvent and the like. Ethylenically unsaturated groups include (meth) acrylic ester groups and from the viewpoints of availability of raw materials, compatibility with formulations in various coating compositions, ease of controlling such compatibility, or polymerization reactivity. The one containing the related group is suitable! / Speak.
ない。  Absent.
以下に本発明で好ましく用いられるフッ素原子を有する重合体の具体例を表すが、 本発明で用いることができるフッ素原子を有する重合体はこれらに限定されるもので はない。  Specific examples of the polymer having a fluorine atom preferably used in the present invention are shown below, but the polymer having a fluorine atom that can be used in the present invention is not limited thereto.
[0109] PF- 1 : 2 へプタデシルフルォロォクチルーェチル アタリレート Zブチルアタリレ 一卜 = 30Z70 (モル比、分子量 3000)  [0109] PF-1: 2 Heptadecylfluorooctylethyl Atalylate Z-Butyl Ataryl 1 g = 30Z70 (Molar ratio, molecular weight 3000)
PF-2 ： 2—へプタデシルフルォロォクチルーェチルアタリレート Ζ2—ェチルへキ シルアタリレー卜 = 25Ζ75 (モル比、分子量 5000)  PF-2: 2—Heptadecylfluorooctyl acetylate Ζ2—Ethylhexyl ateryl 卜 = 25Ζ75 (molar ratio, molecular weight 5000)
PF- 3 : 2 トリデカフルォ口へキシルーェチルアタリレート Ζブチルアタリレート = 2 0Ζ80 (モル比、分子量 8000)  PF- 3: 2 Tridecafluoro mouth hexyl ester butyl butyl acrylate = 2 0 2 80 (molar ratio, molecular weight 8000)
PF-4 : 2 トリデカフルォ口へキシルーェチルアタリレート Ζブチルメクリレート = 1 5Ζ85 (モル比、分子量 5000)  PF-4: 2 Tridecafluoro mouth hexyl acetyl acrylate butyl butyl methacrylate = 1 5 Ζ 85 (molar ratio, molecular weight 5000)
PF-8： 2 へプタデシルフルォロォクチルーェチルアタリレート Ζポリ（平均重合度 5)ォキシエチレンメタタリレート Ζブチルアタリレート = 30Ζ20Ζ50(モル比、分子 量 9000)  PF-8: 2 Heptadecylfluorooctylethyl acrylate A poly (average degree of polymerization 5) Oxyethylene metatalylate Acetyl butyl acrylate = 30-20 20 50 (molar ratio, molecular weight 9000)
PF- 9 : 2-トリデカフルォ口へキシル ェチルアタリレート Ζポリ（平均重合度 5)ォ キシエチレンメタタリレート Ζ2—ェチルへキシルアタリレート ζメチルアタリレート Ζト リエチレングリコール ジメタクリレー卜 = 30Ζ20Ζ30Ζ15Ζ5(モル比、分子量 300 0)  PF-9: 2-Tridecafluor Hexyl Ethyl Atylate ΖPoly (average degree of polymerization 5) Oxyethylene Metatalylate チ ル 2-Ethylhexyl Atylate ζMethyl Atylate ΖTriethylene Glycol Dimethacrylate 卜 = 30Ζ20Ζ30Ζ15Ζ5 (Molar ratio) , Molecular weight 300 0)
[0110] PF- 10 : 2 トリデカフルォ口へキシル—ェチルアタリレート Ζポリ（平均重合度 5) ォキシエチレンアタリレート Ζ2—ブチルアタリレート Ζメチノレメタタリレート Ζテトラエ チレングリコール ジメタクリレー卜 = 30Ζ25Ζ25Ζ15Ζ5 (モル比、分子量 3500) PF- 11 : 2-トリデカフルォ口へキシル -ェチルアタリレート Ζポリ（平均重合度 5) ォキシエチレンメタタリレート Ζ2—へキシルアタリレート Ζメチノレメタタリレート Ζテトラ エチレングリコール ジメタクリレー卜 = 30Z25Z25Z10 (モル比、分子量 6000) PF- 12 : 2-トリデカフルォ口へキシル -ェチルアタリレート Ζポリ（平均重合度 5) ォキシエチレンメタタリレート Ζ2—へキシルアタリレート Ζメチノレメタタリレート = 30Ζ 25Ζ25Ζ20(モル比、分子量 6000) [0110] PF-10: 2 Tridecafluorohexyl-ethyl acrylate: Poly (average degree of polymerization 5) Oxyethylene acrylate: 2-butyl acrylate: Methinoremethacrylate: Tetraethylene glycol Dimethacrylate: 30-25-25-15-5 ( (Molar ratio, molecular weight 3500) PF-11: 2-Tridecafluorohexyl-ethyl acrylate. Poly (average degree of polymerization 5) Oxyethylene metatalate レ ー ト 2-hexyl acrylate. Ethylene glycol dimethacrylate = 30Z25Z25Z10 (molar ratio, molecular weight 6000) PF-12: 2-tridecafluorohexyl-ethyl acrylate. Poly (average polymerization degree 5) oxyethylene methacrylate. Noremetatalylate = 30Ζ25Ζ25Ζ20 (molar ratio, molecular weight 6000)
PF- 13 : 2—へプタデシルフルォロォクチルーェチル アタリレート Ζポリ（平均重 合度 5)ォキシエチレンメタタリレート Ζ2—へキシルアタリレート Ζメチルメタタリレート = 25Ζ25Ζ30Ζ20(モル比、分子量 8000)  PF-13: 2—Heptadecylfluorooctylethyl Atalylate ΖPoly (average degree of polymerization 5) oxyethylene metatalylate Ζ2-Hexyl attalylate メ タ Methyl metatalylate = 25Ζ25Ζ30Ζ20 (molar ratio, molecular weight 8000)
PF- 14 : 2—へプタデシルフルォロォクチルーェチル アタリレート Ζポリ（平均重 合度 5)ォキシエチレンメタタリレート Ζ2—へキシルアタリレート Ζスチレン =30Ζ25 Z35Z10 (モル比、分子量 9000)  PF-14: 2—Heptadecylfluorooctylethyl talylate ΖPoly (average degree of polymerization 5) oxyethylene metatalylate Ζ2-Hexyl acrylate Ζstyrene = 30Ζ25 Z35Z10 (molar ratio, molecular weight 9000)
[0111] (溶融製膜工程） [0111] (Melting process)
(ペレット化）  (Pelletized)
上記セルロース混合エステルと添加物は溶融製膜に先立ちペレツトイ匕するのが好 ましい。  The cellulose mixed ester and additives are preferably subjected to pelletizing prior to melt film formation.
ペレツトイ匕を行なうにあたりセルロース混合エステルは事前に乾燥しておくことが好 ましいが、ベント式押出機を用いることで、これに代用することもできる。乾燥を行なう 場合は、乾燥方法として、加熱炉内にて 90°Cで 8時間以上加熱する方法等を用いる ことができるが、この限りではない。ペレツトイ匕は上記セルロース混合エステルと添カロ 物を 2軸混練押出機を用いて 150°C〜230°Cで溶融後、ヌードル状に押出したもの を水中で固化し裁断することで作成することができる。また、押出機による溶融後水 中に口金より直接押出ながらカットする、アンダーウォーターカット法等によりペレット 化を行っても力まわない。押出機は十分な、溶融混練が得られる限り、任意の公知の 単軸スクリュー押出機、非嚙み合い型異方向回転二軸スクリュー押出機、嚙み合い 型異方向回転二軸スクリュー押出機、嚙み合い型同方向回転二軸スクリュー押出機 などを用いることができる。好ましいペレットの大きさは断面積が lmm2〜300mm2、 長さ lmm〜30mmが好ましぐより好ましくは断面積が 2mm2〜100mm2、長さが 1. 5mm〜 10mmで teる。 It is preferable to dry the cellulose mixed ester in advance when carrying out the perettoy koji, but this can be substituted by using a vented extruder. When drying, a method of heating in a heating furnace at 90 ° C for 8 hours or more can be used as a drying method, but this is not restrictive. Pereztoy rice cake can be prepared by melting the above cellulose mixed ester and additive carotenoid at 150 ° C to 230 ° C using a twin-screw kneading extruder, then extruding the noodle into a solid and cutting it in water. it can. Also, pelletization by the underwater cutting method, in which it is cut while being extruded directly from the die into water after being melted by an extruder, does not work. Any known single-screw extruder, non-mesh type counter-rotating twin-screw extruder, kneading type counter-rotating twin-screw extruder, as long as the melter kneading can be obtained, A meshing type co-rotating twin screw extruder can be used. The size of the preferred pellet lmm 2 to 300 mm 2 cross-sectional area, length lmm~30mm is preferred instrument more preferably the cross-sectional area is 2 mm 2 100 mm 2, Ru te at the 1. 5 mm to 10 mm in length.
[0112] またペレツトイ匕を行なう時に、上記添加物を押出機の途中にある原料投入口やベント ロカ 投入することもできる。押出機の回転数は lOrpm〜： LOOOrpmが好ましぐより 好ましくは、 20rpm〜700rpm、さらにより好ましくは 30rpm〜500rpmである。 lOrp m以上であれば、滞留時間が長くなり過ぎることがなぐ熱劣化による分子量低下や 、黄色味の悪ィ匕を招きにくい。また lOOOrpm以下であれば、剪断による分子の切断 や分子量低下、架橋ゲルの発生量の増加などを回避しやすい。ペレット化における 押出滞留時間は 10秒〜 60分、より好ましくは、 15秒〜 30分である。十分に溶融が できれば、滞留時間は短い方が、榭脂劣化、黄色み発生を抑えることができる点で 好ましい。 [0112] In addition, when performing pellets toy koji, the above additives are added to the raw material inlet and vent in the middle of the extruder. Loca can also be introduced. The rotation speed of the extruder is preferably 10 rpm to: LOOO rpm, more preferably 20 rpm to 700 rpm, and even more preferably 30 rpm to 500 rpm. If it is lOrpm or more, the residence time will not be too long, and it will be difficult to cause a decrease in molecular weight due to thermal deterioration and a yellowish nuisance. Moreover, if it is less than lOOOrpm, it is easy to avoid the cutting | disconnection of the molecule | numerator by shearing, molecular weight fall, and the increase in the generation amount of crosslinked gel. The extrusion residence time in pelletization is 10 seconds to 60 minutes, more preferably 15 seconds to 30 minutes. If sufficient melting is possible, it is preferable that the residence time is short in that the deterioration of the fat and the yellowing can be suppressed.
[0113] (溶融製膜） [0113] (Melting)
1)乾燥  1) Dry
本発明では、上述の方法でペレツトイ匕したものを用いるのが好ましぐ溶融製膜に 先立ちペレット中の含水率を好ましくは 1質量％以下、より好ましくは 0. 5質量％以下 、さらに好ましくは、 0. 01質量％以下にした後、溶融押出し機のホッパーに投入する 。このときホッパーを好ましくは 20°C〜110°C以下、より好ましくは 40°C〜100°C以 下、さらに好ましくは 50°C〜90° 以下にする。  In the present invention, the moisture content in the pellets is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably, prior to melt film formation, which is preferably performed by using the above-described method. , 0.01% by mass or less, and then put into the hopper of the melt extruder. At this time, the hopper is preferably 20 ° C to 110 ° C or less, more preferably 40 ° C to 100 ° C or less, and further preferably 50 ° C to 90 ° C or less.
この際、ホッパーは除湿風エアー等で一定風量 '温度である事が好ましいが、目的 とする含水率が得られるのであればこの限りでは無い。また、ホッパー内を真空密閉 構造とし、窒素等の不活性ガスを封入することがより好ま 、。  At this time, the hopper is preferably dehumidified air or the like and has a constant air volume and temperature, but this is not necessary as long as the desired moisture content can be obtained. More preferably, the hopper has a vacuum-sealed structure and is filled with an inert gas such as nitrogen.
[0114] 2)溶融押出し [0114] 2) Melt extrusion
上述したセルロース混合エステル榭脂は押出機の供給口を介してシリンダー内に 供給される。押出機 22の構造を図 1に示す。シリンダー 32内は供給口 40側力も順に 、供給口カゝら供給したセルロース混合エステル榭脂を定量輸送する供給部 (領域 A) とセルロース混合エステル榭脂を溶融混練'圧縮する圧縮部 (領域 B)と溶融混練'圧 縮されたセルロース混合エステル榭脂を計量する計量部 (領域 C)とで構成される。 榭脂は上述の方法により水分量を低減させるために、乾燥することが好ましいが、残 存する酸素による溶融樹脂の酸ィ匕を防止するために、押出機内を不活性 (窒素等） 気流中、あるいはベント付き押出し機を用いて真空排気しながら実施するのがより好 ましい。押出機のスクリュー圧縮比は 2. 5〜4. 5に設定され、 L/Dは 20〜70に設 定されて!/、ることが好ま 、。ここでスクリュー圧縮比とは供給部 Aと計量部 Cとの容 積比、即ち供給部 Aの単位長さあたりの容積 ÷計量部 Cの単位長さあたりの容積で 表され、供給部 Aのスクリュー軸の外径 dl、計量部 Cのスクリュー軸の外径 d2、供給 部 Aの溝部径 al、および計量部 Cの溝部径 a2とを使用して算出される。また、 LZD とはシリンダー内径に対するシリンダー長さの比である。また、押出温度は 190〜24 0°Cに設定されることが好ましい。押出機内での温度が 230°Cを超える場合には、押 出機とダイとの間に冷却機を設けるようにすることが好ま 、。 The cellulose mixed ester resin described above is supplied into the cylinder through the supply port of the extruder. The structure of the extruder 22 is shown in FIG. In the cylinder 32, the supply port 40 side force is also applied in order, the supply unit (region A) for quantitatively transporting the cellulose mixed ester resin supplied from the supply port, and the compression unit (region B) for melting and kneading and compressing the cellulose mixed ester resin. ) And a measurement part (area C) that measures melt-kneaded 'compressed cellulose mixed ester resin. In order to reduce the water content by the above-mentioned method, it is preferable to dry the resin, but in order to prevent the molten resin from being oxidized by residual oxygen, the inside of the extruder is inert (nitrogen etc.) in a stream of air. Alternatively, it is more preferable to carry out evacuation using a vented extruder. The screw compression ratio of the extruder is set to 2.5 to 4.5, and the L / D is set to 20 to 70. I like to be determined! Here, the screw compression ratio is expressed by the volume ratio of the supply unit A and the measurement unit C, that is, the volume per unit length of the supply unit A ÷ the volume per unit length of the measurement unit C. It is calculated using the outer diameter dl of the screw shaft, the outer diameter d2 of the screw shaft of the measuring part C, the groove part diameter al of the supply part A, and the groove part diameter a2 of the measuring part C. LZD is the ratio of cylinder length to cylinder inner diameter. The extrusion temperature is preferably set to 190 to 240 ° C. When the temperature in the extruder exceeds 230 ° C, it is preferable to install a cooler between the extruder and the die.
[0115] スクリュー圧縮比が小さ過ぎると、十分に溶融混練されず、未溶解部分が発生した り、せん断発熱が小さ過ぎて結晶の融解が不十分となり、製造後のセルロース混合ェ ステルフィルムに微細な結晶が残存し易くなり、さらに、気泡が混入し易くなる傾向が ある。これにより、セルロース混合エステルフィルムの強度が低下したり、あるいはフィ ルムを延伸する場合に、残存した結晶が延伸性を阻害し、配向を十分に上げること ができなくなることがある。逆に、スクリュー圧縮比が大き過ぎると、せん断応力がかか り過ぎて発熱により樹脂が劣化し易くなるので、製造後のセルロース混合エステルフ イルムに黄色味が出易くなる傾向がある。また、せん断応力が力かり過ぎると、分子の 切断が起こり、分子量が低下してフィルムの機械的強度が低下することがある。製造 後のセルロース混合エステルフィルムに黄色味が出にくく且つフィルム強度が強くさ らに延伸破断しにくくするためには、スクリュー圧縮比は 2. 5〜4. 5の範囲が好ましく 、より好ましく ίま 2. 8〜4. 2、特【こ好まし!/ヽの ίま 3. 0〜4. 0の範囲である。 [0115] If the screw compression ratio is too small, it will not melt and knead sufficiently, and undissolved parts will be generated, or the heat generated by shearing will be too small, resulting in insufficient melting of the crystals. Tend to remain, and bubbles tend to be mixed. As a result, when the strength of the cellulose mixed ester film is reduced, or when the film is stretched, the remaining crystals may impair the stretchability and the orientation may not be sufficiently increased. On the other hand, if the screw compression ratio is too large, the shear stress is excessive and the resin tends to deteriorate due to heat generation, so that the cellulose mixed ester film after production tends to be yellowish. In addition, if the shear stress is excessive, molecular cutting may occur, the molecular weight may decrease, and the mechanical strength of the film may decrease. The screw compression ratio is preferably in the range of 2.5 to 4.5, more preferably 0.75, in order to make the cellulose mixed ester film after production hardly yellowish and the film strength is strong and the film is not easily stretched and broken. 2. 8 ~ 4.2, specially [preferably! / ヽ ί] 3. The range is 0 ~ 4.0.
[0116] また、 LZDが小さ過ぎると、溶融不足や混練不足となり、圧縮比が小さい場合と同 様に製造後のセルロース混合エステルフィルムに微細な結晶が残存し易くなる傾向 がある。逆に、 LZDが大き過ぎると、押出機内でのセルロース混合エステル榭脂の 滞留時間が長くなり過ぎ、榭脂の劣化を引き起こし易くなる傾向がある。また、滞留時 間が長くなると分子の切断が起こったり、分子量が低下してセルロース混合エステル フィルムの機械的強度が低下することがある。製造後のセルロース混合エステルフィ ルムに黄色味が出に《且つフィルム強度が強くさらに延伸破断しに《するために は、 LZDは 20〜70の範囲が好ましぐより好ましくは 22〜65の範囲、特に好ましく は 24〜50の範囲である。 また、押出温度が低過ぎると、結晶の融解が不十分となり、製造後のセルロース混 合エステルフィルムに微細な結晶が残存し易くなり、フィルム強度が低下したり、ある いはフィルムを延伸する場合に、残存した結晶が延伸性を阻害し、配向を十分に上 げることができなくなる傾向がある。逆に、押出し温度が高過ぎると、セルロースァシ レート榭脂が劣化し、黄色味 (YI値)の程度が悪ィ匕してしまう傾向がある。製造後のセ ルロース混合エステルフィルムに黄色味が出にくく且つフィルム強度が高く延伸破断 しにくくするためには、押出温度は 180°C〜230°Cとし、好ましくは 185°C〜230°C、 さらに好ましくは 190°C〜225°Cの範囲である。 [0116] On the other hand, if LZD is too small, melting and kneading are insufficient, and fine crystals tend to remain in the cellulose mixed ester film after production, as in the case where the compression ratio is small. On the other hand, if the LZD is too large, the residence time of the cellulose mixed ester resin in the extruder becomes too long and tends to cause deterioration of the resin. In addition, if the residence time is long, the molecules may be broken, or the molecular weight may be reduced to lower the mechanical strength of the cellulose mixed ester film. In order to produce a yellowish color in the cellulose mixed ester film after production, and the film strength is strong and the film is stretched and fractured, the LZD is preferably in the range of 20 to 70, more preferably in the range of 22 to 65. Particularly preferred is the range of 24-50. In addition, if the extrusion temperature is too low, the crystals are not sufficiently melted, and fine crystals are likely to remain in the cellulose mixed ester film after production, and the film strength is reduced or the film is stretched. In addition, the remaining crystals tend to hinder stretchability and fail to sufficiently raise the orientation. Conversely, if the extrusion temperature is too high, the cellulose acylate resin tends to deteriorate and the yellowness (YI value) tends to deteriorate. In order to make the cellulose mixed ester film after production hardly yellowish and the film strength is high and it is difficult to stretch and break, the extrusion temperature is 180 ° C to 230 ° C, preferably 185 ° C to 230 ° C. More preferably, it is in the range of 190 ° C to 225 ° C.
[0117] 上記の如く押出温度が設定された押出機を用いて製膜されたセルロース混合エス テルフィルムは、ヘイズが 2. 0%以下、イェローインデックス (YI値）が 10以下である 特性値を有している。 [0117] The cellulose mixed ester film formed using the extruder having the extrusion temperature set as described above has a characteristic value having a haze of 2.0% or less and a yellow index (YI value) of 10 or less. Have.
ここで、ヘイズは押出温度が低過ぎないかの指標、換言すると製造後のセルロース 混合エステルフィルムに残存する結晶の多少を知る指標になり、ヘイズが 2. 0%を超 えると、製造後のセルロース混合エステルフィルムの強度低下と延伸時の破断が発 生し易くなる。また、イェローインデックス (YI値）は押出温度が高過ぎないかを知る 指標となり、イェローインデックス (YI値）が 10以下であれば、黄色味の点で問題無 い。  Here, the haze is an indicator of whether the extrusion temperature is too low, in other words, an indicator of the amount of crystals remaining in the cellulose mixed ester film after production, and if the haze exceeds 2.0%, The strength of the cellulose mixed ester film is reduced and breakage during stretching tends to occur. The yellow index (YI value) is an index for knowing whether the extrusion temperature is too high. If the yellow index (YI value) is 10 or less, there is no problem in terms of yellowness.
[0118] 押し出し機の種類として、一般的には設備コストの比較的安い単軸押し出し機が用 いられることが多ぐフルフライト、マドック、ダルメージ等のスクリュータイプがあるが、 熱安定性の比較的悪 、セルロース混合エステル榭脂には、フルフライトタイプが好ま しい。また、設備コストは高価である力 スクリューセグメントを変更することにより、途 中でベント口を設けて不要な揮発成分を脱揮させながら押出ができる二軸押出機を 用いることが可能である。二軸押し出し機には大きく分類して同方向と異方向のタイ プがありどちらも用いることが可能である力 滞留部分が発生し難くセルフクリーニン グ性能の高い同方向回転のタイプが好ましい。二軸押出機は設備が高価であるが、 混練性が高ぐ榭脂の供給性能が高いため、低温での押出が可能となるため、セル ロースアセテート榭脂の製膜に適している。ベント口を適正に配置することにより、未 乾燥状態でのセルロールァシレートペレットやパウダーをそのまま使用することも可 能である。また、製膜途中で出たフィルムのミミ等も乾燥させることなしにそのまま再利 用することちでさる。 [0118] As a type of extruder, there are screw types such as full-flight, madok, and dalmage, where single-screw extruders with relatively low equipment costs are generally used. The full flight type is preferred for cellulose mixed ester resin. In addition, it is possible to use a twin screw extruder that can extrude while volatilizing unnecessary volatile components by providing a vent port in the middle by changing the force screw segment, which is expensive in equipment cost. Biaxial extruders can be broadly classified into the same direction and different direction types, and both can be used. The type of co-rotation with high self-cleaning performance is preferred because it is difficult to generate a staying part. Although the twin-screw extruder is expensive, it is suitable for forming cellulose acetate resin because it has high kneadability and high ability to supply the resin so that it can be extruded at low temperatures. It is possible to use cellulose acylate pellets and powder in an undried state by arranging vents appropriately. Noh. Also, it is possible to reuse film smudges, etc., produced during film formation, without drying them.
[0119] なお、好ましいスクリューの直径は目標とする単位時間あたりの押出量によって異な る力 10mm〜300mm、より好ましくは 20mm〜250mm、さらに好ましくは 30mm 〜150mmである。また、厚み精度を向上させるためには、吐出量の変動を減少させ ることが重要であり、押出機出機とダイスの間にギアポンプを設けて、ギアポンプから 一定量のセルロース混合エステル榭脂を供給することは効果がある。ギアポンプとは 、ドライブギアとドリブンギアとからなる一対のギアが互いに嚙み合った状態で収容さ れ、ドライブギアを駆動して両ギアを嚙み合い回転させることにより、ハウジングに形 成された吸引ロカも溶融状態の榭脂をキヤビティ内に吸引し、同じくハウジングに形 成された吐出ロカ その榭脂を一定量吐出するものである。押出機先端部分の榭脂 圧力が若干の変動があっても、ギアポンプを用いることにより変動を吸収し、製膜装 置下流の榭脂圧力の変動は非常に小さなものとなり、厚み変動が改善される。ギアポ ンプを用いることにより、ダイ部分の榭脂圧力の変動巾を ± 1%以内にすることが可 能である。  [0119] Note that a preferable screw diameter is 10 mm to 300 mm, more preferably 20 mm to 250 mm, and still more preferably 30 mm to 150 mm, depending on the target extrusion amount per unit time. In addition, in order to improve the thickness accuracy, it is important to reduce the fluctuation of the discharge amount. A gear pump is provided between the extruder and the die, and a certain amount of cellulose mixed ester resin is obtained from the gear pump. Supplying is effective. A gear pump is housed in a state in which a pair of gears consisting of a drive gear and a driven gear are intertwined with each other, and is formed in a housing by driving the drive gear and interposing and rotating both gears. The suction loca also sucks molten resin into the cavity and discharges a certain amount of the discharge loci formed in the housing. Even if there is a slight fluctuation in the grease pressure at the tip of the extruder, the fluctuation is absorbed by using a gear pump, and the fluctuation in the grease pressure downstream of the film forming apparatus is very small, improving the thickness fluctuation. The By using a gear pump, it is possible to keep the fluctuation range of the resin pressure in the die part within ± 1%.
[0120] ギアポンプによる定量供給性能を向上させるために、スクリューの回転数を変化さ せて、ギアポンプ前の圧力を一定に制御する方法も用いることができる。また、ギアポ ンプのギアの変動を解消した 3枚以上のギアを用いた高精度ギアポンプも有効であ る。ギアポンプを用いるその他のメリットとしては、スクリュー先端部の圧力を下げて製 膜できることから、エネルギー消費の軽減'榭脂温上昇の防止'輸送効率の向上'押 出機内での滞留時間の短縮'押出機の LZDを短縮が期待できる。また、異物除去 のために、フィルターを用いる場合には、ギアポンプが無いと、ろ圧の上昇と共に、ス クリュー力も供給される榭脂量が変動したりすることがあるが、ギアポンプを組み合わ せて用いることにより解消が可能である。一方、ギアポンプのデメリットとしては、設備 の選定方法によっては、設備の長さが長くなり、榭脂の滞留時間が長くなることと、ギ ァポンプ部のせん断応力によって分子鎖の切断を引き起こすことがあり、注意が必要 である。  [0120] In order to improve the quantitative supply performance by the gear pump, a method of controlling the pressure before the gear pump to be constant by changing the rotation speed of the screw can also be used. A high-precision gear pump using three or more gears that eliminates gear pump gear fluctuations is also effective. Other advantages of using a gear pump are that the pressure at the screw tip can be reduced to form a film, reducing energy consumption 'preventing a rise in oil temperature', 'increasing transport efficiency', 'reducing residence time in the extruder', extrusion The machine can be expected to shorten the LZD. In addition, when using a filter to remove foreign matter, if there is no gear pump, the amount of grease to which the screw force is supplied may fluctuate as the filtration pressure increases. It can be solved by using it. On the other hand, the disadvantages of gear pumps are that the length of the equipment increases, the residence time of the resin increases, and the chain breakage occurs due to the shear stress of the gear pump, depending on the equipment selection method. ,Caution must be taken.
[0121] 榭脂が供給ロカ 押出機に入って力 ダイス力 出るまでの榭脂の好ましい滞留 時間は 2分〜 60分であり、より好ましくは 3分〜 40分であり、さらに好ましくは 4分〜 3 0分である。ギアポンプの軸受循環用ポリマーの流れが悪くなることにより、駆動部と 軸受部におけるポリマーによるシールが悪くなり、計量および送液押し出し圧力の変 動が大きくなつたりする問題が発生するため、セルロース混合エステル榭脂の溶融粘 度に合わせたギアポンプの設計 (特にクリアランス）が必要である。また、場合によつ ては、ギアポンプの滞留部分がセルロース混合エステル榭脂の劣化の原因となるた め、滞留のできるだけ少ない構造が好ましい。押出機とギアポンプあるいはギアボン プとダイ等をつなぐポリマー管やアダプタにつ 、ても、できるだけ滞留の少な 、設計 が必要であり、且つ溶融粘度の温度依存性の高!、セルロース混合エステル榭脂の 押出圧力安定化のためには、温度の変動をできるだけ小さくすることが好ましい。一 般的には、ポリマー管の加熱には設備コストの安価なバンドヒーターが用いられること が多 、が、温度変動のより少な 、アルミ铸込みヒーターを用いることがより好ま 、。 さらに押出し機内で G'、 G〃、 tan δ、 r?に最大値、最小値を持たせるために、押出し 機のバレルを 3〜20に分割したヒーターで加熱し溶融することが好ましい。 [0121] Residue of the resin is preferred until the resin enters the supply loca extruder The time is 2 minutes to 60 minutes, more preferably 3 minutes to 40 minutes, and even more preferably 4 minutes to 30 minutes. Since the flow of the polymer for bearing circulation of the gear pump becomes poor, the polymer seal in the drive part and the bearing part becomes poor, causing problems such as large fluctuations in metering and liquid feed extrusion pressure. A gear pump design (especially clearance) that matches the melt viscosity of the resin is required. Further, in some cases, the stay portion of the gear pump causes deterioration of the cellulose mixed ester resin, so that a structure with as little stay as possible is preferable. The polymer pipes and adapters that connect the extruder and gear pump or gear pump and die need to be designed with as little residence as possible, and the temperature dependence of the melt viscosity is high! In order to stabilize the extrusion pressure, it is preferable to make the temperature fluctuation as small as possible. In general, band heaters with low equipment costs are often used for heating polymer tubes, but it is more preferable to use an aluminum encased heater with less temperature fluctuation. Further, in order to give G ′, G〃, tan δ, and r? Maximum and minimum values in the extruder, it is preferable to melt by heating the barrel of the extruder with a heater divided into 3 to 20.
[0122] 上記の如く構成された押出機によってセルロース混合エステル榭脂が溶融され、そ の溶融樹脂が吐出ロカゝらダイに連続的に送られる。ダイはダイス内の溶融榭脂の滞 留が少ない設計であれば、一般的に用いられる Τダイ、フィッシュテールダイ、ハンガ 一コートダイのいずれのタイプでも構わない。また、 Τダイの直前に榭脂温度の均一 性アップのためのスタティックミキサーを入れることも問題ない。 Τダイ出口部分のタリ ァランスは一般的にフィルム厚みの 1. 0〜5. 0倍が良ぐ好ましくは 1. 2〜3倍、さら に好ましくは 1. 3〜2倍である。リップクリアランスがフィルム厚みよりも小さ過ぎる場合 には製膜により面状の良好なシートを得ることが困難になる傾向がある。また、リップ クリアランスがフィルム厚みよりも大き過ぎる場合にはシートの厚み精度が低下する傾 向がある。 [0122] The cellulose mixed ester resin is melted by the extruder configured as described above, and the molten resin is continuously fed to the die from the discharge roller. As long as the die has a design in which the molten resin stays in the die less, any type of commonly used die, fishtail die or hanger-coated die may be used. In addition, there is no problem in placing a static mixer to increase the homogeneity of the temperature of the resin just before the dies.タ The exit balance of the die exit is generally 1.0 to 5.0 times the film thickness, preferably 1.2 to 3 times, and more preferably 1.3 to 2 times. If the lip clearance is too smaller than the film thickness, it tends to be difficult to obtain a good sheet by film formation. Also, if the lip clearance is too large than the film thickness, the sheet thickness accuracy tends to decrease.
[0123] ダイはフィルムの厚み精度を決定する非常に重要な設備であり、厚み調整がシビア にコントロールできるものが好まし、。通常厚み調整は 40〜50mm間隔で調整可能 であるが、好ましくは 35mm間隔以下、さらに好ましくは 25mm間隔以下でフィルム 厚み調整が可能なタイプが好ましい。また、セルロールァシレート榭脂は、溶融粘度 の温度依存性、せん断速度依存性が高いことから、ダイの温度ムラや巾方向の流速 ムラのできるだけ少ない設計が重要である。また、下流のフィルム厚みを計測して、厚 み偏差を計算し、その結果をダイの厚み調整にフィードバックさせる自動厚み調整ダ ィも長期連続生産の厚み変動の低減に有効である。フィルムの製造は設備コストの 安い単層製膜装置が一般的に用いられるが、場合によっては機能層を外層に設け ために多層製膜装置を用いて 2種以上の構造を有するフィルムの製造も可能である 。一般的には機能層を表層に薄く積層することが好ましいが、特に層比を限定するも のではない。 [0123] The die is a very important facility that determines the thickness accuracy of the film. Usually, the thickness can be adjusted at intervals of 40 to 50 mm, but preferably a type capable of adjusting the film thickness at intervals of 35 mm or less, more preferably at intervals of 25 mm or less. In addition, cellulose acylate has a melt viscosity Because of its high temperature dependency and shear rate dependency, it is important to design a die that has as little temperature variation as possible and uneven flow velocity in the width direction as much as possible. An automatic thickness adjustment die that measures the downstream film thickness, calculates the thickness deviation, and feeds the result back to the die thickness adjustment is also effective in reducing the thickness fluctuation in long-term continuous production. For film production, a single-layer film production apparatus with low equipment costs is generally used. Is possible. In general, the functional layer is preferably thinly laminated on the surface layer, but the layer ratio is not particularly limited.
[0124] 榭脂中の異物ろ過のためや異物によるギアポンプ損傷を避けるため押し出し機出 口にフィルター濾材を設ける!/、わゆるブレーカープレート式のろ過を行なうことが好ま しい。また  [0124] Provide filter media at the outlet of the extruder to filter foreign matter in the resin and to avoid damage to the gear pump due to foreign matter! / It is preferable to perform a breaker plate type filtration. Also
さらに精度高く異物ろ過をするために、ギアポンプ通過後にいわゆるリーフ型デイス クフィルターを組み込んだ濾過装置を設けることが好ましい。ろ過は、ろ過部を 1力所 設けて行なうことができ、また複数力所設けて行なう多段ろ過でも良い。フィルター濾 材の濾過精度は高い方が好ましいが、濾材の耐圧や濾材の目詰まりによる濾圧上昇 から、濾過精度は 15 μ m〜3 μ mが好ましくさらに好ましくは 10 μ m〜3 μ mである。 特に最終的に異物ろ過を行なうリーフ型ディスクフィルター装置を使用する場合では 品質の上で濾過精度の高い濾材を使用することが好ましぐ耐圧、フィルターライフ の適性を確保するために装填枚数にて調整することが可能である。濾材の種類は、 高温高圧下で使用される点力 鉄鋼材料を用いることが好ましぐ鉄鋼材料の中でも 特にステンレス鋼，スチールなどを用いることが好ましぐ腐食の点力も特にステンレ ス鋼を用いることがさらに好ましい。濾材の構成としては、線材を編んだものの他に、 例えば金属長繊維あるいは金属粉末を焼結し形成する焼結濾材が使用でき、濾過 精度，フィルターライフの点から焼結濾材が好まし 、。  In order to filter foreign matter with higher accuracy, it is preferable to provide a filtration device incorporating a so-called leaf type disk filter after passing through the gear pump. Filtration can be performed with a single filtration site, or multi-stage filtration with multiple power locations. The filtration accuracy of the filter medium is preferably higher, but the filtration accuracy is preferably 15 μm to 3 μm, more preferably 10 μm to 3 μm, because of the increase in the pressure resistance of the filter medium and the filtration pressure due to clogging of the filter medium. is there. In particular, when using a leaf-type disk filter device that finally filters foreign matter, it is preferable to use a filter medium with high filtration accuracy in terms of quality. It is possible to adjust. The type of filter medium is the point force used under high temperature and pressure. Among the steel materials that are preferred to use, stainless steel, steel, etc. are particularly preferred. More preferably. As the composition of the filter medium, in addition to the knitted wire, for example, a sintered filter medium formed by sintering metal long fibers or metal powder can be used, and the sintered filter medium is preferred from the viewpoint of filtration accuracy and filter life.
[0125] 3)キャスト [0125] 3) Cast
上記方法にて、ダイよりシート上に押し出された溶融榭脂をキャスティングドラム上 で冷却固化し、フィルムを得る。この時、静電印加法、エアナイフ法、エアーチャンバ 一法、バキュームノズル法、タツチロール法等の方法を用い、キャスティングドラムと溶 融押出ししたシートの密着を上げることが好ましい。このような密着向上法は、溶融押 出しシートの全面に実施してもよぐ一部に実施しても良い。特にエッジピユングと呼 ばれる、フィルムの両端部にのみを密着させる方法が取られることも多いが、これに 限定される物ではない。キャスティングドラムは複数本用い、徐冷する法がより好まし い、特に一般的には 3本の冷却ロールを用いることが比較的よく行われている力 こ の限りではない。ロールの直径は 50mm〜5000mmが好ましくより好ましくは、 100 mm〜2000mm、さらに好ましくは 150mm〜 1000mmである。複数本あるロールの 間隔は、面間で 0. 3mm〜300mmが好ましぐより好ましくは、 lmn！〜 100mm、さ らに好ましくは 3mm〜 3 Ommである。 By the above method, the molten resin extruded from the die onto the sheet is cooled and solidified on a casting drum to obtain a film. At this time, using a method such as an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, a touch roll method, etc., It is preferable to increase the adhesion of the melt-extruded sheet. Such adhesion improving method may be performed on the entire surface of the melt-extruded sheet or a part thereof. In particular, a method called “edge-pilling” in which only both ends of the film are brought into close contact with each other is often used, but the method is not limited to this. It is more preferable to use a plurality of casting drums and slowly cool them. In particular, it is not particularly limited to use three cooling rolls that are relatively common. The diameter of the roll is preferably 50 mm to 5000 mm, more preferably 100 mm to 2000 mm, and still more preferably 150 mm to 1000 mm. The interval between multiple rolls is preferably between 0.3 mm and 300 mm, more preferably lmn! -100 mm, more preferably 3 mm-3 Omm.
[0126] キャスティングドラムは 60°C〜160°Cが好ましぐより好ましくは 70°C〜150°C、さら に好ましくは 80°C〜140°Cである。この後、キャスティングドラム力も剥ぎ取り、 -ップ ロールを経た後巻き取る。巻き取り速度は 10mZ分〜 lOOmZ分が好ましぐより好 ましくは 15mZ分〜 80mZ分、さらに好ましくは 20mZ分〜 70mZ分である。  [0126] The casting drum is preferably from 60 ° C to 160 ° C, more preferably from 70 ° C to 150 ° C, and even more preferably from 80 ° C to 140 ° C. After this, peel off the casting drum force. The winding speed is preferably 10 mZ min to lOO mZ min, more preferably 15 mZ min to 80 mZ min, and even more preferably 20 mZ min to 70 mZ min.
製膜幅は好ましくは 0. 7m〜5m、さらに好ましくは lm〜4m、さらに好ましくは 1. 3 m〜3mである。このようにして得られた未延伸フィルムの厚みは 20 μ m〜400 μ m 力 S好ましく、より好ましくは 40 μ m〜300 μ m、さらに好ましくは 50 μ m〜200 μ mで ある。本発明では、得られたセルロース混合エステルフィルムの厚みが 200 μ mを超 える場合には、をさらに延伸することで、本発明の好ましい膜厚にすることができる。 また、いわゆるタツチロール法を用いる場合、タツチロール表面は、ゴム、テフロン等 の榭脂でもよぐ金属ロールでも良い。さらに、金属ロールの厚みを薄くすることでタツ チしたときの圧力によりロール表面が若干くぼみ、圧着面積が広くなりフレキシブル口 ールと呼ばれる様なロールを用いることも可能である。タツチロール温度は 60°C〜16 0°Cが好ましぐより好ましくは 70°C〜150°C、さらに好ましくは 80°C〜140°Cである。  The film forming width is preferably 0.7 m to 5 m, more preferably lm to 4 m, and further preferably 1.3 m to 3 m. The thickness of the unstretched film thus obtained is preferably 20 μm to 400 μm force S, more preferably 40 μm to 300 μm, still more preferably 50 μm to 200 μm. In this invention, when the thickness of the obtained cellulose mixed ester film exceeds 200 micrometers, it can be set as the preferable film thickness of this invention by extending | stretching further. When the so-called touch roll method is used, the surface of the touch roll may be a metal roll such as rubber or Teflon. Furthermore, it is also possible to use a roll called a flexible tool because the surface of the roll is slightly dented by the pressure when touched by reducing the thickness of the metal roll, and the crimping area is increased. The tack roll temperature is preferably 60 ° C to 160 ° C, more preferably 70 ° C to 150 ° C, and still more preferably 80 ° C to 140 ° C.
[0127] (巻き取り）  [0127] (Rewind)
このようにして得たシートは両端をトリミングし、巻き取ることが好ましい。トリミングさ れた部分は、粉砕処理された後、あるいは必要に応じて造粒処理や解重合 '再重合 等の処理を行った後、同じ品種のフィルム用原料としてまたは異なる品種のフィルム 用原料として再利用してもよい。トリミングカッターはロータリーカッター、シヤー刃、ナ ィフ等いずれのタイプの物を用いても構わない。材質についても、炭素鋼、ステンレ ス鋼いずれを用いても構わない。一般的には、超硬刃、セラミック刃を用いると刃物 の寿命が長ぐまた切り粉の発生が抑えられて好ましい。 The sheet thus obtained is preferably trimmed at both ends and wound up. The trimmed part is pulverized or, if necessary, granulated or depolymerized and re-polymerized, and then used as a raw material for film of the same type or as a raw material for film of a different type. It may be reused. The trimming cutter is a rotary cutter, shear blade, Any type of material such as a gift may be used. Regarding the material, either carbon steel or stainless steel may be used. In general, it is preferable to use a cemented carbide blade or a ceramic blade because the life of the blade is long and the generation of chips is suppressed.
[0128] また、巻き取り前に、少なくとも片面にラミフィルムを付けることも、傷防止の観点力 好ましい。好ましい巻き取り張力は好ましくは lkg/m幅〜 50kg/幅、より好ましくは 2k g/m幅〜 40kg/幅、さらに好ましくは 3kg/m幅〜 20kg/幅である。巻き取り張力が小 さ過ぎると、フィルムを均一に巻き取ることが困難になる傾向がある。逆に、巻き取り張 力が大き過ぎると、フィルムが堅卷きになってしまい、巻き外観が悪ィ匕するのみでなく 、フィルムのコブの部分がクリープ現象により延びてフィルムの波うちの原因になった り、あるいはフィルムの伸びによる残留複屈折が生じやすくなる傾向がある。巻き取り 張力は、ラインの途中のテンションコントロールにより検知し、一定の巻き取り張力に なるようにコントロールされながら巻き取ることが好ましい。製膜ラインの場所により、フ イルム温度に差がある場合には熱膨張により、フィルムの長さが僅かに異なる場合が あるため、 -ップロール間のドロー比率を調整し、ライン途中でフィルムに規定以上の 張力が力からない様にすることが必要である。巻き取り張力はテンションコントロール の制御により、一定張力で巻き取ることもできる力 巻き取った直径に応じてテーパー をつけ、適正な巻き取り張力にすることがより好ましい。一般的には卷き径が大きくな るにつれて張力を少しずつ小さくする力 場合によっては、卷き径が大きくなるにした 力 て張力を大きくする方が好ましい場合もある。  [0128] It is also preferable to attach a laminated film on at least one surface before winding, from the viewpoint of preventing scratches. The preferred winding tension is preferably 1 kg / m width to 50 kg / width, more preferably 2 kg / m width to 40 kg / width, and even more preferably 3 kg / m width to 20 kg / width. If the winding tension is too small, it tends to be difficult to wind the film uniformly. On the other hand, if the take-up tension is too large, the film becomes stiff and not only the winding appearance is deteriorated, but also the bump portion of the film extends due to the creep phenomenon, causing the film to wavy. Or residual birefringence tends to occur easily due to film elongation. The winding tension is preferably detected by tension control in the middle of the line and wound while being controlled so as to have a constant winding tension. If there is a difference in film temperature depending on the location of the film production line, the length of the film may be slightly different due to thermal expansion. It is necessary to prevent the above tension from being applied. The take-up tension is a force that can be taken up at a constant tension by controlling the tension control. It is more preferable to taper the take-up tension in accordance with the diameter of the take-up to obtain an appropriate take-up tension. In general, the force that gradually decreases the tension as the winding diameter increases. In some cases, it may be preferable to increase the tension by increasing the winding diameter.
[0129] (溶融製膜工程）  [0129] (Melting process)
次の本発明の溶融製膜工程とその条件などについて記載する。  Next, the melt film-forming process of the present invention and its conditions will be described.
一般に、溶融製膜はセルロース混合エステルを予め所定の温度に予熱し、添加物 などを混合する混練 ·押し出し工程、キャスト工程、延伸工程、緩和工程、冷却工程、 巻き取り工程、加工工程を通じて、所望のセルロース混合エステルフィルムを得るも のである。溶融製膜条件の最適化について、以下に詳細に記述する。  In general, melt film formation is performed through a kneading / extrusion process, casting process, stretching process, relaxation process, cooling process, winding process, and processing process in which cellulose mixed ester is preheated to a predetermined temperature and mixed with additives. A cellulose mixed ester film is obtained. The optimization of melt film forming conditions is described in detail below.
[0130] (セルロース混合エステルの予熱）  [0130] (Preheating cellulose mixed ester)
セルロース混合エステルは予め十分に乾燥した後に、溶融押出し機のホッパーに 投入されるのが好ましい。好ましい乾燥としては、セルロース混合エステル中の水分 量が 0. 5質量％以下であり、より好ましくは 0. 2質量％であり、特には 0. 1質量％以 下である。これにより溶融中に発現するセルロース混合エステルの加水分解を抑制し 、これに伴う異物の発生を抑止できる。このような乾燥は、セルロース混合エステルを 好ましくは 80°C〜180°Cで、好ましくは 0. 1時間〜 100時間乾燥することで達成でき る。なお、この処理は、空気雰囲気下で行っても、不活性気体 (例えば窒素）雰囲気 下で行っても、真空中で行ってもよい。該前処理により製膜中に発生する異物も軽減 することができる。特に減圧下での加熱による乾燥が好ましい。これは異物の発生源 がセルロース混合エステルの水による加水分解物、あるいは結合硫酸による硫酸脱 離による脱水反応、さらには酸素による酸ィ匕分解などに主に起因しているためである 。本発明で好ましく使用されるホッパーの加熱温度は、セルロース混合エステルの好 ましくは (Tg— 50°C)〜 (Tg + 30°C)、より好ましくは (Tg— 40°C)〜 (Tg + 10°C)、 さらに好ましくは (Tg— 30°C)〜Tgに加熱しておくことが推奨される。これによりホッ パー内でのセルロース混合エステルへの空気中からの水分再吸着が抑制できる。 (混練押出し） It is preferable that the cellulose mixed ester is sufficiently dried in advance and then charged into a hopper of a melt extruder. As the preferred drying, moisture in the cellulose mixed ester The amount is 0.5% by mass or less, more preferably 0.2% by mass, and particularly 0.1% by mass or less. As a result, hydrolysis of the cellulose mixed ester that develops during melting can be suppressed, and generation of foreign substances associated therewith can be suppressed. Such drying can be achieved by drying the cellulose mixed ester preferably at 80 ° C to 180 ° C, preferably for 0.1 hour to 100 hours. This treatment may be performed in an air atmosphere, an inert gas (for example, nitrogen) atmosphere, or in a vacuum. Foreign substances generated during film formation can be reduced by the pretreatment. In particular, drying by heating under reduced pressure is preferable. This is because the source of foreign substances is mainly due to the hydrolyzate of cellulose mixed ester with water, the dehydration reaction by sulfuric acid desorption with bound sulfuric acid, and the acid decomposition with oxygen. The heating temperature of the hopper preferably used in the present invention is preferably (Tg—50 ° C) to (Tg + 30 ° C), more preferably (Tg—40 ° C) to (Tg + 10 ° C), more preferably (Tg—30 ° C) to Tg is recommended. As a result, moisture re-adsorption from the air to the cellulose mixed ester in the hopper can be suppressed. (Kneading extrusion)
溶融押し出し機に設置されている 2〜15の圧縮比を有する混練スクリューを用い、 予熱過程で加熱された所望の溶融温度で、セルロース混合エステルを混練する。す なわち、本発明ではダイスジを解消するために、本発明におけるセルロース混合エス テルの溶融温度を 180°C〜230°Cとし、好ましくは 190°C〜225°C、さらに好ましくは 190°C〜220°Cで実施する。 230°C以上の高い温度で溶融した場合、本発明にお けるセルロース混合エステルに分解が生じ、該分解物がダイ内に残留することで発 生するダイラインが引き起こし、厚みムラが著しく悪化する。さらに着色も著しく発生し 、製膜時に発生する耳部のロス分を再利用できないという、問題を引き起こす。本発 明では、先願の実施例に記載されて ヽる方法ではセルロース混合エステルの分解が 著しい高温で実施されていることを鑑みて改良したものである。なお、溶融温度を 18 0°C未満に低下させると溶融不良が発生し、これがブッを発生する原因となりやすい 。そこで本発明では、低温でも不溶解を発生させないために、高圧縮比のスクリュー を用いていることも推奨される。好ましい圧縮比は 2〜15であり、 3〜15がより好ましく 、 4〜12が更に好ましぐ 5〜： L0が特に好ましい。通常は 3未満の圧縮比で溶融する のが一般的である。 Using a kneading screw having a compression ratio of 2 to 15 installed in a melt extruder, the mixed cellulose ester is kneaded at a desired melting temperature heated in the preheating process. That is, in the present invention, in order to eliminate die lines, the melting temperature of the cellulose mixed ester in the present invention is set to 180 ° C to 230 ° C, preferably 190 ° C to 225 ° C, more preferably 190 ° C. Perform at ~ 220 ° C. When melted at a high temperature of 230 ° C. or higher, the cellulose mixed ester in the present invention is decomposed, and a die line is generated due to the decomposition product remaining in the die, and the thickness unevenness is remarkably deteriorated. Furthermore, the coloring is remarkably generated, which causes a problem that the ear loss generated during film formation cannot be reused. In the present invention, the method described in the examples of the prior application is improved in view of the fact that the decomposition of the cellulose mixed ester is carried out at a remarkably high temperature. Note that when the melting temperature is lowered to less than 180 ° C., poor melting occurs, and this tends to cause bumps. Therefore, in the present invention, it is also recommended to use a screw with a high compression ratio so as not to cause insolubility even at low temperatures. A preferred compression ratio is 2 to 15, 3 to 15 is more preferred, 4 to 12 is even more preferred 5: L0 is particularly preferred. Usually melts at a compression ratio of less than 3 It is common.
[0132] この際には、溶融温度は一定温度で行ってもよぐいくつかに分割して制御して得 られた溶融温度で実施してもよ!/、。より好ましくは上流側（ホッパー側）の温度を下流 側 (T—ダイ側）の温度より 1°C〜50°C、より好ましくは 2°C〜30°C、さらに好ましくは 3 °C〜20°C高くするほうが、セルロース混合エステルの分解をより抑制できて好ましい 。また、溶融を効率よく実施するためには、好ましくは送液上流部をより高温にし、溶 融された後はセルロース混合エステルの分解を抑制するために、温度を低めにする ことが好ましい。更に、好ましい混練時間は 2分間〜 60分間であり、より好ましくは 3 分間〜 40分間であり、さらに好ましくは 4分間〜 30分間である。さらに、溶融押出し 機内を不活性 (窒素等)気流中で実施するのも好まし ヽ。  [0132] In this case, the melting temperature may be a constant temperature or may be performed at a melting temperature obtained by dividing into several parts and controlling! /. More preferably, the temperature on the upstream side (hopper side) is 1 ° C to 50 ° C, more preferably 2 ° C to 30 ° C, even more preferably 3 ° C to 20 ° C from the temperature on the downstream side (T-die side) A higher temperature is preferable because decomposition of the cellulose mixed ester can be further suppressed. Further, in order to efficiently perform the melting, it is preferable to lower the temperature in order to suppress the decomposition of the cellulose mixed ester after melting, preferably at a higher temperature in the upstream portion of the liquid feeding. Furthermore, a preferable kneading time is 2 minutes to 60 minutes, more preferably 3 minutes to 40 minutes, and further preferably 4 minutes to 30 minutes. It is also preferable to carry out the inside of the melt extruder in an inert (nitrogen, etc.) stream.
[0133] (キャスト）  [0133] (Cast)
溶融したセルロース混合エステルは、ギヤポンプに通して押し出し機の脈動を除去 されるのが好ましい。その後に続いて、金属メッシュフィルタ一等でろ過を行うのが好 ましい。メッシュの目の大きさは 2〜30 mが好ましぐより好ましくは 2〜20 /ζ πι、さら に好ましくは 2〜： LO mである。この際、加圧を行い、濾過に要する時間をできるだ け短縮することが好ましい。濾過圧は、 0. 5MPa〜15MPaが好ましぐ 2Pa〜15M Paがさらに好ましぐ 10Pa〜15MPaがもっとも好ましい。濾過圧は、高いほうが濾過 時間を短くすることができるので好ま U、が、フィルターの破損が起こらな 、範囲の高 圧を用いることが好ましい。濾過の時の温度は 180°C〜230°Cが好ましぐ 180°C〜 220°Cがさらに好ましぐ 190〜220°Cがさらに好ましい。濾過時の温度が該上限値 以下であれば、熱劣化が進行するなどの問題が生じにくいので好ましぐ該下限値 以上であれば、濾過に時間が力かりすぎて熱劣化が進行するなどの不都合が生じに くいので好ましい。濾過に要する時間はできるだけ短くして、フィルムの黄変を防止す るのがよい。フィルター lcm2当たり 1分間の濾過量は、 0. 05〜： LOOcm3力 子ましく、 0. 1〜： LOOcm3がさらに好ましぐ 0. 5〜： L 00cm3がもっとも好ましい。 The molten cellulose mixed ester is preferably passed through a gear pump to remove the pulsation of the extruder. Following that, it is preferable to filter with a metal mesh filter or the like. The mesh size is preferably 2 to 30 m, more preferably 2 to 20 / ζ πι, and even more preferably 2 to LO m. At this time, it is preferable to apply pressure to shorten the time required for filtration as much as possible. The filtration pressure is preferably 0.5 MPa to 15 MPa, more preferably 2 Pa to 15 MPa, and most preferably 10 Pa to 15 MPa. A higher filtration pressure is preferable because the filtration time can be shortened. However, it is preferable to use a high pressure within a range in which the filter does not break. The temperature during filtration is preferably 180 ° C to 230 ° C, more preferably 180 ° C to 220 ° C, and further preferably 190 ° C to 220 ° C. If the temperature at the time of filtration is less than or equal to the upper limit value, problems such as the progress of thermal degradation are unlikely to occur, so if it is greater than or equal to the preferred lower limit value, too much time is required for filtration and the thermal degradation proceeds. This is preferable because the inconvenience is not likely to occur. The time required for filtration should be as short as possible to prevent yellowing of the film. The amount of filtration per minute per filter lcm 2 is 0.05-: LOOcm 3 forceful, 0.1-: LOOcm 3 is more preferable 0.5-: L 00 cm 3 is most preferable.
[0134] 次に、製膜ダイとしては例えば T型ダイ (T—ダイ)またはハンガー型 (ハンガーコー トダイ）が挙げられるが、 T—ダイが好ましい。ダイ力も搬送する冷却ドラム上にシート 状に押し出すが、前述のように溶融温度より低い温度に制御したダイ力 押出すこと が好ましい。なお、溶融温度が溶融押出し機内で複数に分割し異なる温度にするこ とも可能である力 その場合はダイに最も近いところの溶融温度を基準にする。この 後、上述のようにダイとキャスティングドラムとの間を一定の距離（l〜50cmが好まし い）に保つ。この際、この間の温度変動が少ないよう、ケーシング内に入れることが好 ましい。さらに本発明では、ダイの温度を溶融温度より 5°C〜30°C低くすることが好ま しい。これは、ダイ上で滞留しセルロース混合エステルが分解し焦げつき、これがダイ ラインを引き起こすのを防ぐため、ダイの温度を下げたことが特徴である。通常の製膜 では溶融混練機力 ダイまで同じ温度ある 、はそれ以上にし、溶融粘度を低くするこ とで、発生したダイラインをレベリングイ匕するのが一般的である力 熱分解しやすいセ ルロース混合エステルを溶融製膜する場合は前記のように温度を下げることが有効 である。 [0134] Next, examples of the film forming die include a T-type die (T-die) and a hanger type (hanger-coated die), and a T-die is preferable. The die force is also extruded in the form of a sheet onto the cooling drum that conveys it, but as described above, the die force is controlled to a temperature lower than the melting temperature. Is preferred. Note that the melt temperature can be divided into multiple parts in the melt extruder and made different. In this case, the melt temperature closest to the die is used as a reference. After this, keep a certain distance (preferably 1-50 cm) between the die and the casting drum as described above. At this time, it is preferable to put in the casing so that the temperature fluctuation during this period is small. Furthermore, in the present invention, it is preferable that the die temperature is 5 ° C to 30 ° C lower than the melting temperature. This is characterized by the fact that the temperature of the die was lowered in order to prevent it from staying on the die and decomposing and burning the cellulose mixed ester, which would cause die line. In normal film formation, melt kneading machine power is the same temperature up to the die, or higher, and by lowering the melt viscosity, it is common to level the generated die line. When the mixed ester is melt-cast, it is effective to lower the temperature as described above.
[0135] また、セルロース混合エステルフィルムの横ダン（幅方向に発生する段々状のムラ） を解消するために、本発明ではダイとキャスティングドラムとの間を 2cm〜50cm離す ことが好ましい。より好ましくは 5cm〜40cm、さらに好ましくは 7cm〜35cmである。 通常はネックインを防ぐためにダイとキャスティングドラムとの間はなるべく近づけるの が一般的であり、本発明では l〜3cm間隔に近づけることが好ましいとされている。 しかし、本発明ではセルロース混合エステルがネックインしにくいため、前記のよう にキャスティングドラムとダイとの間を広くとることが好ましい。この際のキャスティングド ラムの温度は (Tg— 30°C)〜Tgが好ましぐより好ましくは (Tg— 20°C)〜 (Tg— 1°C )、さらに好ましくは (Tg— 15°C)〜(Tg— 2°C)である。さらにこのようにダイ、キャステ イングドラム間の距離を長くすることは、前記ダイ筋をレべリング化させ軽減させる効 果も有する。なお、本発明のセルロース混合エステルの Tgは 70°C〜180°Cが好まし ぐより好ましくは 80°C〜160°C、さらに好ましくは 90°C〜150°Cである。  [0135] Further, in order to eliminate the horizontal dan (stepwise unevenness generated in the width direction) of the cellulose mixed ester film, it is preferable that the die and the casting drum be separated from each other by 2 to 50 cm. More preferably, it is 5 cm to 40 cm, and further preferably 7 cm to 35 cm. Usually, in order to prevent neck-in, it is common to make the die and the casting drum as close as possible. In the present invention, it is preferable to make the distance close to 1 to 3 cm. However, in the present invention, since the cellulose mixed ester is difficult to neck-in, it is preferable to take a wide space between the casting drum and the die as described above. The temperature of the casting drum at this time is preferably (Tg—30 ° C) to Tg, more preferably (Tg—20 ° C) to (Tg—1 ° C), and even more preferably (Tg—15 ° C). ) To (Tg—2 ° C.). Furthermore, increasing the distance between the die and the casting drum in this way also has the effect of leveling and reducing the die line. The Tg of the cellulose mixed ester of the present invention is preferably 70 ° C to 180 ° C, more preferably 80 ° C to 160 ° C, and still more preferably 90 ° C to 150 ° C.
[0136] 押出しは単層で行ってもよぐマルチマ-ホールドダイやフィールドブロックダイを用 いて複数層押出してもよい。この後、適宜選ばれた直径（10〜200cmが好ましい）、 本数（2〜20本が好まし 、）、温度 (Tg— 30°Cが好まし 、）のキャスティングドラム上 に押出す。この際、静電印加法、エアナイフ法、エアーチャンバ一法、バキュームノズ ル法、タツチロール法等の方法を用い、キャスティングドラムと溶融押出ししたシート の密着を上げることが好ましい。このような密着向上法は、溶融押出しシートの前面 に実施してもよぐ一部に実施してもよい。 [0136] Extrusion may be performed in a single layer, or a multi-layer extrusion may be performed using a multi-hold die or a field block die. After that, it is extruded onto a casting drum having an appropriately selected diameter (preferably 10 to 200 cm), number (preferably 2 to 20), and temperature (Tg-30 ° C is preferred). At this time, a sheet that has been melt-extruded with a casting drum by using an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, a touch roll method, or the like. It is preferable to increase the adhesion. Such adhesion improving method may be performed on the front surface of the melt-extruded sheet or on a part thereof.
[0137] 次に T—ダイ力も押出された溶融されたセルロース混合エステル (メルト）は、キャス ティングドラム上で冷却固化する時間をできるだけ長くすることが好ましい。即ち、 T ダイから Tg以上で押出されたメルトがキャスティングドラム上で Tg近傍以下になり 収縮する。この際、面内方向の収縮はメルトとキャスティングドラムとの摩擦で抑制さ れるため、厚み方向の収縮が支配的になる。即ちここで面配向が形成され厚み方向 のレターデーシヨン (Rth) (以下、「Rth」と称する場合がある。）が発現する。この収 縮が急激であると、 Rthのムラを発現し易ぐ前記のようにゆっくり冷却することがボイ ントである。即ち（Tg + 30°C)から Tgの間を 10°CZ秒〜 100°CZ秒の速度（固化速 度)で冷却し固化するのが好ましぐより好ましい固化速度は 15°CZ秒〜 80°CZ秒、 さらに好ましくは 20°CZ秒〜 60°CZ秒で冷却するのが好ましい。通常の榭脂の場合 は、 300°CZ秒以上で固化させるため、本発明の冷却における前記範囲は十分に 遅い冷却速度である。そのために、キャスティングドラムと T—ダイとの間を温調する のが好ましぐ好ましい温度は (Tg— 30°C)〜(Tg + 50°C)、より好ましくは (Tg— 20 °C)〜 (Tg+40°C)、さらに好ましくは (Tg— 10°C)〜 (Tg + 30°C)である。  [0137] Next, it is preferable that the time for cooling and solidifying the molten cellulose mixed ester (melt), which is also extruded with the T-die force, on the casting drum is as long as possible. That is, the melt extruded above Tg from the T die shrinks to below Tg on the casting drum. At this time, since shrinkage in the in-plane direction is suppressed by friction between the melt and the casting drum, shrinkage in the thickness direction becomes dominant. That is, a plane orientation is formed here, and letter-thickness (Rth) in the thickness direction (hereinafter sometimes referred to as “Rth”) is developed. If this contraction is abrupt, the point is to cool slowly as described above, which easily develops Rth unevenness. That is, it is preferable to cool and solidify between (Tg + 30 ° C) and Tg at a speed (solidification speed) of 10 ° CZ seconds to 100 ° CZ seconds. A more preferable solidification rate is 15 ° CZ seconds to 80 ° C. It is preferable to cool at ° CZ seconds, more preferably 20 ° CZ seconds to 60 ° CZ seconds. In the case of ordinary resin, it is solidified in 300 ° CZ seconds or more, so the above-mentioned range in the cooling of the present invention is a sufficiently slow cooling rate. Therefore, it is preferable to adjust the temperature between the casting drum and the T-die (Tg-30 ° C) to (Tg + 50 ° C), more preferably (Tg-20 ° C). To (Tg + 40 ° C), more preferably (Tg—10 ° C) to (Tg + 30 ° C).
[0138] 本発明では、好ましいキャスティングドラムの本数は 2本〜 10本、より好ましくは 2本 〜6本、さらに好ましくは 3本〜 5本である。これらのキャスティングドラムの温度は同じ であってもよぐ異なっていてもよい。最上流のキャスティングドラムの温度を最下流の キャスティングドラムより低くすることがより好ましい。 3本以上配置する場合は、これら の間のキャスティングドラム温度を、その前段のロールの温度より高くても低くても構 わない。即ち、最上流とり最下流の温度を低くすればよぐその間のロール温度は任 意に設定してょ 、。これらのキャスティングドラムの直径は通常 20cm〜200cmであ る。これらの製膜速度は、 15mZ分〜 300mZ分の速度で製膜することが好ましい。 より好ましくは 20mZ分〜 200mZ分、さらに好ましくは 30mZ分〜 1 OOmZ分であ る。  [0138] In the present invention, the number of casting drums is preferably 2 to 10, more preferably 2 to 6, and further preferably 3 to 5. The temperature of these casting drums may be the same or different. More preferably, the temperature of the most upstream casting drum is lower than that of the most downstream casting drum. When three or more are disposed, the casting drum temperature between them may be higher or lower than the temperature of the preceding roll. In other words, the temperature of the uppermost stream and the lowermost stream should be lowered, and the roll temperature during that time should be set arbitrarily. The diameter of these casting drums is usually 20cm to 200cm. It is preferable to form these films at a rate of 15 mZ to 300 mZ. More preferably, it is 20 mZ minutes to 200 mZ minutes, and further preferably 30 mZ minutes to 1 OOmZ minutes.
[0139] 冷却した後、セルロース混合エステルフィルムは、キャスティングドラム力も剥ぎ取ら れ、ニップロールを経て、ニップロールで張力カットした後、巻き取り時の張力が 0. 0 lkgZcm2〜10kgZcm2で巻き取るのが好ましぐより好ましくは 0. 10kgZcm2〜9 kg/cm2,さら〖こ好ましくは 0. 10kgZcm2〜9kgZcm2である。巻き取り速度は 10m Z分〜 lOOmZ分が好ましぐより好ましくは 15mZ分〜 80mZ分、さらに好ましくは 20mZ分〜 70mZ分である。製膜幅は好ましくは 1. 5m〜5m、より好ましくは 1. 6 m〜4m、さらに好ましくは 1. 7m〜3mである。キャスティングドラムから剥ぎ取った直 後のシートは Tgに近い温度のため、巻き取り張力により延伸され Re、 Rthが発現し、 これは中央部より端部において顕著になる。 [0139] After cooling, the cellulose mixed ester film was stripped of the casting drum force, passed through the nip roll, cut with the nip roll, and then wound up with a tension of 0.0. lkgZcm 2 ~10kgZcm more preferably preferably wound up is fitting in 2 0. 10kgZcm 2 ~9 kg / cm 2, further 〖This preferably 0. 10kgZcm 2 ~9kgZcm 2. The winding speed is preferably 10 mZ min to lOO mZ min, more preferably 15 mZ min to 80 mZ min, and even more preferably 20 mZ min to 70 mZ min. The film forming width is preferably 1.5 m to 5 m, more preferably 1.6 m to 4 m, and still more preferably 1.7 m to 3 m. Since the sheet immediately after peeling off from the casting drum is close to Tg, it is stretched by the winding tension to develop Re and Rth, and this becomes more prominent at the end than at the center.
[0140] このため、正面レターデーシヨン (Re) (以下、「Re」と称する場合がある。 ) , Rthが 放物線状のムラを発現する。キャスティングドラムの後に-ップロールを設置し、巻き 取り張力のカットする方法が挙げられる力 完全にはカットできず僅かに張力がキャス ティングドラム剥ぎ取り後のシートまで伝播する。これが Re, Rthムラを引き起こす。こ のようなムラは、幅方向全域に渡っておこるため、小さなサイズでは検知し難ぐ大き なサイズを切り出したときに、問題となる。このため、前記のような弱い張力で巻き取る ことがポイントである（通常は 20kg/cm2以上で巻かれる）。このような低張力で卷くこ とで巻きズレが発生し易くなる力 これには両端にナーリング (厚みだし)加工を付与 することで対策できる。このようにして得られたフィルムの厚みは 20 μ m〜400 μ mが 好ましく、さら〖こ好ましくは 40 μ m〜200 μ m、特〖こ好ましくは 50 μ m〜150 μ mであ る。本発明では、得られたセルロース混合エステルフィルムの厚みが 200 μ mを超え る場合には、をさらに延伸することで、本発明の好ましい膜厚にすることができる。 [0140] For this reason, front letter determination (Re) (hereinafter sometimes referred to as "Re"), Rth develops parabolic unevenness. A force that includes a method of installing a roll-up roll after the casting drum to cut the take-up tension is not possible. The tension cannot be completely cut, and the tension is slightly propagated to the sheet after the casting drum is peeled off. This causes Re, Rth unevenness. Since such unevenness occurs over the entire width direction, it becomes a problem when cutting out a large size that is difficult to detect with a small size. For this reason, it is important to wind with such a weak tension (usually wound at 20 kg / cm 2 or more). Such a force that causes winding misalignment by rolling with low tension. This can be dealt with by applying a knurling process to both ends. The thickness of the film thus obtained is preferably 20 μm to 400 μm, more preferably 40 μm to 200 μm, and particularly preferably 50 μm to 150 μm. In this invention, when the thickness of the obtained cellulose mixed ester film exceeds 200 micrometers, it can be set as the preferable film thickness of this invention by extending | stretching further.
[0141] また、未延伸フィルムを延伸することで、厚みムラ、 Reムラ、 Rthムラ、 Re, Rthの湿 度変動の小さな延伸フィルムを得ることも可能である。このようにして得たシートは両 端をトリミングし、巻き取ることが好ましい。トリミングされた部分は、粉砕処理された後 、あるいは必要に応じて造粒処理や解重合'再重合等の処理を行った後、同じ品種 のフィルム用原料としてまたは異なる品種のフィルム用原料として再利用してもよい。 また、巻き取り前に、少なくとも片面にラミネートフィルムを付けることも、傷防止の観 点から好ましい。  [0141] Further, by stretching an unstretched film, it is possible to obtain a stretched film having small thickness unevenness, Re unevenness, Rth unevenness, and Re and Rth humidity fluctuations. The sheet thus obtained is preferably trimmed at both ends and wound up. The trimmed portion is crushed or reprocessed as a raw material for film of the same type or as a raw material for film of a different type after being subjected to processing such as granulation or depolymerization and re-polymerization as necessary. May be used. In addition, it is also preferable from the viewpoint of scratch prevention to attach a laminate film on at least one side before winding.
[0142] (延伸工程） [0142] (Stretching process)
溶融製膜工程にぉ 、てフィルム化されたセルロース混合エステルフィルムは、延伸 工程にお ヽて少なくとも 1方向に延伸されることが好ま ヽ。延伸は Tg〜 (Tg + 50°C )で実施するのが好ましぐより好ましくは (Tg+ l°C)〜(Tg + 30°C)、さらに好ましく は (Tg + 2°C)〜 (Tg + 20°C)である。好ま 、延伸倍率は少なくとも 1方向に— 10 %〜50%延伸することが好ましい。延伸倍率は 1%〜150%がより好ましぐさらに好 ましくは 1%〜100%、特に好ましくは 1%〜50%である。これらの延伸は 1段で実施 しても、多段で実施してもよい。ここで云う延伸倍率は、以下の式を用いて求めたもの である。 The cellulose mixed ester film formed into a film during the melt film-forming process is stretched. The process is preferably stretched in at least one direction. Stretching is preferably performed at Tg to (Tg + 50 ° C), more preferably (Tg + l ° C) to (Tg + 30 ° C), and even more preferably (Tg + 2 ° C) to (Tg + 20 ° C). Preferably, the stretching ratio is preferably at least 10% to 50% stretched in one direction. The draw ratio is preferably 1% to 150%, more preferably 1% to 100%, and particularly preferably 1% to 50%. These stretching operations may be performed in one stage or in multiple stages. The draw ratio here is determined using the following equation.
延伸倍率 (％) = 100 X { (延伸後の長さ） - (延伸前の長さ） }Z延伸前の長さ このような延伸は出口側の周速を速くした 2対以上の-ップロールを用いて、長手 方向に延伸してもよく（縦延伸）、フィルムの両端をチャックで把持しこれを直交方向（ 長手方向および直角方向）に広げてもよい (横延伸）。  Stretch ratio (%) = 100 X {(Length after stretching)-(Length before stretching)} Z Length before stretching Two or more pairs of up-rolls with such a stretch that increased the peripheral speed on the exit side The film may be stretched in the longitudinal direction (longitudinal stretching), or both ends of the film may be held by a chuck and spread in the orthogonal direction (longitudinal direction and perpendicular direction) (lateral stretching).
[0143] 一般にいずれの場合も、延伸倍率を大きくすると、 Re, Rthとも大きくすることができ る。さらに Re、 Rthの比を自由に制御するには、縦延伸の場合、 -ップロール間をフ イルム幅で割った値 (縦横比）を制御することで達成できる。即ち縦横比を小さくする ことで、 RthZRe比を大きくすることができる。横延伸の場合、直交方向に延伸すると 同時に縦方向にも延伸したり、逆に緩和させることで制御することができる。即ち縦方 向に延伸することで RthZRe比を大きくすることができ、逆に縦方向に緩和すること で RthZRe比を小さくすることができる。このような延伸速度は 10%Z分〜 10000% Z分が好ましぐより好ましくは 20%Z分〜 1000%Z分、さらに好ましくは 30%Z分 〜800%Z分である。 [0143] Generally, in either case, when the draw ratio is increased, both Re and Rth can be increased. Furthermore, the ratio of Re and Rth can be freely controlled by controlling the value (aspect ratio) divided by the film width in the case of longitudinal stretching. In other words, the RthZRe ratio can be increased by reducing the aspect ratio. In the case of transverse stretching, it can be controlled by stretching in the orthogonal direction and simultaneously stretching in the longitudinal direction, or conversely relaxing. That is, the RthZRe ratio can be increased by stretching in the vertical direction, and the RthZRe ratio can be decreased by relaxing in the vertical direction. Such a stretching speed is preferably 10% Z min to 10000% Z min, more preferably 20% Z min to 1000% Z min, and further preferably 30% Z min to 800% Z min.
[0144] 本発明にお!/、ては、 Re, Rth、厚みのムラをより小さくするために、ムラの少な!/、原 反を用いることに加えて、延伸温度に幅方向に勾配を持たせるのが好ましい。即ち縦 延伸の場合でも、横延伸の場合でも両端部の延伸が進みやすく Re, Rthが発現し易 いため、中央部より端部の温度を高くすることが好ましい。端部とは、全幅に対し 10 %の領域を指し、ここを中央部より 6°C〜40°C、より好ましくは 7°C〜30°C、さらに好 ましくは 8°C〜25°C高くすることで達成できる。このように両端の温度を上げるには、 両端部に熱源 (パネルヒーター、赤外線ヒーター等)を増設してもよぐ熱風の噴出し 口を増設してもよい。このように敢えて温度分布を付与することで、一定の温度で延 伸するより一層均一な延伸が達成できる。このような減少はセルロース混合エステル フィルム特有の現象である。 [0144] In the present invention, in order to reduce the unevenness of Re, Rth, and thickness, less unevenness is used! In addition to using the original fabric, the stretching temperature has a gradient in the width direction. It is preferable to have it. That is, in both the case of longitudinal stretching and the case of lateral stretching, stretching at both ends tends to proceed easily, and Re and Rth are likely to be expressed. The end refers to a region of 10% of the total width, which is 6 ° C to 40 ° C, more preferably 7 ° C to 30 ° C, and more preferably 8 ° C to 25 ° from the center. Can be achieved by increasing C. In order to raise the temperature at both ends in this way, a hot air outlet may be added at either end, or a heat source (panel heater, infrared heater, etc.) may be added. By deliberately assigning a temperature distribution in this way, it is possible to extend More uniform stretching can be achieved than stretching. Such a decrease is a phenomenon peculiar to a cellulose mixed ester film.
[0145] ここで、熱処理後の冷却温度は、熱処理温度やフィルム厚みによって異なるが、通 常— 40°C〜（Tg— 10)°Cの温度範囲において空冷する。好ましくは、 0〜40°Cであ る。この際、フィルムの表面と裏面を冷却する空気等の冷却媒体の温度差が、得られ る（二軸)延伸フィルムの非熱変形性に影響を及ぼす。冷却気体の温度差が大き過 ぎると、得られる（二軸)延伸フィルムの表裏両面の熱収縮率差が大きくなり、加熱時 にフィルムが歪み、ソリが生じ易くなり、変形が大きくなる。力かる点を考慮すると、フィ ルムの表面と裏面を冷却する空気等の冷却媒体の温度差は小さ 、方が好まし 、が、 本発明の目的を達成するためには、該温度差を 5°C以内に調整することが重要であ る。  [0145] Here, the cooling temperature after the heat treatment varies depending on the heat treatment temperature and the film thickness, but is usually air-cooled in a temperature range of -40 ° C to (Tg-10) ° C. Preferably, it is 0 to 40 ° C. At this time, the temperature difference of the cooling medium such as air that cools the front and back surfaces of the film affects the non-thermal deformability of the obtained (biaxial) stretched film. If the temperature difference of the cooling gas is too large, the difference in heat shrinkage between the front and back surfaces of the obtained (biaxial) stretched film becomes large, and the film is easily distorted and warped during heating, resulting in large deformation. Considering the points to be applied, the temperature difference between the cooling medium such as air for cooling the front and back surfaces of the film is preferably small. However, in order to achieve the object of the present invention, the temperature difference is 5%. It is important to adjust within ° C.
[0146] これらの延伸前、延伸後のセルロース混合エステルフィルムは、 105°C、 5時間での 縦および横の寸法収縮率は ±0. 1%以下であることが好ましぐ 80°C'相対湿度 90 %における寸法収縮率が縦および横とも ±0. 5%未満であることが好ましぐヘイズ は 1. 2%以下が好ましぐ 0. 6%以下であることがより好ましい。また、引き裂き強度 は縦、横とも 10g以上であることが好ましぐ引っ張り強度が縦、横とも 50NZmm2以 上であることが好ましぐ弾性率が縦、横とも 3kNZmm2以上であることが好ましい。 これらの未延伸、延伸セルロース混合エステルフィルムは単独で使用してもよぐこ れらと偏光板組み合わせて使用してもよぐこれらの上に液晶層や屈折率を制御した 層（低反射層）ゃノヽードコート層を設けて使用してもよい。 [0146] These stretched cellulose ester films before and after stretching preferably have a longitudinal and lateral dimensional shrinkage of ± 0.1% or less at 105 ° C for 5 hours. 80 ° C ' The haze that the dimensional shrinkage at 90% relative humidity is preferably less than ± 0.5% in both length and width is preferably 1.2% or less, and more preferably 0.6% or less. Further, tear strength both vertically and horizontally preferably fixture tensile strength is at 10g or vertical, preferably it is horizontal with a on 50NZmm 2 or more members modulus vertical, that is transverse with 3KNZmm 2 or more preferable. These unstretched and stretched cellulose mixed ester films can be used alone or in combination with a polarizing plate. A liquid crystal layer or a layer with a controlled refractive index (low reflection layer) can be used on these films. Nyanide coat layer may be provided and used.
[0147] 延伸フィルムは、未延伸フィルムを延伸することで達成できる。その際に、 Reムラの 小さな未延伸フィルム (原反）を延伸することで Reムラの小さな延伸フィルムを達成で き、 Rthムラ、厚みムラ、 Re, Rthの温度変化に対しても有効である。本発明では、上 述のように厚みムラを小さくしたフィルムを用いることで、厚みもレターデーシヨンも均 一な延伸を行なうことができる (本発明のような手法を実施していない前述の特開 20 00— 352620号公報記載のような厚みムラの存在するフィルムを延伸すると、力学的 に弱い薄いところ力 延伸されるため、厚みムラが増幅され易い。延伸により厚みムラ が軽減されるような印象をもたれる場合がある力 このようなセルロース混合エステル フィルムの場合はこの逆である）。 [0147] The stretched film can be achieved by stretching an unstretched film. At that time, a stretched film with small Re unevenness can be achieved by stretching an unstretched film (raw material) with small Re unevenness. . In the present invention, by using a film with reduced thickness unevenness as described above, it is possible to perform uniform stretching in both thickness and letter-decision. When a film with thickness unevenness as described in Japanese Unexamined Patent Publication No. 2000-352620 is stretched, the thickness unevenness is easily amplified because the film is stretched mechanically weakly and thinly, and the thickness unevenness is reduced by stretching. Forces that can make an impression Such cellulose mixed esters The reverse is true for film).
[0148] (セルロース混合エステルフィルムの特性）  [0148] (Characteristics of cellulose mixed ester film)
(厚み）  (Thickness)
本発明のセルロース混合エステルフィルムの膜厚は 20〜200 μ mであることを特徴 とし、より好ましくは 20 μ m〜160 μ m、さらに好ましくはは 30 μ m〜120 μ mが好ま しぐ特には40〜120 111が好ましぃ。したがって、延伸する場合は未延伸フィルム の膜厚は、延伸倍率により予め厚めの原反押し出し膜厚として所望のセルロース混 合エステルフィルムが作製されるものである。また製膜方向（長手方向）と、フィルムの Reの遅相軸とのなす角度 0が 0° 、 + 90° もしくは— 90° に近いほど好ましい。 本発明のセルロース混合エステルフィルムの厚みムラは、厚み方向、幅方向いずれ も 0〜5 μ mが好ましぐより好ましくは 0〜3 μ m、さらに好ましくは 0〜2 μ mである。  The film thickness of the cellulose mixed ester film of the present invention is 20 to 200 μm, more preferably 20 μm to 160 μm, and even more preferably 30 μm to 120 μm. I like 40 ~ 120 111. Therefore, in the case of stretching, the film thickness of the unstretched film is such that a desired cellulose mixed ester film is prepared in advance as a thick original extruded film thickness depending on the stretch ratio. Further, it is preferable that the angle 0 formed by the film forming direction (longitudinal direction) and the slow axis of Re of the film is close to 0 °, + 90 ° or −90 °. The thickness unevenness of the cellulose mixed ester film of the present invention is preferably 0 to 3 μm, more preferably 0 to 2 μm, more preferably 0 to 5 μm in both the thickness direction and the width direction.
[0149] (キシミ値） [0149] (Kishimi value)
本発明の製造方法は、セルロース混合エステルに微粒子を添加することでキシミ値 を軽減し搬送性を改良するものである。本発明において、セルロース混合エステルフ イルムの動的および静的キシミ値は共に、 0. 2〜1. 5であることが好ましぐより好ま しくは 0. 2〜1. 3であり、さら〖こは 0. 256-1. 0が好ましい。微粒子の存在状態が粗 大である場合は、そのキシミ値が小さくなる場合と大きくなる場合があり、共に搬送性 は好ましくないばかりか、傷つきの発生を伴 、推奨されな 、。  In the production method of the present invention, fine particles are added to a cellulose mixed ester to reduce the squeegee value and improve the transportability. In the present invention, the dynamic and static kimi values of the cellulose mixed ester film are both preferably 0.2 to 1.5, more preferably 0.2 to 1.3. Is preferably 0.256-1. When the presence state of the fine particles is coarse, the kishimi value may be small or large. In both cases, the transportability is not preferable, and it is not recommended due to the occurrence of scratches.
前記キシミ値の測定は、以下に従って求めたものである。試料 lOOmm X 200mm および 75mm X 100mmの試料を、 25°C .相対湿度 60%の条件下で 2時間調湿し、 テンシロン引張試験機 (RTA— 100,オリエンテック (株)製）にて、大きいフィルムを 台の上に固定し、 200gのおもりをつけた小さいフィルムを載せる。次いで、おもりを 水平方向に引っ張り、動きだした時の力、動いているときの力を測定し、静摩擦係数 、動摩擦係数をそれぞれ算出して、靜的キシミ値および動的キシミ値とした。  The measurement of the kimimi value is determined according to the following. Samples lOOmm X 200mm and 75mm X 100mm samples were conditioned for 2 hours at 25 ° C and 60% relative humidity, and large with a Tensilon tensile tester (RTA-100, manufactured by Orientec Co., Ltd.) Secure the film on the table and place a small film with 200g weight on it. Next, the weight was pulled in the horizontal direction, the force when moving and the force when moving were measured, and the static friction coefficient and the dynamic friction coefficient were calculated, respectively, and were used as the artificial and dynamic kimi values.
F = X W (F :キシミ値、 μ：摩擦係数、 W：おもりの重さ（kgf ) )  F = X W (F: Kishimi, μ: Friction coefficient, W: Weight of weight (kgf))
[0150] (算術平均粗さ） [0150] (Arithmetic mean roughness)
また、本発明の製造方法によって製造される微粒子を含有したセルロース混合エス テルフィルムは、その表面の粗さが適度な範囲内にあることが特徴である。前記セル ロース混合エステルフィルムの表面粗さとしては、一般に用いられて 、る算術平均粗 さ（Ra)で示される。本発明において、前記セルロース混合エステルフィルムの算術 平均粗さ（Ra)は 3ηπ！〜 200nmであることが好ましぐより好ましくは 5nm〜100nm であり、特に好ましくは 5ηπ！〜 80nmである。算術平均粗さ (Ra)の測定は、一般に使 用されている接触式あるいは非接触式表面粗さ測定機で求めることができる。 In addition, the cellulose mixed ester film containing fine particles produced by the production method of the present invention is characterized in that the surface roughness is within an appropriate range. The cell As the surface roughness of the loin mixed ester film, it is generally used and indicated by the arithmetic average roughness (Ra). In the present invention, the arithmetic average roughness (Ra) of the cellulose mixed ester film is 3ηπ! It is more preferable that the thickness is ~ 200 nm, more preferably 5 nm to 100 nm, and particularly preferably 5ηπ! ~ 80nm. Arithmetic mean roughness (Ra) can be measured with a commonly used contact or non-contact surface roughness measuring instrument.
[0151] (光学特性） [0151] (Optical properties)
次に、本発明の製造方法によって製造された本発明のセルロース混合エステルフ イルムの光学特性について好ましい例を示す力 本発明は、これに限定されるもので はない。  Next, the power which shows a preferable example about the optical characteristic of the cellulose mixed ester film of this invention manufactured by the manufacturing method of this invention This invention is not limited to this.
[0152] 本明細書において、 Re (え）、 Rth( )は各々、波長えにおける面内のレターデーシ ヨンおよび厚さ方向のレターデーシヨンを表す。 Re( )は KOBRA 21ADHまたは WR (王子計測機器 (株)製）にお ヽて波長 λ nmの光をフィルム法線方向に入射させ て測定される。  [0152] In the present specification, Re (E) and Rth () respectively represent in-plane letter thickness and thickness direction letter decisions at the wavelength. Re () is measured using KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments) with light of wavelength λ nm incident in the normal direction of the film.
測定されるフィルムがー軸または二軸の屈折率楕円体で表されるものである場合に は、以下の方法により Rth ( λ )は算出される。  When the film to be measured is represented by a biaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rt ( X )は前記 Re ( λ )を、面内の遅相軸（KOBRA 21 ADHまたは WRにより判 断される）を傾斜軸（回転軸）として (遅相軸がない場合にはフィルム面内の任意の方 向を回転軸とする）のフィルム法線方向に対して法線方向から 50° から + 50° ま で 10° ステップで各々その傾斜した方向力も波長 λ nmの光を入射させて全部で 11 点測定し、その測定されたレタデーシヨン値と平均屈折率および入力された膜厚値を 基に KOBRA 21ADHまたは WRが算出する。  Rt (X) is the above-mentioned Re (λ), with the in-plane slow axis (determined by KOBRA 21 ADH or WR) as the tilt axis (rotary axis) (if there is no slow axis, it is in the film plane) (In any direction of the rotation axis) with respect to the normal direction of the film (in the direction of rotation) from the normal direction to the angle of 50 ° to + 50 ° in 10 ° steps. A total of 11 points are measured, and KOBRA 21ADH or WR calculates based on the measured retardation value, average refractive index, and input film thickness value.
上記において、 λに関する記載が特になぐ Re、 Rthとのみ記載されている場合は 、波長 590nmの光を用いて測定した値のことを表す。また、法線方向から面内の遅 相軸を回転軸として、ある傾斜角度にレターデーシヨンの値がゼロとなる方向をもつ フィルムの場合には、その傾斜角度より大きい傾斜角度でのレターデーシヨン値はそ の符号を負に変更した後、 KOBRA 21 ADHまたは WRが算出する。  In the above description, when only the description about λ is described as Re or Rth, it represents a value measured using light having a wavelength of 590 nm. In addition, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis as the rotation axis from the normal direction, letter data at a tilt angle larger than the tilt angle is used. The Chillon value is calculated by KOBRA 21 ADH or WR after changing its sign to negative.
なお、遅相軸を傾斜軸（回転軸）として (遅相軸がない場合にはフィルム面内の任 意の方向を回転軸とする）、任意の傾斜した 2方向からレタデーシヨン値を測定し、そ の値と平均屈折率および入力された膜厚値を基に、以下の式 (b)および式 (c)より Rt hを算出することちでさる。 The slow axis is the tilt axis (rotation axis) (if there is no slow axis, the arbitrary direction in the film is the rotation axis), and the retardation value is measured from any two tilted directions, So Rth is calculated from the following formulas (b) and (c) based on the above values, average refractive index, and input film thickness value.
[数 1]  [Number 1]
Figure imgf000056_0001
Figure imgf000056_0001
[式中、 Re ( Θ )は法線方向から角度 Θ傾斜した方向におけるレタ—デーシヨン値を あらわす。また、 nxは面内における遅相軸方向の屈折率を表し、 nyは面内において nxに直交する方向の屈折率を表し、 nzは nxおよび nyに直交する方向の屈折率を表 す。]  [In the equation, Re (Θ) represents the retardation value in the direction inclined by angle Θ from the normal direction. Also, nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. ]
式（c) : Rth = ( (nx + ny ) / 2 - nz) X d Formula (c): Rth = ((nx + ny) / 2-nz) X d
測定されるフィルムがー軸や二軸の屈折率楕円体で表現できないもの、いわゆる 光学軸（optic axis)がないフィルムの場合には、以下の方法により Rth ( λ )は算出 される。  If the film to be measured cannot be expressed by a biaxial refractive index ellipsoid, that is, a film without a so-called optic axis, Rth (λ) is calculated by the following method.
Rth ( l )は前記 Re ( λ )を、面内の遅相軸（KOBRA 21 ADHまたは WRにより判 断される）を傾斜軸（回転軸）としてフィルム法線方向に対して― 50度から + 50度ま で 10度ステップで各々その傾斜した方向力 波長 λ nmの光を入射させて 11点測 定し、その測定されたレターデーシヨン値と平均屈折率および入力された膜厚値を基 に KOBRA 21ADHまたは WRが算出する。  Rth (l) is the above-mentioned Re (λ), and the in-plane slow axis (determined by KOBRA 21 ADH or WR) is the tilt axis (rotation axis). Each tilted directional force wavelength λ nm is incident in steps of 10 degrees up to 50 degrees and measured at 11 points. Based on the measured letter value, average refractive index, and input film thickness value. Calculated by KOBRA 21ADH or WR.
これら平均屈折率と膜厚を入力することで、 KOBRA 21八011または1\^は1^、 n y、 nzを算出する。この算出された nx、 ny、 nzより Nz= (nx— nz)Z(nx— ny)がさら に算出される。 By inputting these average refractive index and film thickness, KOBRA 21 8 011 or 1 \ ^ calculates 1 ^, ny, nz. Nz = (nx−nz) Z (nx−ny) is further calculated from the calculated nx, ny, and nz.
本発明のセルロース混合エステルフィルムの波長 590nmにおける正面レターデー シヨン（Re)は、 0〜10nmであることが好ましぐかつ厚さ方向のレターデーシヨン (Rt h)の絶対値が 0〜60nmであることが好ましい。さらに好ましくは、正面レターデーシ ヨン (Re)は、 0〜8nmであることが好ましぐかつ厚さ方向のレターデーシヨン (Rth) の絶対値カ^〜 50nmであり、特には正面レターデーシヨン (Re)力 0〜5nmであり 、厚さ方向のレターデーシヨン (Rth)の絶対値力^〜 40nmである。好ましい Reムラ は 0〜10nmが好ましぐより好ましくは 0〜5 μ m、さらに好ましくは 0〜3 μ mである。 好ましい Rthムラは 0〜10%が好ましぐより好ましくは 0%〜7%、さらに好ましくは 0 %〜5%である。これらの光学特性を有する本発明のセルロース混合エステルフィル ムは、偏光子の保護膜としてこの上なく好まし 、ものである。 The front-face letter retardation (Re) of the cellulose mixed ester film of the present invention at a wavelength of 590 nm is preferably 0 to 10 nm, and the absolute value of the thickness direction letter retardation (Rth) is 0 to 60 nm. It is preferable. More preferably, the front letter decision (Re) is preferably from 0 to 8 nm, and the absolute value of the letter direction (Rth) in the thickness direction is ~ 50 nm. Re) force is 0-5nm The absolute value of letterthickness (Rth) in the thickness direction is ~~ 40nm. The preferable Re unevenness is 0 to 5 nm, more preferably 0 to 5 μm, and still more preferably 0 to 3 μm. The preferred Rth unevenness is preferably 0% to 0%, more preferably 0% to 7%, and still more preferably 0% to 5%. The cellulose mixed ester film of the present invention having these optical properties is most preferable as a protective film for a polarizer.
[0154] また、湿度変化による光学特性問題も本発明では改良できるものであり、 25°Cに於 ける相対湿度 10%の光学特性と 80%の光学特性との差が小さいことが特徴である。 すなわち、本発明のセルロース混合エステルフィルムは、 Reの湿度変化による変化 量をその絶対値で評価するものであり、 Re湿度変化 (nm)は、 Re (相対湿度 80%)と Re (相対湿度 10%)との差の絶対値であり、湿度変化による Rth湿度変化 (nm)は、 Rth (相対湿度 80%)と Rth (相対湿度 10%)との差の絶対値で表わされる。本発明 のセルロース混合エステルフィルムは、 Reの湿度変化が 10nm以下であることが好ま しぐさらには 5nmが実現でき、また lnmも実現することができる。また、 Rth湿度変 化は、 25nm以下であることが好ましぐさらには 20nmが実現でき、また 15nmも実 現できる。これは、従来のセルローストリアセテートに比較すると、 2/3〜1/2の好まし い湿度変化量である。 [0154] Further, the present invention can also improve the optical characteristic problem due to humidity change, and is characterized by a small difference between the optical characteristic of 10% relative humidity and the optical characteristic of 80% at 25 ° C. . That is, the cellulose mixed ester film of the present invention evaluates the amount of change due to humidity change of Re by its absolute value, and the change of Re humidity (nm) is Re (relative humidity 80%) and Re (relative humidity 10%). %), And Rth humidity change (nm) due to humidity change is expressed by the absolute value of the difference between Rth (relative humidity 80%) and Rth (relative humidity 10%). In the cellulose mixed ester film of the present invention, the change in humidity of Re is preferably 10 nm or less, more preferably 5 nm can be realized, and lnm can also be realized. Moreover, it is preferable that the Rth humidity change is 25 nm or less, and further 20 nm can be realized, and 15 nm can also be realized. This is a preferred humidity change of 2/3 to 1/2 compared to conventional cellulose triacetate.
[0155] 本発明のセルロース混合エステルフィルムは、波長に対する光学特性の挙動をコン トロールすることも可能である。すなわち、波長 400nmおよび 700nmにおけるそれ ぞれの Re (400)、 Re (700)の差の絶対値力^〜 15nmであることが好ましぐ Rth (4 00)、 Rth (700)の差の絶対値が 0〜35nmであることが好まし!/、。  [0155] The cellulose mixed ester film of the present invention can also control the behavior of optical properties with respect to wavelength. That is, it is preferable that the absolute value of the difference between Re (400) and Re (700) at wavelengths of 400 nm and 700 nm is ~ 15 nm. The absolute value of the difference between Rth (400) and Rth (700) The value is preferably 0-35nm! / ,.
即ち、式で表すと、本発明のセルロース混合エステルフィルムの波長 400nmおよ び 700nmにおけるそれぞれの正面レターデーシヨン (Re)および厚さ方向のレター デーシヨン (Rth)は、下記式 (A— 1)および (A— 2)を満たすことが好まし!/、。  That is, when expressed in terms of the formula, the front letter-deposition (Re) and thickness-direction letter-decrease (Rth) at wavelengths of 400 nm and 700 nm of the cellulose mixed ester film of the present invention are represented by the following formula (A-1): And it is preferable to satisfy (A—2)! /.
式 (A— 1) 0≤ I Re (700) -Re (400) | ≤15nm  Formula (A— 1) 0≤ I Re (700) -Re (400) | ≤15nm
式 (A— 2) 0≤ I Rth (700) -Rth (400) | ≤35nm  Formula (A— 2) 0≤ I Rth (700) -Rth (400) | ≤35nm
(式中、 Re (400)および Re (700)は、波長 400nmおよび 700nmにおける正面レ ターデーシヨン (Re)を表し、 Rth (400)および Rth (700)は、波長 400nmおよび 70 Onmにおける厚さ方向のレターデーシヨン (Rth)を表す。） [0156] また、本発明のセルロース混合エステルフィルムにおける光学特性の表示方法であ る固有複屈折は、 25°C '相対湿度 60%環境下で波長 590nmにおける面内方向の 固有複屈折が 0〜0. 001であることが好ましぐ厚さ方向の固有複屈折の絶対値が 0 〜0. 003であることが好ましい。より好ましくは、面内方向の固有複屈折が 0〜0. 00 08であることが好ましぐ厚さ方向の固有複屈折の絶対値が 0〜0. 0025であり、さら には面内方向の固有複屈折が 0〜0. 0006であること力 子ましく、厚さ方向の固有複 屈折の絶対値が 0〜0. 001であることが好ましい。 (Where Re (400) and Re (700) represent frontal retardation (Re) at wavelengths of 400 nm and 700 nm, and Rth (400) and Rth (700) are thickness-wise at wavelengths of 400 nm and 70 Onm. Represents letter decision (Rth).) [0156] In addition, the intrinsic birefringence, which is a method for displaying the optical properties of the cellulose mixed ester film of the present invention, has an intrinsic birefringence in the in-plane direction at a wavelength of 590 nm in an environment of 25 ° C 'relative humidity of 60% and 0 to The absolute value of the intrinsic birefringence in the thickness direction, which is preferably 0.001, is preferably 0 to 0.003. More preferably, the absolute value of the intrinsic birefringence in the thickness direction is preferably 0 to 0.0025, and the in-plane direction intrinsic birefringence is preferably 0 to 0.0008. The intrinsic birefringence is preferably 0 to 0.0006, and the absolute value of the intrinsic birefringence in the thickness direction is preferably 0 to 0.001.
[0157] (軸ズレ）  [0157] (Axis misalignment)
本発明のセルロース混合エステルフィルムは、光学遅相軸が流延方向あるいは幅 方向に対して平行ある 、は直角であることが好ま 、。特に延伸処理を施した場合に は、流延方向に延伸した場合は 0° に近いほど好ましぐ 0± 3° が好ましぐより好ま しくは 0± 1. 5° であり、さらに好ましくは 0±0. 5° である。幅方向に延伸した場合 は、 90± 3° あるいはー90± 3° が好ましぐより好ましくは 90± 1.5° あるいはー9 0± 1. 5° 、さらに好ましくは 90±0. 5° あるいは一 90±0. 5° である。  In the cellulose mixed ester film of the present invention, it is preferable that the optical slow axis is parallel to the casting direction or the width direction and is perpendicular. In particular, when stretching is performed, when it is stretched in the casting direction, 0 ± 3 ° is preferred as it is closer to 0 °, more preferably 0 ± 1.5 °, and more preferably 0 ± 0.5 °. When stretched in the width direction, 90 ± 3 ° or −90 ± 3 ° is preferred, more preferably 90 ± 1.5 ° or −90 ± 1.5 °, and even more preferably 90 ± 0.5 ° or one. 90 ± 0.5 °.
[0158] (透過率） [0158] (Transmittance)
試料 20mm X 70mmを、 25°C .相対湿度 60%で透明度測定器 (AKA光電管比 色計、 KOTAKI製作所社製)で可視光 (615nm)の透過率を測定した。本発明のセ ルロース混合エステルフィルムは、好ましくは透過率が 90%以上であり、さらに好まし くは 91%以上であり、特には透過率が 92%以上である。  The transmittance of visible light (615 nm) was measured on a 20 mm × 70 mm sample at 25 ° C. and a relative humidity of 60% with a transparency measuring device (AKA photoelectric tube colorimeter, manufactured by KOTAKI Corporation). The cellulose mixed ester film of the present invention preferably has a transmittance of 90% or more, more preferably 91% or more, and particularly a transmittance of 92% or more.
[0159] (ヘイズ） [0159] (Haze)
試料 40mm X 80mmを、 25°C '相対湿度 60%においてヘイズメーター（HGM— 2 DP、スガ試験機）で JIS K— 6714に従って測定する。本発明のセルロース混合ェ ステルフィルムは、ヘイズが 0〜1.5%の範囲であることが好ましぐより好ましくは 0〜 1.2%であり、さらに好ましくは 0〜0. 8%であり、特には 0. 1〜0. 5%が好ましい。  Sample 40mm x 80mm is measured according to JIS K-6714 with a haze meter (HGM-2 DP, Suga Tester) at 25 ° C 'relative humidity 60%. The cellulose mixed ester film of the present invention preferably has a haze in the range of 0 to 1.5%, more preferably 0 to 1.2%, still more preferably 0 to 0.8%, and particularly 0. 1 to 0.5% is preferred.
[0160] 以上の観点から、本発明のセルロース混合エステルフィルムは、ヘイズが 0. 1〜1. [0160] From the above viewpoint, the haze of the cellulose mixed ester film of the present invention is 0.1 to 1.
2%であり、可視光透過率が 91%以上であり、 25°C *相対湿度 60%環境下で波長 5 90nmにおける面内方向の固有複屈折が 0〜0. 001であり、厚さ方向の固有複屈折 の絶対値が 0〜0. 003であることが好ましい。 [0161] (セルロース混合エステルフィルムの機能化） 2%, visible light transmittance of 91% or more, 25 ° C * relative humidity 60% environment, in-plane intrinsic birefringence at wavelength 5 90nm is 0 to 0.001, thickness direction It is preferable that the absolute value of the intrinsic birefringence is from 0 to 0.003. [0161] (Functionalization of cellulose mixed ester film)
表面処理  surface treatment
次に本発明のセルロース混合エステルフィルムについて、さらに機能を付与する場 合の好まし!/、態様を記述する。まずセルロース混合エステルフィルムの表面処理方 法について記述する。  Next, the preferred case of adding functions to the cellulose mixed ester film of the present invention is described. First, the surface treatment method for cellulose mixed ester film is described.
セルロース混合エステルフィルムは、場合により表面処理を行なうことによって、セ ルロース混合エステルフィルムと各機能層（例えば、下塗層およびバック層）との接着 性の向上を達成することができる。前記表面処理としては、例えば、グロ一放電処理 、紫外線照射処理、コロナ処理、火炎処理、酸またはアルカリ処理を用いることがで きる。前記グロ一放電処理とは、 10— 3〜20Torr (約 0. 13〜2666Pa)の低圧ガス下 でおこる、いわゆる低温プラズマのことも示すが、大気圧下でのグロ一放電処理でも よい。 The cellulose mixed ester film can be optionally subjected to a surface treatment to improve the adhesion between the cellulose mixed ester film and each functional layer (for example, the undercoat layer and the back layer). As the surface treatment, for example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment refers to so-called low-temperature plasma that occurs under a low pressure gas of 10 −3 to 20 Torr (about 0.13 to 2666 Pa), but may be a glow discharge treatment under atmospheric pressure.
[0162] まず、低圧下でのグロ一放電処理は、米国特許第 3, 462, 335号明細書、同 3, 7 61, 299号明細書、同 4, 072, 769号明細書および英国特許第 891, 469号明細 書に記載されている。また不活性ガス、酸化窒素類、有機化合物ガス等の特定のガ ス等を導入することも行われる。ポリマーの表面をグロ一放電処理する際には大気圧 でもよいし減圧下で実施されてもよい。また、グロ一放電処理の雰囲気に酸素、窒素 、ヘリウムあるいはアルゴンのような種々のガスや水を導入しながら実施してもよい。 グロ一放電処理時の真空度は 0. 005〜20Torr(0. 67〜2666Pa)力 子ましく、より 好ましくは 0. 02〜2Torr (2. 67〜267Pa)である。また、グロ一放電処理時の電圧 は 500〜5000Vの間力 子ましぐより好まし <は 500〜3000Vである。使用する放電 周波数は、直流から数千 MHz、より好ましくは 50Hz〜20MHz、さらに好ましくは 1 ΚΗζ〜1ΜΗζである。また、放電処理強度は、 0. OIKV'A'分 Ζπι2〜5Κν·Α·分 Zm2が好ましぐより好ましくは 0. 151 ^'分71112〜11 ^'分71112でぁる。 [0162] First, glow discharge treatment under low pressure is performed in US Pat. Nos. 3,462,335, 3,761,299, 4,072,769, and British patents. No. 891, 469. It is also possible to introduce specific gases such as inert gases, nitric oxides and organic compound gases. When the surface of the polymer is subjected to a glow discharge treatment, it may be performed at atmospheric pressure or under reduced pressure. Further, it may be carried out while introducing various gases such as oxygen, nitrogen, helium or argon and water into the atmosphere of the glow discharge treatment. The degree of vacuum during the glow discharge treatment is preferably 0.005 to 20 Torr (0.67 to 2666 Pa) force, more preferably 0.02 to 2 Torr (2.67 to 267 Pa). In addition, the voltage during glow discharge treatment is preferably 500 to 3000V, more preferably between 500 and 5000V. The discharge frequency used is from DC to several thousand MHz, more preferably 50 Hz to 20 MHz, and still more preferably 1 ΚΗζ to 1 ΜΗζ. The discharge treatment intensity, 0. OIKV'A 'partial Zetapaiiota 2 preferably than ~5Κν · Α · min Zm 2 is preferably tool is 0.151 ^' min 7111 2-11 ^ 'min 7111 2 Dearu.
[0163] 本発明のセルロース混合エステルフィルムの表面処理としては、紫外線照射法も好 ましく用いられる。紫外線照射法に使用される水銀灯は石英管力 なる高圧水銀灯 で、紫外線の波長が 180ηπ！〜 380nmの間であるものが好ましい。紫外線照射の方 法について、セルロース混合エステルフィルムの表面温度が 150°C前後にまで上昇 することが支持体性能上問題なければ、光源は主波長が 365nmの高圧水銀灯ラン プを使用することができる。また、低温処理が必要とされる場合には主波長が 254η mの低圧水銀灯が好ましい。またオゾンレスタイプの高圧水銀ランプ、および低圧水 銀ランプを使用する事も可能である。処理光量に関しては処理光量が多いほどセル ロース混合エステルフィルムと被接着層との接着力は向上するが、光量の増加に伴 い支持体が着色し、また支持体が脆くなるという問題が発生する。従って、 365nmを 主波長とする高圧水銀ランプで、照射光量 20〜： LOOOO (miZcm2)が好ましぐより 好ましくは 50〜2000 (m]/cm )である。 254nmを主波長とする低圧水銀ランプの 場合には、照射光量 100〜10000 (mjZcm2)が好ましぐより好ましくは 300〜150 0 (mjZcm2)である。 [0163] As the surface treatment of the cellulose mixed ester film of the present invention, an ultraviolet irradiation method is also preferably used. The mercury lamp used in the ultraviolet irradiation method is a high-pressure mercury lamp with quartz tube power, and the wavelength of ultraviolet light is 180ηπ! Those between ˜380 nm are preferred. Regarding the UV irradiation method, the surface temperature of cellulose mixed ester film rises to around 150 ° C. If this does not affect the performance of the support, a high-pressure mercury lamp with a dominant wavelength of 365 nm can be used as the light source. When low temperature treatment is required, a low pressure mercury lamp having a dominant wavelength of 254 ηm is preferable. Ozone-less high-pressure mercury lamps and low-pressure mercury lamps can also be used. Regarding the amount of processed light, the greater the amount of processed light, the better the adhesive strength between the cellulose mixed ester film and the adherend layer, but the problem arises that the support becomes colored and the support becomes brittle as the amount of light increases. . Therefore, in a high-pressure mercury lamp having a dominant wavelength of 365 nm, the irradiation light quantity is 20 to: LOOOO (miZcm 2 ) is more preferable, and preferably 50 to 2000 (m) / cm 2. In the case of a low-pressure mercury lamp having a main wavelength of 254 nm, the irradiation light quantity is preferably from 100 to 10,000 (mjZcm 2 ), more preferably from 300 to 1500 (mjZcm 2 ).
[0164] 更に本発明のセルロース混合エステルフィルムの表面処理としてはコロナ放電処理 も好ましい。前記コロナ放電処理を行うコロナ放電処理装置は、 Pillar社製ソリッドス テートコロナ処理機、 LEPEL型表面処理機、 VETAPHON型処理機等を用いるこ とができる。コロナ放電処理は、空気中、常圧で行なうことができる。処理時の放電周 波数は、 5〜40kHz、より好ましくは 10〜30kHzであり、波形は交流正弦波が好まし い。電極と誘電体ロールとのギャップクリアランスは 0. lmm〜10mmが好ましぐより 好ましくは 1. Omn！〜 2. Ommである。放電は、放電帯域に設けられた誘電サポート ローラーの上方で処理し、処理量は、 0. 3〜0. 4Κν·Α·分/ m2、より好ましくは 0. 34〜0. 38Κν·Α·分 Zm2である。 [0164] Further, corona discharge treatment is also preferable as the surface treatment of the cellulose mixed ester film of the present invention. As the corona discharge treatment apparatus for performing the corona discharge treatment, a solid state corona treatment machine manufactured by Pillar, a LEPEL type surface treatment machine, a VETAPHON type treatment machine, or the like can be used. The corona discharge treatment can be performed in air at normal pressure. The discharge frequency during processing is 5 to 40 kHz, more preferably 10 to 30 kHz, and the waveform is preferably an AC sine wave. The gap clearance between the electrode and the dielectric roll is preferably 0.1 mm to 10 mm, more preferably 1. Omn! ~ 2. Omm. The discharge is processed above the dielectric support roller provided in the discharge zone, and the throughput is 0.3 to 0.4Κν · Α · min / m 2 , more preferably 0.34 to 0.38Κ38 · ν · Α · is the partial Zm 2.
[0165] 次に前記表面処理の一種である火炎処理について説明する。前記火炎処理に用 いられるガスは、天然ガス、液化プロパンガス、都市ガスのいずれでもかまわないが、 空気との混合比が重要である。天然ガス Z空気の好ま 、混合比は容積比で 1Z6 〜1Z10、好ましくは 1Z7〜： LZ9である。また、液ィ匕プロパンガス Z空気の場合は 1 Z14〜： LZ22、好ましくは 1Z16〜： LZ19、都市ガス Z空気の場合は 1Z2〜： LZ8 、好ましくは 1Z3〜： LZ7である。  [0165] Next, flame treatment which is a kind of the surface treatment will be described. The gas used for the flame treatment may be natural gas, liquefied propane gas, or city gas, but the mixing ratio with air is important. Natural gas Z air is preferably mixed in a volume ratio of 1Z6 to 1Z10, preferably 1Z7 to LZ9. In the case of liquid propane gas Z air, 1Z14 ~: LZ22, preferably 1Z16 ~: LZ19, and in the case of city gas Z air, 1Z2 ~: LZ8, preferably 1Z3 ~: LZ7.
また、火炎処理量は l〜50Kcal/m2、より好ましくは 3〜20Kcal/m2の範囲で行 なうとよい。 Further, the flame treatment amount may be 1 to 50 Kcal / m 2 , more preferably 3 to 20 Kcal / m 2 .
[0166] 次に、本発明のセルロース混合エステルフィルムの表面処理として好ましく用いら れるアルカリケン化処理を具体的に説明する。セルロース混合エステルフィルム表面 をアルカリ溶液に浸漬した後、酸性溶液で中和し、水洗して乾燥するサイクルで行わ れることが好ましい。 [0166] Next, it is preferably used as a surface treatment of the cellulose mixed ester film of the present invention. The alkali saponification treatment will be specifically described. It is preferable that the cellulose mixed ester film surface is immersed in an alkaline solution, then neutralized with an acidic solution, washed with water and dried.
前記アルカリ溶液としては、水酸ィ匕カリウム溶液、水酸化ナトリウム溶液が挙げられ Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution.
、水酸化イオンの濃度は 0. lmolZL〜4. OmolZLであることが好ましぐ 0. 5mol ZL〜3. 5molZLであることがさらに好ましい。前記アルカリ溶液の液温は、室温〜 90°Cの範囲が好ましぐ 40°C〜70°Cがさらに好ましい。前記アルカリケン化処理は アルカリ溶液に浸漬した後、一般には水洗され、しカゝる後に酸性水溶液を通過させた 後に、水洗して表面処理したセルロース混合エステルフィルムを得る。 The concentration of hydroxide ions is preferably 0.1 mol ZL to 4. Omol ZL, more preferably 0.5 mol ZL to 3.5 mol ZL. The temperature of the alkaline solution is preferably in the range of room temperature to 90 ° C, more preferably 40 ° C to 70 ° C. In the alkali saponification treatment, after immersing in an alkali solution, it is generally washed with water, and after passing through an acidic aqueous solution, it is washed with water to obtain a surface-treated cellulose mixed ester film.
[0167] この際、酸性水溶液としては塩酸、硝酸、硫酸、酢酸、蟻酸、クロ口酢酸、シユウ酸 などの水溶液であり、その濃度は 0. 01molZL〜3. OmolZLであることが好ましぐ 0. 05molZL〜2. OmolZLであることがさらに好ましい。アルカリケン化時間は、 20 〜600秒で実施されるがことが好ましくは、さらには 30〜300秒が好ましぐ特には 4 0〜210秒であることが好ましい。また酸性溶液による中和は、 20〜600秒で実施さ れることが好ましぐより好ましくは 30〜250秒、特には 40〜180秒であるであること が好ましい。さらに中和後の水洗については、 20〜400秒で実施されることが好まし ぐより好ましくは 30〜300秒、特には 40〜210秒であるであることが好ましい。  [0167] In this case, the acidic aqueous solution is an aqueous solution of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, black acetic acid, oxalic acid, and the like, and the concentration is preferably 0.01 molZL to 3. OmolZL. .05 molZL to 2. OmolZL is more preferable. The alkali saponification time is preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and particularly preferably 40 to 210 seconds. The neutralization with an acidic solution is preferably carried out for 20 to 600 seconds, more preferably 30 to 250 seconds, and particularly preferably 40 to 180 seconds. Further, the water washing after neutralization is preferably carried out for 20 to 400 seconds, more preferably 30 to 300 seconds, and particularly preferably 40 to 210 seconds.
[0168] これらの方法で得られた固体の表面エネルギーは、「ぬれの基礎と応用」（リアライ ズ社 1989. 12. 10発行）に記載のように接触角法、湿潤熱法、および吸着法によ り求めることができ、接触角法を用いることが好ましい。本発明のセルロース混合エス テルフィルム表面の水の接触角（25°CZ相対湿度 60%)は、 45° 以下であることが 好ましぐ 10〜45° であることが更に好ましぐ 10〜40° が特に好ましぐ 10〜30 ° が最も好ましい。  [0168] The surface energy of the solid obtained by these methods is determined by the contact angle method, the wet heat method, and the adsorption method as described in "Basics and Application of Wetting" (Realize Corp., issued on Dec. 10, 1989). It is preferable to use the contact angle method. The water contact angle (25 ° CZ relative humidity 60%) on the cellulose mixed ester film surface of the present invention is preferably 45 ° or less, more preferably 10 to 45 °, and even more preferably 10 to 40. A temperature of 10 to 30 ° is most preferable.
[0169] (接着層）  [0169] (Adhesive layer)
本発明のセルロース混合エステルフィルムは、機能性層を接着させるために、表面 活性化処理をしたのち、直接セルロース混合エステルフィルム上に機能層を塗布し て接着力を得る方法と、ー且何力しらの表面処理をした後、あるいは表面処理なしで 、下塗層 (接着層）を設けこの上に機能層を塗布する方法とがある。 前記下塗層の構成としても種々の工夫が行われており、例えば、 1層の下塗り層を 一層で構成する単層法や、第 1層として支持体 (セルロース混合エステルフィルム）に よく接着する層（以下、「下塗第 1層」と称する場合がある。）を設け、その上に第 2層と して機能層とよく接着する下塗り第 2層を塗布する所謂重層法がある。 The cellulose mixed ester film of the present invention is a method for obtaining adhesion by directly applying a functional layer on a cellulose mixed ester film after surface activation treatment in order to adhere the functional layer. There is a method in which an undercoat layer (adhesive layer) is provided after a surface treatment or without a surface treatment and a functional layer is applied thereon. Various ideas have been made for the constitution of the undercoat layer. For example, it is well adhered to a support (cellulose mixed ester film) as a single layer method in which one undercoat layer is composed of one layer or as a first layer. There is a so-called multi-layer method in which a layer (hereinafter sometimes referred to as “first undercoat layer”) is provided, and a second undercoat layer that adheres well to the functional layer as a second layer is applied thereon.
[0170] 前記単層法においては、セルロース混合エステルフィルムを膨張させ、下塗層素材 と界面混合させることによって良好な接着性を達成している場合が多い。前記下塗層 に使用する下塗ポリマーとしては、水溶性ポリマー、セルロース混合エステル、ラテツ タスポリマー、水溶性ポリエステルなどが例示される。前記水溶性ポリマーとしては、 ゼラチン、ゼラチン誘導体、カゼイン、寒天、アルギン酸ナトリウム、でんぷん、ポリビ ニールアルコール、ポリアクリル酸共重合体、無水マレイン酸共重合体などであり、セ ルロース混合エステルとしてはカルボキシメチルセルロース、ヒドロキシェチルセル口 ースなどである。ラテックスポリマーとしては塩ィ匕ビュル含有共重合体、塩ィ匕ビ -リデ ン含有共重合体、アクリル酸エステル含有共重合体、酢酸ビュル含有共重合体、ブ タジェン含有共重合体などが挙げられる。 In the single-layer method, good adhesion is often achieved by expanding the cellulose mixed ester film and interfacial mixing with the undercoat layer material. Examples of the primer polymer used in the primer layer include water-soluble polymers, cellulose mixed esters, latex polymers, and water-soluble polyesters. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the cellulose mixed ester includes carboxymethyl cellulose. And hydroxyethyl cellulose mouth. Examples of the latex polymer include a salty vinyl-containing copolymer, a salty-vinylidene-containing copolymer, an acrylic ester-containing copolymer, an acetic acid-bule-containing copolymer, and a butagen-containing copolymer. .
前記重層法における下塗第 1層では、例えば、塩化ビュル、塩ィ匕ビユリデン、ブタ ジェン、メタクリル酸、アクリル酸、ィタコン酸、無水マレイン酸などの中力 選ばれた 単量体を出発原料とする共重合体を始めとして、ポリエチレンィミン、エポキシ榭脂、 グラフトイ匕ゼラチン、ニトロセルロース、等のオリゴマーもしくはポリマーなどを用いるこ とがでさる。  In the first undercoat layer in the multi-layer method, for example, a medium-selected monomer such as butyl chloride, salt vinylidene, butadiene, methacrylic acid, acrylic acid, itaconic acid or maleic anhydride is used as a starting material. In addition to copolymers, oligomers or polymers such as polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, etc. can be used.
前記下塗第 2層では、例えば、前述の水溶性ポリマー、セルロース混合エステル、 ラテックスポリマー、水溶性ポリエステルなど等を用いることができる。  In the second undercoat layer, for example, the aforementioned water-soluble polymer, cellulose mixed ester, latex polymer, water-soluble polyester, and the like can be used.
[0171] また本発明のセルロース混合エステルフィルムには好ましい態様としては、偏光子 と接着するための親水性バインダー力もなる親水性バインダー層が設けられることで ある。前記親水性バインダーとしては、例えば、 COOM基含有の酢酸ビュル—マ レイン酸共重合体化合物、または親水性セルロース誘導体 (例えばメチルセルロース 、カルボキシメチルセルロース、ヒドロキシアルキルセルロース等）、ポリビュルアルコ ール誘導体（例えば酢酸ビュル ビュルアルコール共重合体、ポリビュルァセター ル、ポリビュルホルマール、ポリビュルベンザール等）天然高分子化合物（例えばゼ ラチン、カゼインアラビアゴム等）、親水基含有ポリエステル誘導体 (例えばスルホン 基含有ポリエステル共重合体)が挙げられる。 [0171] Further, the cellulose mixed ester film of the present invention is preferably provided with a hydrophilic binder layer that also has a hydrophilic binder force for adhering to a polarizer. Examples of the hydrophilic binder include a COOM group-containing butyl-maleic acid copolymer compound, or a hydrophilic cellulose derivative (for example, methylcellulose, carboxymethylcellulose, hydroxyalkylcellulose, etc.), a polybutyl alcohol derivative (for example, Butyl acetate, butyl alcohol copolymer, polybuluacetal, polybule formal, polybulb benzal, etc.) Latin, casein gum arabic, etc.), and hydrophilic group-containing polyester derivatives (for example, sulfone group-containing polyester copolymers).
[0172] 本発明セルロース混合エステルフィルムに場合により施される下塗り層には、機能 層の透明性などを実質的に損なわない程度に無機または、有機の微粒子をマット剤 として含有させることができる。  [0172] The undercoating layer optionally applied to the cellulose mixed ester film of the present invention can contain inorganic or organic fine particles as a matting agent to such an extent that the transparency of the functional layer is not substantially impaired.
無機の微粒子のマット剤としてはシリカ（SiO ) ,二酸化チタン (TiO ) ,炭酸カルシ  Inorganic particulate matting agents include silica (SiO 2), titanium dioxide (TiO 2), calcium carbonate
2 2  twenty two
ゥム、炭酸マグネシウムなどを使用することができる。有機の微粒子マット剤としては、 ポリメチルメタタリレート、セルロースアセテートプロピオネート、ポリスチレン、米国特 許第 4, 142, 894号明細書に記載されている処理液可溶性のもの、米国特許第 4, 396, 706号明細書に記載されているポリマーなどを用いることができる。  Um, magnesium carbonate, etc. can be used. Examples of the organic fine-particle matting agent include polymethylmetatalylate, cellulose acetate propionate, polystyrene, a processing solution-soluble one described in US Pat. No. 4,142,894, US Pat. The polymers described in 396, 706 can be used.
これらの微粒子マット剤の平均粒子サイズは 0. 01〜10 mのものが好ましい。より 好ましくは、 0. 05〜5 /ζ πιである。また、その含有量は 0. 5〜600mg/m2が好まし ぐさらに好ましくは、 l〜400mgZm2である。前記下塗液は、一般に良く知られた塗 布方法、例えばディップコート法、エアーナイフコート法、カーテンコート法、ローラー コート法、ワイヤーバーコート法、グラビアコート法、スライドコート法、あるいは、米国 特許第 2, 681, 294号明細書に記載のホッパーを使用するエタストルージョンコート 法により塗布することができる。 These fine particle matting agents preferably have an average particle size of 0.01 to 10 m. More preferably, it is 0.05 to 5 / ζ πι. The content is preferably 0.5 to 600 mg / m 2, more preferably 1 to 400 mg Zm 2 . The undercoat liquid may be a generally well-known coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, or US Patent No. It can be applied by an etching coating method using a hopper described in the specification of 2, 681, 294.
[0173] (導電性層） [0173] (Conductive layer)
本発明のセルロース混合エステルフィルムが利用される偏光板用保護膜の構成に おいては、フィルムの少なくとも一層に帯電防止層を設けたり、偏光子と接着するた めの親水性バインダー層が設けられることが好ましい。  In the configuration of the protective film for polarizing plate in which the cellulose mixed ester film of the present invention is used, an antistatic layer is provided on at least one layer of the film, or a hydrophilic binder layer for adhering to the polarizer is provided. It is preferable.
まず、前記導電性層について以下に説明する。前記導電性層に含まれる導電性素 材としては、導電性金属酸化物や導電性ポリマーが好ましい。なお、蒸着ゃスパッタ リングによる透明導電性膜でもよい。前記導電性金属酸ィ匕物の例としては、 ZnO、 Ti O、 SnO、 Al O、 In O、 SiO、 MgO、 BaO、 MoO、 V O等、あるいはこれらの複 First, the conductive layer will be described below. The conductive material contained in the conductive layer is preferably a conductive metal oxide or a conductive polymer. The vapor deposition may be a transparent conductive film formed by sputtering. Examples of the conductive metal oxide include ZnO, Ti 2 O, SnO, Al 2 O, In 2 O, SiO 2, MgO, BaO, MoO, and V 2 O, or a combination of these.
2 2 2 3 2 3 2 2 2 5 2 2 2 3 2 3 2 2 2 5
合酸化物が好ましぐ特に ZnO、 SnOあるいは V Oが好ましい。  A mixed oxide is preferred, and ZnO, SnO or V 2 O is particularly preferred.
2 2 5  2 2 5
前記複合酸化物の異種原子例としては、 Al、 In、 Ta、 Sb、 Nb、ハロゲン、 Agの添 加が効果的であり、添加量は 0. 01mol%〜25mol%の範囲が好ましい。 [0174] また、これらの導電性を有する金属酸化物粉体の体積抵抗率は 107 Ω 'cmであるこ と力 子ましく、特に 105 Ω 'cm以下であることが好ましい。また、前記金属酸化物粉体 の 1次粒子サイズは 100A〜0. 2 mであることが好ましぐ前記導電性層は、これら 凝集体の高次構造の長径が 300 Α〜6 μ mである特定の構造を有する粉体を体積 分率で 0. 01%〜20%含んでいることが好ましい。この導電性微粒子 (金属酸化物 粉体）の使用量は 0. 01-5. Og/m2が好ましぐ特に 0. 005〜： Lg/m2が好ましい As examples of hetero atoms of the composite oxide, addition of Al, In, Ta, Sb, Nb, halogen, and Ag is effective, and the addition amount is preferably in the range of 0.01 mol% to 25 mol%. [0174] The volume resistivity of these conductive metal oxide powders is preferably 10 7 Ω'cm, particularly preferably 10 5 Ω'cm or less. In addition, it is preferable that the primary particle size of the metal oxide powder is 100 A to 0.2 m. It is preferable to contain 0.01% to 20% by volume of a powder having a specific structure. The amount of the conductive fine particles (metal oxide powder) used is preferably 0.01-5. Og / m 2 is particularly preferable. 0.005: Lg / m 2 is preferable.
[0175] 前記導電性微粒子の分散用バインダーは、フィルム形成能を有する物であれば特 に限定されるものではないが、例えば、ゼラチン、カゼイン等のタンパク質;カルボキ シメチノレセノレロース、ヒドロキシェチノレセノレロース、ァセチノレセノレロース、ジァセチノレ セルロース、トリァセチルセルロース等のセルロース化合物；デキストラン、寒天、アル ギン酸ナトリウム、デンプン誘導体等の糖類、ポリビュルアルコール、ポリ酢酸ビニル 、ポリアクリル酸エステル、ポリメタクリル酸エステル、ポリスチレン、ポリアクリルアミド、 ポリ—N—ビュルピロリドン、ポリエステル、ポリ塩化ビュル、ポリアクリル酸等の合成 ポリマー等を挙げることができる。 [0175] The conductive fine particle-dispersing binder is not particularly limited as long as it has a film-forming ability, and examples thereof include proteins such as gelatin and casein; carboxymethylenosenolellose, hydroxye, and the like. Cellulose compounds such as chinorecenolose, acetylenolosenolose, dicetinolecellulose, triacetylcellulose; sugars such as dextran, agar, sodium alginate, starch derivatives, polybulu alcohol, polyvinyl acetate, polyacrylate, Examples thereof include synthetic polymers such as polymethacrylic acid ester, polystyrene, polyacrylamide, poly-N-butylpyrrolidone, polyester, polychlorinated butyl, and polyacrylic acid.
[0176] また、前記導電性層はイオン導電性物質を含んでいてもよい。前記イオン導電性物 質とは、電気伝導性を示し、電気を選ぶ担体であるイオンを含有する物質のことであ る。この例としては、イオン性高分子化合物と電解質を含む金属酸化物ゾルとを挙げ ることができる。これらの導電性層の電気抵抗は 1012Ω (25°C.相対湿度 10%)以下 が好ましぐより好ましくは 101()Ω以下、特に好ましくは 109Ω以下である。さらに導電 性材料として、有機電子伝導性材料も好ましぐ例えば、ポリア-リン誘導体、ポリチ ォフェン誘導体、ポリピロール誘導体、ポリアセチレン誘導体などを挙げることができ る。 [0176] The conductive layer may contain an ion conductive substance. The ion conductive substance is a substance that shows electric conductivity and contains ions that are carriers for selecting electricity. Examples thereof include ionic polymer compounds and metal oxide sols containing electrolytes. The electric resistance of these conductive layers is preferably 10 12 Ω (25 ° C., relative humidity 10%) or less, more preferably 10 1 () Ω or less, and particularly preferably 10 9 Ω or less. Further, as the conductive material, an organic electron conductive material is also preferable. Examples thereof include polyarine derivatives, polythiophene derivatives, polypyrrole derivatives, and polyacetylene derivatives.
[0177] (界面活性剤）  [0177] (Surfactant)
本発明のセルロース混合エステルフィルムの利用にお 、ては機能層の形成等に界 面活性剤が好ましく用いられる。本発明における機能層の形成に使用される界面活 性剤はその使用目的によって、分散剤、塗布剤、濡れ剤、帯電防止剤などに分類さ れるが、以下に述べる界面活性剤を適宜使用することで、それらの目的は達成できる 。本発明で使用される界面活性剤は、ノ-オン性、イオン性 (ァ-オン、カチオン、ベ タイン)いずれも使用できる。さらにフッ素系低分子界面活性剤も有機溶媒中での塗 布剤としたり、帯電防止剤として好ましく用いられる。使用される層としてはセルロース 混合エステル力もなるフィルム中でもよいし、その他の機能層のいずれでもよい。光 学用途で利用される場合は、機能層の例としては下塗り層、中間層、配向制御層、 屈折率制御層、保護層、防汚層、粘着層、バック下塗り層、バック層などである。その 使用量は目的を達成するために必要な量であれば特に限定されないが、一般には 添加する層の全質量に対して、 0. 0001〜5質量％が好ましぐさらには 0. 0005- 2質量％が好ましい。その場合の界面活性剤の塗設量は、 lm2当り 0. 02〜： LOOOm g力 S女子ましく、 0. 05〜200mg力女子まし!/ヽ。 In using the cellulose mixed ester film of the present invention, a surfactant is preferably used for forming a functional layer. The surfactant used for forming the functional layer in the present invention is classified into a dispersant, a coating agent, a wetting agent, an antistatic agent, and the like depending on the purpose of use. The surfactant described below is appropriately used. So that those goals can be achieved. . As the surfactant used in the present invention, either a nonionic property or an ionic property (a-on, cation, betaine) can be used. Further, a fluorine-based low molecular surfactant is preferably used as a coating agent in an organic solvent or as an antistatic agent. The layer to be used may be a film having cellulose mixed ester power or any other functional layer. When used in optical applications, examples of functional layers include an undercoat layer, an intermediate layer, an orientation control layer, a refractive index control layer, a protective layer, an antifouling layer, an adhesive layer, a back undercoat layer, and a back layer. . The amount used is not particularly limited as long as it is an amount necessary to achieve the purpose, but generally 0.0001 to 5% by mass is preferable with respect to the total mass of the layer to be added. 2% by mass is preferred. In that case, the coating amount of the surfactant is 0.02 per lm 2 : LOOOmg g force S girlish, 0.05-200 mg force girlish! / ヽ.
[0178] (滑り層） [0178] (Sliding layer)
また、セルロース混合エステルフィルムはフィルム上に付与される!、ずれかの層に 滑り剤を含有させてもよぐ特に最外層に含有させることが好ましい。用いられる滑り 剤としては、例えば、特公昭 53— 292号公報に開示されているようなポリオルガノシ ロキサン;米国特許第 4, 275, 146号明細書に開示されているような高級脂肪酸アミ ド;特公昭 58— 33541号公報、英国特許第 927、 446号明細書あるいは特開昭 55 In addition, the cellulose mixed ester film is applied on the film! It is preferable that a slipping agent is contained in any one of the layers, and it is particularly preferred that the cellulose mixed ester film is contained in the outermost layer. Examples of the slip agent used include polyorganosiloxane as disclosed in JP-B-53-292; higher fatty acid amide as disclosed in US Pat. No. 4,275,146; JP 58-33541, British Patent Nos. 927 and 446 or JP 55
— 126238号および同 58— 90633号公報に開示されているような高級脂肪酸エス テル（炭素数 10〜24の脂肪酸と炭素数 10〜24のアルコールとのエステル）；米国特 許第 3, 933, 516号明細書に開示されているような高級脂肪酸金属塩;特開昭 58— Higher fatty acid esters (esters of fatty acids having 10 to 24 carbon atoms and alcohols having 10 to 24 carbon atoms) as disclosed in Japanese Patent Nos. 126238 and 58-90633; US Pat. No. 3,933, Higher fatty acid metal salts as disclosed in 516;
— 50534号公報に開示されているような、直鎖高級脂肪酸と直鎖高級アルコールと のエステル；国際公開第 90Z108115. 8号パンフレットに開示されているような分岐 アルキル基を含む高級脂肪酸一高級アルコールエステル等が知られている。 — Esters of linear higher fatty acids and linear higher alcohols as disclosed in Japanese Patent No. 50534; higher fatty acid one higher alcohols containing branched alkyl groups as disclosed in WO 90Z108115. Esters are known.
[0179] このうちポリオルガノシロキサンとしては、一般的に知られている、ポリジメチルシロ キサンポリジェチルシロキサン等のポリアルキルシロキサンやポリジフエニルシロキサ ン、ポリメチルフエ-ルシロキサン等のポリアリールシロキサンのほかに、特公昭 53— 292号公報、特公昭 55— 49294号公報、特開昭 60— 140341号公報等に示され るような、炭素数 5以上のアルキル基を持つオルガノポリシロキサン、側鎖にポリオキ シアルキレン基を有するアルキルポリシロキサン、側鎖にアルコキシ、ヒドロキシ、水 素、カルボキシル、アミ入メルカプト基を有するようなオルガノポリシロキサン等の変 性ポリシロキサンを用いることもでき、更に、シロキサンユニットを有するブロックコポリ マーや、特開昭 60— 191240号公報に示されるようなシロキサンユニットを側鎖に持 つグラフトコポリマーを用いることもできる。前記滑り剤の塗設にあたっては，皮膜形 成能のあるバインダーと共に用いることもできる。このようなポリマーとしては，公知の 熱可塑性榭脂、熱硬化性榭脂、放射線硬化性榭脂、反応性榭脂、およびこれらの混 合物、ゼラチンなどの親水性バインダーを使用することができる。滑り性能は静摩擦 係数が 0. 25以下であることが好ましぐ試料を温度 25°C '相対湿度 60%で 2時間調 湿した後、 HEIDON— 10静摩擦係数測定機により、 5mm φのステンレス鋼球を用 V、て測定した値であり、数値が小さ!/、程滑り性はよ!/、。 [0179] Of these, polyorganosiloxanes are generally known polyalkylsiloxanes such as polydimethylsiloxane polyjetylsiloxane and polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenol siloxane. In addition, organopolysiloxanes having an alkyl group having 5 or more carbon atoms, as shown in JP-B-53-292, JP-B-55-49294, JP-A-60-140341, and the like. Alkyl polysiloxane having a polyoxyalkylene group at the side chain, alkoxy, hydroxy, water Modified polysiloxanes such as organopolysiloxanes having silicon, carboxyl, and amide-containing mercapto groups can also be used. Further, as shown in block copolymers having siloxane units and JP-A-60-191240. A graft copolymer having a simple siloxane unit in the side chain can also be used. When the slip agent is applied, it can be used together with a binder capable of forming a film. As such polymers, known thermoplastic resins, thermosetting resins, radiation-curable resins, reactive resins, mixtures thereof, and hydrophilic binders such as gelatin can be used. . For sliding performance, a sample whose static friction coefficient is preferably 0.25 or less is conditioned for 2 hours at a temperature of 25 ° C and a relative humidity of 60%, and then 5 mm φ stainless steel using a HEIDON-10 static friction coefficient measuring machine. It is a value measured using V for a sphere, and the numerical value is small!
[0180] (機能層のマット剤）  [0180] (Matting agent for functional layer)
本発明のセルロース混合エステルフィルムの機能層にお!/、て、フィルムの易滑性や 高湿度下での耐接着性の改良のためにマット剤を使用することが好まし 、。その場 合、表面の突起物の平均高さが 0. 005〜10 111カ 子ましく、より好ましくは 0. 01〜 5 mである。また、その突起物は表面に多数ある程よいが、必要以上に多いとヘイ ズが悪ィ匕する場合がある。好ましい突起物は突起物の平均高さを有する範囲であれ ば、例えば球形、不定形のいずれであってもよい。前記マット剤で突起物を形成する 場合はその含有量が 0. 5〜600mgZm2であり、より好ましいのは l〜400mgZm2 である。この際、使用されるマット剤としてはその組成において特に限定されず、無機 物でも有機物でもよく 2種類以上の混合物でもよい。 In the functional layer of the cellulose mixed ester film of the present invention, it is preferable to use a matting agent for improving the slipperiness of the film and the adhesion resistance under high humidity. In that case, the average height of the protrusions on the surface is preferably 0.005 to 10 111 m, more preferably 0.01 to 5 m. In addition, it is better that there are many protrusions on the surface, but if there are more protrusions than necessary, the haze may deteriorate. A preferable protrusion may be, for example, a spherical shape or an indefinite shape as long as it has an average height of the protrusion. When forming the projections in the matting agent is its content of 0. 5~600mgZm 2, and more preferred is l~400mgZm 2. In this case, the matting agent used is not particularly limited in its composition, and may be inorganic or organic, or a mixture of two or more.
[0181] 前記マット剤は無機化合物または有機化合物のいずれであってもぐ例えば、硫酸 ノ リウム、マンガンコロイド、二酸化チタン、硫酸ストロンチウムバリウム、二酸化ケイ素 、などの無機物の微粉末;湿式法ゃケィ酸のゲル化より得られる合成シリカ等の二酸 化ケィ素やチタンスラッグと硫酸とにより生成する二酸化チタン (ルチル型ゃアナター ス型)等が挙げられる。また、前記マット剤は、粒子サイズの比較的大きい、例えば 20 m以上の無機物力も粉砕した後、分級 (振動ろ過、風力分級など)することによって ち得られる。  [0181] The matting agent may be either an inorganic compound or an organic compound, for example, fine powder of an inorganic substance such as normosulfate, manganese colloid, titanium dioxide, strontium barium sulfate, or silicon dioxide; Examples thereof include silicon dioxide (such as synthetic silica) obtained by gelation, and titanium dioxide (rutile type anatase type) produced by titanium slug and sulfuric acid. The matting agent can be obtained by pulverizing an inorganic substance having a relatively large particle size, for example, 20 m or more, and then classifying (vibration filtering, air classification, etc.).
[0182] 前記マット剤としては、その他、ポリテトラフルォロエチレン、セルロースアセテート、 ポリスチレン、ポリメチルメタタリレート、ポリプピルメタタリレート、ポリメチルアタリレート 、ポリエチレンカーボネート、澱粉等の有機高分子化合物の粉砕分級物も挙げられる[0182] Examples of the matting agent include polytetrafluoroethylene, cellulose acetate, Examples include pulverized and classified products of organic polymer compounds such as polystyrene, polymethylmetatalylate, polypropylmetatalylate, polymethyltalarylate, polyethylene carbonate, and starch.
。また、懸濁重合法で合成した高分子化合物、スプレードライ法あるいは分散法等に より球型にした高分子化合物、または無機化合物を用いることもできる。 . In addition, a high molecular compound synthesized by a suspension polymerization method, a high molecular compound made spherical by a spray drying method or a dispersion method, or an inorganic compound can also be used.
[0183] (他の機能層）  [0183] (Other functional layers)
本発明のセルロース混合エステルフィルムには、透明ハードコート層を設けることが できる。前記透明ハードコート層としては活性線硬化性榭脂層あるいは熱硬化榭脂 層が好ましく用いられる。前記活性線硬化性榭脂層とは紫外線や電子線のような活 性線照射により架橋反応などを経て硬化する榭脂 (活性線硬化性榭脂)を主たる成 分とする層を!ヽぅ。前記活性線硬化性榭脂としては紫外線硬化性榭脂ゃ電子線硬化 性榭脂などが代表的なものとして挙げられるが、紫外線や電子線以外の活性線照射 によって硬化する榭脂でもよい。前記紫外線硬化性榭脂としては、例えば、紫外線硬 化型アクリルウレタン系榭脂、紫外線硬化型ポリエステルアタリレート系榭脂、紫外線 硬化型エポキシアタリレート系榭脂、紫外線硬化型ポリオールアタリレート系榭脂、ま たは紫外線硬化型エポキシ榭脂等を挙げることができる。なお、特開 2003— 03901 4号公報には、塗布されたフィルムを巻き回しや幅方向に把持して乾燥し、活性線硬 化物質を含む塗布液を硬化処理等することにより、高い平面性を有する発明が記載 されており、この発明は本発明にも適応できる。  The cellulose mixed ester film of the present invention can be provided with a transparent hard coat layer. As the transparent hard coat layer, an actinic radiation curable resin layer or a thermosetting resin layer is preferably used. The actinic radiation curable resin layer is a layer mainly composed of a resin (active radiation curable resin) that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays and electron beams. . Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, and an ultraviolet curable polyol acrylate resin. Or UV curable epoxy resin. In JP-A-2003-039014, a coated film is wound or gripped in the width direction and dried, and a coating solution containing an actinic ray-hardening substance is cured, so that high flatness is obtained. This invention is applicable to the present invention.
[0184] 本発明のセルロース混合エステルフィルムには、反射防止層を設けて反射防止フィ ルムを形成することもできる。反射防止層の構成としては、単層、多層等各種知られ ているが、多層のものとしては高屈折率層、低屈折率層を交互に積層した構造のも のが一般的である。構成の例としては、透明基材側から高屈折率層 Z低屈折率層の 2層の順から構成されたものや、屈折率の異なる 3層を、中屈折率層 (透明基材ある いはハードコート層よりも屈折率が高く、高屈折率層よりも屈折率の低!、層） Z高屈 折率層 Z低屈折率層の順に積層されているもの等があり、さらに多くの反射防止層 を積層するものも提案されている。中でも、耐久性、光学特性、コストや生産性などか ら、ハードコート層を有する基材上に、高屈折率層 Z中屈折率層 Z低屈折率層の順 に塗布することが好まし 、構成である。 [0185] 本発明のセルロース混合エステルフィルムは防眩層を設けることもできる。前記防 眩層は表面に凹凸を有する構造をもたせることにより、防眩層表面または防眩層内 部において光を散乱させることにより防眩機能発現させる為、微粒子物質を層中に 含有した構成をとつている。これらの層として好ましい構成は以下に示される態様で ある。前記防眩層は膜厚 0. 5〜5. O /z mであって、平均粒子サイズ 0. 25〜10 /ζ πι の 1種以上の微粒子を含む層であることが好ましい。また、前記防眩層は、平均粒子 サイズが当該膜厚の 1. 1〜2倍のニ酸ィ匕ケィ素粒子と平均粒子サイズが 0. 005 m〜0. 1 μ mの二酸化ケイ素微粒子とを、例えば、ジァセチルセルロースのようなバ インダ一中に含有する層であって、これによつて防眩機能を発揮することができる。こ の「粒子」としては、無機粒子および有機粒子が挙げられる。 [0184] The cellulose mixed ester film of the present invention may be provided with an antireflection layer to form an antireflection film. Various configurations such as a single layer and a multilayer are known as the antireflection layer, but a multilayer structure generally has a structure in which a high refractive index layer and a low refractive index layer are alternately laminated. Examples of the configuration include two layers of the high refractive index layer Z and the low refractive index layer in order from the transparent substrate side, or three layers with different refractive indexes, the medium refractive index layer (transparent substrate or Are higher in refractive index than the hard coat layer, lower in refractive index than the high refractive index layer !, layer) Z high refractive index layer Z low refractive index layer, etc. A layer with an antireflection layer has also been proposed. Among them, from the viewpoint of durability, optical properties, cost and productivity, it is preferable to apply the high refractive index layer Z, the middle refractive index layer Z, and the low refractive index layer in this order on the substrate having the hard coat layer. It is a configuration. [0185] The cellulose mixed ester film of the present invention may be provided with an antiglare layer. Since the antiglare layer has a structure having irregularities on the surface, the antiglare function is expressed by scattering light on the surface of the antiglare layer or inside the antiglare layer. It is. Preferred configurations for these layers are the embodiments shown below. The antiglare layer is preferably a layer having a film thickness of 0.5 to 5. O / zm and containing one or more fine particles having an average particle size of 0.25 to 10 / ζ πι. Further, the antiglare layer is composed of nitric acid silicate particles having an average particle size of 1.1 to 2 times the film thickness, and silicon dioxide fine particles having an average particle size of 0.005 m to 0.1 μm. For example, in a binder such as diacetyl cellulose, which can exhibit an antiglare function. Examples of the “particles” include inorganic particles and organic particles.
[0186] 本発明のセルロース混合エステルフィルムには、カール防止加工を施すこともでき る。カール防止加工とは、これを施した面を内側にして丸まろうとする機能を付与する ものであり、前記カール防止加工を施すことによって、透明榭脂フィルムの片面に何 らかの表面カ卩ェをして、両面に異なる程度 ·種類の表面力卩ェを施した際に、その面を 内側にしてカールしようとするのを防止する働きをするものである。前記カール防止 層は基材の防眩層または反射防止層を有する側と反対側に設ける態様、あるいは、 例えば透明榭脂フィルムの片面に易接着層を塗設する場合もある。また、逆面に力 ール防止加工を塗設するような態様も挙げられる。  [0186] The cellulose mixed ester film of the present invention may be subjected to anti-curl processing. The anti-curl process gives the function of curling with the surface on which the curl is applied. By applying the anti-curl process, some surface coating is applied to one side of the transparent resin film. This function serves to prevent curling with the surface facing inward when different degrees and types of surface force are applied to both surfaces. The anti-curl layer may be provided on the side of the substrate opposite to the side having the anti-glare layer or anti-reflection layer, or, for example, an easy-adhesion layer may be provided on one side of the transparent resin film. In addition, a mode in which a force prevention process is applied to the opposite surface is also included.
[0187] 《本発明のセル口ース混合エステルフィルムの利用》  [0187] << Use of Cell Mouth Mixed Ester Film of the Present Invention >>
本発明のセルロース混合エステルフィルムには、発明協会公開技報 (公技番号 20 01— 1745、 2001年 3月 15日発行、発明協会） 32頁〜 45頁に詳細に記載されてい る機能性層を組み合わせ各光学フィルムを構成することが好まし 、。中でも好ま 、 のが、偏光膜の付与 (偏光板)、光学補償層の付与 (光学補償シート)、反射防止層 の付与 (反射防止フィルム)である。  The cellulose mixed ester film of the present invention has a functional layer described in detail on pages 32 to 45 of the Japan Institute of Invention Publication (Public Technical No. 20 01-1745, published on March 15, 2001, Japan Institute of Invention). It is preferable to compose each optical film in combination. Among them, preferred are application of a polarizing film (polarizing plate), application of an optical compensation layer (optical compensation sheet), and application of an antireflection layer (antireflection film).
[0188] (1)偏光膜の付与 (偏光板の作製）  [0188] (1) Application of polarizing film (Preparation of polarizing plate)
現在、市販の偏光膜は、延伸したポリマーを、浴槽中のヨウ素もしくは二色性色素 の溶液に浸漬し、バインダー中にヨウ素、もしくは二色性色素を浸透させることで作製 されるのが一般的である。偏光膜におけるヨウ素および二色性色素は、バインダー中 で配向することで偏光性能を発現する。二色性色素は、親水性置換基 (例えば、スル ホ、アミ入ヒドロキシル)を有することが好ましい。例えば、発明協会公開技法 (公技 番号 2001— 1745号、 2001年 3月 15日発行、発明協会） 58頁に記載の化合物が 挙げられる。 Currently, a commercially available polarizing film is generally produced by immersing a stretched polymer in a solution of iodine or dichroic dye in a bath and allowing the iodine or dichroic dye to penetrate into the binder. It is. Iodine and dichroic dye in the polarizing film are in the binder. The polarizing performance is expressed by orienting at. The dichroic dye preferably has a hydrophilic substituent (for example, sulfo, amide-containing hydroxyl). For example, the compounds described in page 58 of the Japan Society of Invention Open Technique (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention and Innovation) are listed.
[0189] 偏光膜のバインダーは、それ自体架橋可能なポリマーあるいは架橋剤により架橋さ れるポリマーのいずれも使用することができ、これらの組み合わせを複数使用するこ とができる。ノ インダ一には、例えば特開平 8— 338913号公報の段落番号 [0022] に記載の水溶性ポリマー（例えば、ポリ（N—メチロールアクリルアミド）、カルボキシメ チルセルロース、ゼラチン、ポリビュルアルコール、変性ポリビュルアルコール）が好 ましぐゼラチン、ポリビュルアルコールおよび変性ポリビニルアルコールがさらに好 ましぐポリビュルアルコールおよび変性ポリビュルアルコールが最も好ましい。変性 ポリヒ、、ニノレアノレコーノレ【こつ ヽて ίま、特開平 8— 338913号、同 9 152509号および 同 9— 316127号の各公報に記載がある。バインダー厚みは、 1 m〜50 mである ことが好ましぐより好ましくは 2 μ m〜50 μ mであり、さらには 5 μ m〜30 μ mである 。また、偏光膜のバインダーは架橋していてもよい。架橋性のホウ素化合物 (例えば、 ホウ酸、硼砂)も、架橋剤として用いることができる。ノインダ一の架橋剤の添加量は 、 ノ インダーに対して、 0. 1〜20質量0 /0が好ましい。 [0189] As the binder of the polarizing film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used. For example, the water-soluble polymer (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polybulual alcohol, modified poly (polyethylene alcohol) described in paragraph No. [0022] of JP-A-8-338913 can be used. (Buyl alcohol) is preferred, and gelatin, polybulu alcohol and modified polyvinyl alcohol are more preferred. Modified polyphenols, ninoreanoleconore, described in JP-A-8-338913, JP-A-9152509 and JP-A-9-316127. The binder thickness is preferably 1 m to 50 m, more preferably 2 μm to 50 μm, and further 5 μm to 30 μm. Further, the binder of the polarizing film may be crosslinked. Crosslinkable boron compounds (for example, boric acid and borax) can also be used as a crosslinking agent. Noinda amount of one cross-linking agent with respect to Roh Indah, 0.1 to 20 weight 0/0 are preferred.
[0190] 偏光膜は、偏光膜を延伸する力 (延伸法)、もしくはラビングした (ラビング法)後に、 ヨウ素、二色性染料で染色することが好ましい。 [0190] The polarizing film is preferably dyed with iodine or a dichroic dye after the force for stretching the polarizing film (stretching method) or rubbing (rubbing method).
前記延伸法の場合、延伸倍率は 2. 5〜30. 0倍が好ましぐ 3. 0〜10. 0倍がさら に好ましい。延伸は平行延伸法、特開 2002— 86554号公報に記載の斜め方向に 傾斜め方向に張り出したテンターを用い延伸する方法を用いることができる。前記ケ ン化後のセルロース混合エステルフィルムと、延伸して調製した偏光膜を貼り合わせ 偏光板を作製する。偏光膜を張り合わせる方向は、セルロース混合エステルフィルム の流延軸方向と偏光板の延伸軸方向が 45° になるように行なうのが好ましい。  In the case of the stretching method, the stretching ratio is preferably 2.5 to 30.0 times, more preferably 3.0 to 10.0 times. For stretching, a parallel stretching method, or a method of stretching using a tenter projecting in an oblique direction as described in JP-A-2002-86554 can be used. The cellulose mixed ester film after the saponification and a polarizing film prepared by stretching are bonded together to produce a polarizing plate. The direction of laminating the polarizing film is preferably such that the casting axis direction of the cellulose mixed ester film and the stretching axis direction of the polarizing plate are 45 °.
偏光膜とセルロース混合エステルフィルムとを貼り合わせる際に用いられる接着剤 は特に限定されないが、例えば、 PVA系榭脂（ァセトァセチル基、スルホン酸基、力 ルポキシル基、ォキシアルキレン基等の変性 PVAを含む）やホウ素化合物水溶液等 が挙げられ、中でも PVA系榭脂が好ましい。接着剤層厚みは乾燥後に 0. ！〜 10 μ mが好ましく、 0. 05 μ m〜5 μ mが特に好ましい。 The adhesive used when laminating the polarizing film and the cellulose mixed ester film is not particularly limited. For example, PVA resin (modified PVA such as acetoacetyl group, sulfonic acid group, force oxyxyl group, oxyalkylene group, etc.) And boron compound aqueous solution Among them, PVA-based resin is preferable. The adhesive layer thickness is 0 after drying! ˜10 μm is preferable, and 0.05 μm to 5 μm is particularly preferable.
[0191] (2)光学補償層の付与 (光学補償シートの作製） [0191] (2) Application of optical compensation layer (production of optical compensation sheet)
光学異方性層は、液晶表示装置の黒表示における液晶セル中の液晶化合物を補 償するためのものであり、セルロース混合エステルフィルムの上に配向膜を形成し、さ らに光学異方性層を付与することで形成される。前記表面処理したセルロース混合 エステルフィルム上に配向膜を設ける。この膜は、液晶性分子の配向方向を規定す る機能を有する。しかし、液晶性ィ匕合物を配向後にその配向状態を固定してしまえ ば、配向膜はその役割を果たしているために、本発明の構成要素としては必ずしも 必須のものではない。即ち、配向状態が固定された配向膜上の光学異方性層のみ を偏光子上に転写して本発明の偏光板を作製することも可能である。配向膜は、有 機化合物 (好ましくはポリマー）のラビング処理、無機化合物の斜方蒸着、マイクログ ループを有する層の形成、あるいはラングミュア'ブロジェット法 (LB膜）による有機ィ匕 合物（例えば、 ω—トリコサン酸、ジォクタデシルメチルアンモ -ゥムクロライド、ステア リル酸メチル)の累積のような手段で設けることができる。さらに、電場の付与、磁場の 付与あるいは光照射により、配向機能が生じる配向膜も知られている。  The optically anisotropic layer is used to compensate for the liquid crystal compound in the liquid crystal cell in the black display of the liquid crystal display device. An optically anisotropic layer is formed on the cellulose mixed ester film by forming an alignment film. It is formed by applying a layer. An alignment film is provided on the surface-treated cellulose mixed ester film. This film has a function of defining the alignment direction of liquid crystalline molecules. However, if the alignment state is fixed after the alignment of the liquid crystalline compound, the alignment film plays the role, and is not necessarily an essential component of the present invention. That is, it is also possible to produce the polarizing plate of the present invention by transferring only the optically anisotropic layer on the alignment film in which the alignment state is fixed onto the polarizer. The alignment film may be an organic compound (for example, a rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroup, or a Langmuir'Blodgett method (LB film). , Ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.
[0192] 配向膜の塗布方法は、スピンコーティング法、ディップコーティング法、カーテンコ 一ティング法、エタストルージョンコーティング法、ロッドコーティング法またはロールコ 一ティング法が好ましぐ特にロッドコーティング法が好ましい。また、乾燥後の膜厚は 0. mが好ましい。加熱乾燥は、 20°C〜110°Cで行なうことができる。充 分な架橋を形成するためには 60°C〜100°Cが好ましぐ特に 80°C〜100°Cが好まし い。乾燥時間は 1分間〜 36時間で行なうことができる力 好ましくは 1分間〜 30分で ある。 pHも、使用する架橋剤に最適な値に設定することが好ましぐダルタルアルデ ヒドを使用した場合は、 pH4. 5〜5. 5で、特に 5が好ましい。このようにして得た配向 膜の膜厚は、 0. 1〜： L0 mの範囲にあることが好ましい。  [0192] As a method for applying the alignment film, a spin coating method, a dip coating method, a curtain coating method, an etching coating method, a rod coating method or a roll coating method is preferable, and a rod coating method is particularly preferable. The film thickness after drying is preferably 0. m. Heating and drying can be performed at 20 ° C to 110 ° C. In order to form a sufficient crosslink, 60 ° C to 100 ° C is preferable, and 80 ° C to 100 ° C is particularly preferable. The drying time is a force that can be carried out for 1 minute to 36 hours, preferably 1 minute to 30 minutes. The pH is 4.5 to 5.5, and 5 is particularly preferable when the pH is preferably set to the optimum value for the cross-linking agent to be used. The thickness of the alignment film thus obtained is preferably in the range of 0.1 to L0 m.
[0193] 次に、配向膜の上に光学異方性層の液晶性分子を配向させる。その後、必要に応 じて、配向膜ポリマーと光学異方性層に含まれる多官能モノマーとを反応させるか、 あるいは、架橋剤を用いて配向膜ポリマーを架橋させる。 光学異方性層に用いる液晶性分子には、棒状液晶性分子および円盤状液晶性分 子が含まれる。棒状液晶性分子および円盤状液晶性分子は、高分子液晶でも低分 子液晶でもよぐさらに、低分子液晶が架橋され液晶性を示さなくなつたものも含まれ る。 Next, the liquid crystalline molecules of the optically anisotropic layer are aligned on the alignment film. Thereafter, if necessary, the alignment film polymer is reacted with the polyfunctional monomer contained in the optically anisotropic layer, or the alignment film polymer is crosslinked using a crosslinking agent. The liquid crystalline molecules used in the optically anisotropic layer include rod-like liquid crystalline molecules and discotic liquid crystalline molecules. The rod-like liquid crystal molecule and the disc-like liquid crystal molecule may be either a polymer liquid crystal or a low molecular liquid crystal, and further include those in which a low molecular liquid crystal is crosslinked and does not exhibit liquid crystallinity.
[0194] 棒状液晶性分子  [0194] Rod-like liquid crystalline molecules
前記棒状液晶性分子は、（液晶）ポリマーと結合して 、てもよ 、。  The rod-like liquid crystal molecules may be combined with a (liquid crystal) polymer.
前記棒状液晶性分子については、季刊化学総説第 22卷液晶の化学（1994)日本 化学会編の第 4章、第 7章および第 11章、および液晶デバイスハンドブック日本学術 振興会第 142委員会編の第 3章に記載がある。  The rod-like liquid crystalline molecules are described in Chapters 4, 7 and 11 of the Chemistry of Liquid Crystal Chemistry (1994) Japan Chemistry Association, Chapter 142, and Chapter 142 of the Japan Society for the Promotion of Science. Is described in Chapter 3.
前記棒状液晶性分子の複屈折率は、 0. 001〜0. 7の範囲にあることが好ましい。 前記棒状液晶性分子は、その配向状態を固定するために、重合性基を有することが 好ましい。前記重合性基は、ラジカル重合性不飽基或はカチオン重合性基が好まし ぐ具体的には、例えば特開 2002— 62427号公報の段落番号 [0064]〜[0086] に記載の重合性基、重合性液晶化合物が挙げられる。  The birefringence of the rod-like liquid crystalline molecule is preferably in the range of 0.001 to 0.7. The rod-like liquid crystalline molecules preferably have a polymerizable group in order to fix the alignment state. The polymerizable group is preferably a radically polymerizable unsaturated group or a cationically polymerizable group. Specifically, for example, the polymerizable groups described in paragraphs [0064] to [0086] of JP-A-2002-62427 are disclosed. Group and a polymerizable liquid crystal compound.
[0195] 円盤状液晶性分子 [0195] Discotic liquid crystalline molecules
前記円盤状液晶性分子としては、分子中心の母核に対して、直鎖のアルキル基、 アルコキシ基、置換べンゾィルォキシ基が母核の側鎖として放射線状に置換した構 造である液晶性を示す化合物も含まれる。分子または分子の集合体が、回転対称性 を有し、一定の配向を付与できる化合物であることが好ましい。円盤状液晶性分子か ら形成する光学異方性層は、最終的に光学異方性層に含まれる化合物が円盤状液 晶性分子である必要はなぐ例えば、低分子の円盤状液晶性分子が熱や光で反応 する基を有しており、結果的に熱、光で反応により重合または架橋し、高分子量化し 液晶性を失ったィ匕合物も含まれる。  The discotic liquid crystalline molecule has a liquid crystalline property in which a linear alkyl group, an alkoxy group, and a substituted benzoyloxy group are radially substituted as a side chain of the mother nucleus with respect to the mother nucleus at the center of the molecule. The compounds shown are also included. The molecule or the assembly of molecules is preferably a compound having rotational symmetry and imparting a certain orientation. The optically anisotropic layer formed from the discotic liquid crystalline molecules does not necessarily require that the compound finally contained in the optically anisotropic layer is a discotic liquid crystalline molecule, for example, a low molecular weight discotic liquid crystalline molecule. Includes a compound that reacts with heat or light, and as a result, is polymerized or cross-linked by reaction with heat or light to increase the molecular weight and lose liquid crystallinity.
[0196] 前記円盤状液晶性分子の好ましい例は、特開平 8— 50206号公報に記載されて いる。また、円盤状液晶性分子の重合については、特開平 8— 27284公報に記載が ある。円盤状液晶性分子を重合により固定するためには、円盤状液晶性分子の円盤 状コアに、置換基として重合性基を結合させる必要がある。円盤状コアと重合性基は 、連結基を介して結合する化合物が好ましぐこれにより重合反応においても配向状 態を保つことができる。例えば、特開 2000— 155216号公報の段落番号 [0151]〜 [0168]に記載の化合物等が挙げられる。 [0196] Preferred examples of the discotic liquid crystalline molecules are described in JP-A-8-50206. The polymerization of discotic liquid crystalline molecules is described in JP-A-8-27284. In order to fix the discotic liquid crystalline molecules by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline molecules. The discotic core and the polymerizable group are preferably compounds that are bonded via a linking group. I can keep the state. Examples thereof include compounds described in paragraph numbers [0151] to [0168] of JP-A No. 2000-155216.
[0197] 一光学異方性層の他の組成物一  [0197] Another composition of one optically anisotropic layer
前記光学異方性層は、前記の液晶性分子と共に、可塑剤、界面活性剤、重合性モ ノマ一等を併用して、塗工膜の均一性、膜の強度、液晶分子の配向性等を向上する ことができる。液晶性分子と相溶性を有し、液晶性分子の傾斜角の変化を与えられる 力 ある 、は配向を阻害しな 、ことが好まし!/、。  The optically anisotropic layer uses a plasticizer, a surfactant, a polymerizable monomer, etc. in combination with the liquid crystal molecules, and the uniformity of the coating film, the strength of the film, the orientation of the liquid crystal molecules, etc. Can be improved. It is preferable that it is compatible with liquid crystal molecules and has the ability to change the tilt angle of liquid crystal molecules without disturbing the orientation! /.
[0198] 一光学異方性層の形成一  [0198] Formation of an optically anisotropic layer
前記光学異方性層は、液晶性分子および必要に応じて後述の重合性開始剤や任 意の成分を含む塗布液を、配向膜の上に塗布することで形成できる。光学異方性層 の厚さは、 0. 1 m〜20 μ mであることが好ましぐ 0. 5 m〜15 μ mであることがさ らに好ましぐ： L m〜： L0 mであることが最も好ましい。配向させた液晶性分子を、 配向状態を維持して固定することができる。固定ィ匕は、重合反応により実施すること が好ましい。重合反応には、熱重合開始剤を用いる熱重合反応と光重合開始剤を用 いる光重合反応とが含まれる。光重合反応が好ましい。  The optically anisotropic layer can be formed by applying a coating liquid containing liquid crystalline molecules and, if necessary, a polymerizable initiator described later and optional components on the alignment film. The thickness of the optically anisotropic layer is preferably from 0.1 m to 20 μm, more preferably from 0.5 m to 15 μm: L m to: L0 m Most preferably. The aligned liquid crystalline molecules can be fixed while maintaining the alignment state. It is preferable that the fixation is carried out by a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred.
[0199] この光学補償フィルムと上述の偏光膜とを組み合わせることも好ましい。具体的に は、前記のような光学異方性層用塗布液を偏光膜の表面に塗布することにより光学 異方性層を形成する。その結果、偏光膜と光学異方性層との間にポリマーフィルムを 使用することなぐ偏光膜の寸度変化にともなう応力 (歪み X断面積 X弾性率)が小 さ ヽ薄 、偏光板が作製される。本発明に従う偏光板を大型の液晶表示装置に取り付 けると、光漏れなどの問題を生じることなぐ表示品位の高い画像を表示することがで きる。偏光膜と光学補償層の傾斜角度は、 LCDを構成する液晶セルの両側に貼り合 わされる 2枚の偏光板の透過軸と液晶セルの縦または横方向のなす角度にあわせる ように延伸することが好ましい。通常の傾斜角度は 45° である。しかし、最近は、透 過型、反射型および半透過型 LCDにおいて必ずしも 45° でない装置が開発されて おり、延伸方向は LCDの設計にあわせて任意に調整できることが好ましい。  [0199] It is also preferable to combine this optical compensation film with the polarizing film described above. Specifically, the optically anisotropic layer is formed by applying the coating liquid for the optically anisotropic layer as described above to the surface of the polarizing film. As a result, the stress (strain X cross-sectional area X elastic modulus) associated with the dimensional change of the polarizing film without using a polymer film between the polarizing film and the optically anisotropic layer is small, and a polarizing plate is produced. Is done. When the polarizing plate according to the present invention is attached to a large liquid crystal display device, an image with high display quality can be displayed without causing problems such as light leakage. The inclination angle of the polarizing film and the optical compensation layer is stretched so as to match the angle formed by the transmission axis of the two polarizing plates bonded to both sides of the liquid crystal cell constituting the LCD and the vertical or horizontal direction of the liquid crystal cell. It is preferable. The normal inclination angle is 45 °. Recently, however, devices that are not necessarily 45 ° have been developed for transmissive, reflective, and transflective LCDs, and it is preferable that the stretching direction can be arbitrarily adjusted according to the design of the LCD.
[0200] (液晶表示装置への利用）  [0200] (Use for liquid crystal display devices)
一一般的な液晶表示装置の構成一 本発明のセルロース混合エステルフィルムは、様々な用途で用いることができる。本 発明のセルロース混合エステルフィルムは、液晶表示装置の光学補償シートとして用 いると有効である。なお、フィルムそのものを光学補償シートとして用いる場合は、偏 光素子 (後述）の透過軸と、セルロース混合エステルフィルムカゝらなる光学補償シート の遅相軸とを実質的に平行または垂直になるように配置することが好ましい。このよう な偏光素子と光学補償シートとの配置については、特開平 10— 48420号公報に記 載がある。液晶表示装置は、二枚の電極基板の間に液晶を担持してなる液晶セル、 その両側に配置された二枚の偏光素子、および該液晶セルと該偏光素子との間に 少なくとも一枚の光学補償シートを配置した構成を有している。 Configuration of a general liquid crystal display device The cellulose mixed ester film of the present invention can be used in various applications. The cellulose mixed ester film of the present invention is effective when used as an optical compensation sheet for liquid crystal display devices. When the film itself is used as an optical compensation sheet, the transmission axis of the polarizing element (described later) and the slow axis of the optical compensation sheet such as a cellulose mixed ester film are substantially parallel or perpendicular to each other. It is preferable to arrange in. The arrangement of such a polarizing element and an optical compensation sheet is described in JP-A-10-48420. The liquid crystal display device comprises a liquid crystal cell having a liquid crystal supported between two electrode substrates, two polarizing elements disposed on both sides thereof, and at least one sheet between the liquid crystal cell and the polarizing element. An optical compensation sheet is arranged.
[0201] 液晶セルの液晶層は、通常は、二枚の基板の間にスぺーサーを挟み込んで形成し た空間に液晶を封入して形成する。透明電極層は、導電性物質を含む透明な膜とし て基板上に形成する。液晶セルには、さらにガスバリアー層、ハードコート層あるいは (透明電極層の接着に用いる）アンダーコート層を設けてもよい。これらの層は、通常 、基板上に設けられる。液晶セルの基板は、ー般に80 111〜500 111の厚さを有す る。 [0201] The liquid crystal layer of the liquid crystal cell is usually formed by sealing liquid crystal in a space formed by sandwiching a spacer between two substrates. The transparent electrode layer is formed on the substrate as a transparent film containing a conductive substance. The liquid crystal cell may further be provided with a gas barrier layer, a hard coat layer, or an undercoat layer (used for adhesion of the transparent electrode layer). These layers are usually provided on the substrate. The substrate of the liquid crystal cell generally has a thickness of 80 111 to 500 111.
[0202] 光学補償シートは、液晶画面の着色を取り除くための複屈折率フィルムである。本 発明のセル口ース混合エステルフィルムそのものを、光学補償シートとして用いること ができる。さらに反射防止層、防眩性層、 λ Z4層や 2軸延伸セルロース混合エステ ルフィルムとして機能を付与してもよい。また、液晶表示装置の視野角を改良するた め、本発明のセルロース混合エステルフィルムと、それとは（正 Ζ負の関係力 逆の複 屈折を示すフィルムを重ねて光学補償シートとして用いてもょ 、。光学補償シートの 厚さの範囲は、前述した本発明のセルロース混合エステルフィルムの好まし!/、厚さと 同じである。  [0202] The optical compensation sheet is a birefringent film for removing the coloration of the liquid crystal screen. The cell mouth mixed ester film of the present invention itself can be used as an optical compensation sheet. Furthermore, the function may be imparted as an antireflection layer, an antiglare layer, a λZ4 layer or a biaxially stretched cellulose mixed ester film. In addition, in order to improve the viewing angle of the liquid crystal display device, the cellulose mixed ester film of the present invention may be used as an optical compensation sheet by superimposing a film showing birefringence (positive / negative relational force). The thickness range of the optical compensation sheet is the same as the preferred thickness of the cellulose mixed ester film of the present invention described above.
[0203] 偏光素子の偏光膜には、ヨウ素系偏光膜、二色性染料を用いる染料系偏光膜ゃポ リエン系偏光膜がある。いずれの偏光膜も、一般にポリビニルアルコール系フィルム を用いて製造する。偏光板の保護膜は、 25 /ζ πι〜350 /ζ πιの厚さを有することが好 ましぐ 40 m〜200 mの厚さを有することがさらに好ましい。液晶表示装置には、 表面処理膜を設けてもよい。表面処理膜の機能には、ハードコート、防曇処理、防眩 処理および反射防止処理が含まれる。 [0203] The polarizing film of the polarizing element includes an iodine-based polarizing film and a dye-based polarizing film using a dichroic dye. Both polarizing films are generally produced using a polyvinyl alcohol film. The protective film of the polarizing plate preferably has a thickness of 25 / ζ πι to 350 / ζ πι, more preferably 40 m to 200 m. The liquid crystal display device may be provided with a surface treatment film. The surface treatment film functions include hard coating, anti-fogging treatment and anti-glare. Treatment and antireflection treatment are included.
[0204] 前述したように、支持体の上に液晶（特にディスコティック液晶性分子）を含む光学 的異方性層を設けた光学補償シートも提案されている (特開平 3— 9325号、同 6—1 48429号、同 8— 50206号、同 9— 26572号の各公報記載）。本発明のセルロース 混合エステルフィルムは、そのような光学補償シートの支持体としても用いることがで きる。  [0204] As described above, there has also been proposed an optical compensation sheet in which an optically anisotropic layer containing a liquid crystal (particularly, discotic liquid crystalline molecules) is provided on a support (Japanese Patent Laid-Open No. 3-9325, the same document). 6-1 48429, 8-50206, 9-26572). The cellulose mixed ester film of the present invention can also be used as a support for such an optical compensation sheet.
[0205] ディスコティック液晶性分子を含む光学的異方性層  [0205] Optically anisotropic layer containing discotic liquid crystalline molecules
光学的異方性層は、傾斜配向したディスコティック液晶性分子を含む層であること が好ましい。ディスコティック液晶性分子の円盤面と支持体面とのなす角は、光学的 異方性層の深さ方向にぉ 、て変化して 、る（ハイブリッド配向して 、る）ことが好まし い。ディスコティック液晶性分子の光軸は、円盤面の法線方向に存在する。ディスコ ティック液晶性分子は、円盤面の法線方向の屈折率よりも円盤面方向の屈折率が大 きな複屈折性を有する。ディスコティック液晶性分子は、支持体表面に対して実質的 に水平に配向させてもよい。  The optically anisotropic layer is preferably a layer containing discotic liquid crystal molecules that are tilted and aligned. The angle formed by the disc surface of the discotic liquid crystal molecule and the support surface is preferably changed (hybridly aligned) in the depth direction of the optically anisotropic layer. The optical axis of the discotic liquid crystalline molecule exists in the normal direction of the disk surface. The discotic liquid crystalline molecule has birefringence in which the refractive index in the disc surface direction is larger than the refractive index in the normal direction of the disc surface. The discotic liquid crystalline molecules may be aligned substantially horizontally with respect to the support surface.
[0206] (VA型液晶表示装置）  [0206] (VA type liquid crystal display device)
本発明のセルロース混合エステルフィルムは、 VAモードの液晶セルを有する VA 型液晶表示装置の光学補償シートの支持体としても有効に用いられる。 VA型液晶 表示装置に用いる光学補償シートには、レターデーシヨンの絶対値が最小となる方 向が光学補償シートの面内にも法線方向にも存在しな ヽことが好ま ヽ。 VA型液晶 表示装置に用いる光学補償シートの光学的性質は、光学的異方性層の光学的性質 、支持体の光学的性質および光学的異方性層と支持体との配置により決定される。 VA型液晶表示装置に光学補償シートを二枚使用する場合は、光学補償シートの面 内レターデーシヨンを、 5nm〜5nmの範囲内にすることが好ましい。従って、二枚 の光学補償シートの各面内レターデーシヨンの絶対値は、 0〜5とすることが好ましい  The cellulose mixed ester film of the present invention is also effectively used as a support for an optical compensation sheet of a VA liquid crystal display device having a VA mode liquid crystal cell. In the optical compensation sheet used for the VA liquid crystal display device, it is preferable that the direction in which the absolute value of the letter decision is minimized does not exist in the plane of the optical compensation sheet or in the normal direction. The optical properties of the optical compensation sheet used in the VA liquid crystal display device are determined by the optical properties of the optically anisotropic layer, the optical properties of the support, and the arrangement of the optically anisotropic layer and the support. . When two optical compensation sheets are used in the VA type liquid crystal display device, it is preferable that the in-plane lettering of the optical compensation sheet is in the range of 5 nm to 5 nm. Therefore, the absolute value of the in-plane letter decision of the two optical compensation sheets is preferably 0-5.
[0207] VA型液晶表示装置に光学補償シートを一枚使用する場合は、光学補償シートの 面内レターデーシヨンを、 ΙΟηπ！〜 lOnmの範囲内にすることが好ましい。このよう な光学特性範囲になるように、本発明のセルロース混合エステルフィルムは各種 VA セルに対応した光学特性を付与すればよい。その範囲は、セルギャップに対応して 一枚型セルロース混合エステルフィルムでは、 Re力 0〜120nmであり、好ましくは R e力 0〜： LOOnmであり、特には 50〜90nmである。また、 Rthが 160〜300nmであ り、好ましくは Rthが 170〜260nmであり、特には 180〜240nmである。また、 VA型 液晶表示装置に光学補償シートを二枚使用する場合は、本発明のセルロース混合 エステルフィルムは各種 VAセルに対応した光学特性を付与すればょ ヽ。その範囲 は、セルギャップに対応して二枚型セルロース混合エステルフィルムでは、 Reが 20 〜80nmであり、好ましくは Re力 30〜70nmであり、特には 30〜60nmである。また、 Rth力 0〜200nmであり、好ましくは Rthが 90〜180nmであり、特には 95〜165n mである。 [0207] When one optical compensation sheet is used in the VA liquid crystal display device, the in-plane letter decision of the optical compensation sheet is ΙΟηπ! It is preferable to be within the range of ~ lOnm. The cellulose mixed ester film of the present invention has various VA so as to have such an optical characteristic range. What is necessary is just to provide the optical characteristic corresponding to a cell. The range corresponds to the cell gap, and in the single-sheet cellulose mixed ester film, the Re force is 0 to 120 nm, preferably the Re force is 0 to: LOOnm, particularly 50 to 90 nm. Further, Rth is 160 to 300 nm, preferably Rth is 170 to 260 nm, particularly 180 to 240 nm. In addition, when two optical compensation sheets are used in a VA type liquid crystal display device, the cellulose mixed ester film of the present invention should have optical characteristics corresponding to various VA cells. The range corresponds to the cell gap, and in the double-type cellulose mixed ester film, Re is 20 to 80 nm, preferably Re force is 30 to 70 nm, and particularly 30 to 60 nm. Further, the Rth force is 0 to 200 nm, preferably Rth is 90 to 180 nm, and particularly 95 to 165 nm.
[0208] (OCB型液晶表示装置および HAN型液晶表示装置）  [0208] (OCB type liquid crystal display device and HAN type liquid crystal display device)
本発明のセルロース混合エステルフィルムは、 OCBモードの液晶セルを有する OC B型液晶表示装置あるいは HANモードの液晶セルを有する HAN型液晶表示装置 の光学補償シートの支持体としても有利に用いられる。 OCB型液晶表示装置あるい は HAN型液晶表示装置に用 、る光学補償シートには、レターデーションの絶対値 が最小となる方向が光学補償シートの面内にも法線方向にも存在しないことが好まし V、。 OCB型液晶表示装置ある 、は HAN型液晶表示装置に用いる光学補償シート の光学的性質も、光学的異方性層の光学的性質、支持体の光学的性質および光学 的異方性層と支持体との配置により決定される。本発明のセルロース混合エステルフ イルムは各種 OCBモードの液晶セルに対応した光学特性を付与すればょ 、。その 範囲は、 Re力 S20nm〜100nmであり、好ましくは Reが 30nm〜80nmであり、特に は 30nm〜60nmである。また、 Rth力 l50nm〜300nmであり、好ましくは Rthが 16 Onm〜 260nmであり、特には 170nm〜 250nmである。  The cellulose mixed ester film of the present invention is also advantageously used as a support for an optical compensation sheet of an OC B type liquid crystal display device having an OCB mode liquid crystal cell or a HAN type liquid crystal display device having a HAN mode liquid crystal cell. The optical compensation sheet used for the OCB-type liquid crystal display device or HAN-type liquid crystal display device has no direction in which the absolute value of retardation is minimum in the plane of the optical compensation sheet or in the normal direction. V is preferred. The optical properties of the optical compensation sheet used in the OCB type liquid crystal display device and the HAN type liquid crystal display device are the optical properties of the optically anisotropic layer, the optical properties of the support, and the optically anisotropic layer and support. Determined by placement with the body. The cellulose mixed ester film of the present invention should have optical properties corresponding to various OCB mode liquid crystal cells. The range is Re force S20 nm to 100 nm, preferably Re is 30 nm to 80 nm, particularly 30 nm to 60 nm. The Rth force is from 50 nm to 300 nm, preferably the Rth is from 16 Onm to 260 nm, particularly from 170 nm to 250 nm.
[0209] (その他の液晶表示装置）  [0209] (Other liquid crystal display devices)
本発明のセルロース混合エステルフィルムは、 ASM (Axially Symmetric Alligned M icrocell )モードの液晶セルを有する ASM型液晶表示装置の光学補償シートの支持 体としても有利に用いられる。 ASMモードの液晶セルは、セルの厚さが位置調整可 能な榭脂スぺーサ一により維持されているとの特徴がある。その他の性質は、 TNモ ードの液晶セルと同様である。 ASMモードの液晶セルと ASM型液晶表示装置につ いては、タメ（Kume)外の論文（Kume et al., SID 98 Digest 1089 (1998))に記載があ る。本発明のセルロース混合エステルフィルムを、 TNモードの液晶セルを有する TN 型液晶表示装置の光学補償シートの支持体として用いてもょ 、。 TNモードの液晶セ ルと TN型液晶表示装置については、古くから良く知られている。 TN型液晶表示装 置に用いる光学補償シートについては、特開平 3— 9325号、同 6— 148429号、同 8— 50206号、同 9— 26572号の各公報に記載がある。これらの各種液晶表示装置 に対する光学補償シート用として、本発明のセルロース混合エステルはその光学特 性を所望の範囲で付与すればょ 、。 The cellulose mixed ester film of the present invention is also advantageously used as a support for an optical compensation sheet of an ASM type liquid crystal display device having a liquid crystal cell of ASM (Axially Symmetric Alligned Microcell) mode. The ASM mode liquid crystal cell is characterized in that the cell thickness is maintained by a position-adjustable resin spacer. Other properties are TN This is the same as the liquid crystal cell of the card. ASM-mode liquid crystal cells and ASM-type liquid crystal display devices are described in a paper by Kume et al. (Kume et al., SID 98 Digest 1089 (1998)). The cellulose mixed ester film of the present invention may be used as a support for an optical compensation sheet of a TN type liquid crystal display device having a TN mode liquid crystal cell. TN mode liquid crystal cells and TN liquid crystal display devices have been well known for a long time. The optical compensation sheet used in the TN type liquid crystal display device is described in JP-A-3-9325, JP-A-6-148429, JP-A-8-50206 and JP-A-9-26572. For the optical compensation sheet for these various liquid crystal display devices, the cellulose mixed ester of the present invention should have its optical properties within a desired range.
[0210] 《測定方法および評価方法》  [0210] <Measuring method and evaluation method>
以下にセルロース混合エステルフィルムに関する測定方法と評価方法ついて記載 する。さらに追加の特性評価方法は、別途後述した。  The measurement method and evaluation method for the cellulose mixed ester film are described below. Further additional characteristic evaluation methods are described later.
[0211] (Reおよび Rth並びに、湿度に伴う Reおよび Rth変動）  [0211] (Re and Rth and Re and Rth fluctuations with humidity)
セルロース混合エステルフィルムを 25°C .相対湿度 60%にて 24時間調湿後、自動 複屈折計 (KOBRA— 21ADH：王子計測機器 (株)製)を用いて、 25°C ·相対湿度 6 0%において、上記の方法により正面レターデーシヨン値 (Re)と膜厚方向のレターデ ーシヨン値 (Rth)とを算出させた。  Cellulose mixed ester film was conditioned for 24 hours at 25 ° C and 60% relative humidity, and then using an automatic birefringence meter (KOBRA-21ADH: Oji Scientific Instruments), 25 ° C and relative humidity 60 %, The front letter value (Re) and the film thickness direction letter value (Rth) were calculated by the above method.
[0212] さらに、これらの試料を、 25°C *相対湿度 10%で同様に測定し Re (相対湿度 10%) 、 Rth (相対湿度 10%)を求めた。さらにこれらの試料を 25°C *相対湿度 80%で同様 に測定し、 Re (相対湿度 80%)、 Rth (相対湿度 80%)を求めた。各試料について、 下記式に従 ヽ湿度 Re変動、湿度 Rth変動を求めた。  [0212] Further, these samples were similarly measured at 25 ° C * relative humidity 10%, and Re (relative humidity 10%) and Rth (relative humidity 10%) were obtained. Further, these samples were measured in the same manner at 25 ° C * relative humidity 80%, and Re (relative humidity 80%) and Rth (relative humidity 80%) were obtained. For each sample, humidity Re fluctuation and humidity Rth fluctuation were determined according to the following formula.
•湿度 Re変動（％Z相対湿度％) = [100 X {Re (相対湿度 80%)と Re (相対湿度 10 %)の差の絶対値 }ZRe (相対湿度 60%) ]Z70  • Humidity Re fluctuation (% Z relative humidity%) = [100 X {absolute value of difference between Re (relative humidity 80%) and Re (relative humidity 10%)} ZRe (relative humidity 60%)] Z70
•湿度 Rth変動（％Z相対湿度％) = [100 X {Rth (相対湿度 80%)と Rth (相対湿 度 10%)の差の絶対値 }ZRth (相対湿度 60%) ]Z70  • Humidity Rth fluctuation (% Z relative humidity%) = [100 X {absolute value of difference between Rth (relative humidity 80%) and Rth (relative humidity 10%)} ZRth (relative humidity 60%)] Z70
[0213] (Reムラ、 Rthムラ、厚みムラ） [0213] (Re unevenness, Rth unevenness, uneven thickness)
MD方向サンプリングは、長手方向に lm間隔で 100点、 1cm四方の大きさにサン プリングした。また、 TD方向サンプリングは製膜全幅にわたり、 1cm四方の大きさに 5 cm等間隔でサンブルングした。それぞれ得られたサンプルの各最大値と最小値の 差を、各平均値で割り、百分率で示したものを Reムラ、 Rthムラとした。また、厚みム ラも各サンプルの厚みを測定し、 MD方向、 TD方向の各最大値と最小値の差を、各 平均値で割り、百分率で示したものを厚みムラとした。 In the MD direction sampling, 100 points were sampled at 1-m intervals in the longitudinal direction, and 1 cm square was sampled. In addition, the sampling in the TD direction is 1cm square across the entire width of the film formation. The samples were sampled at equal intervals. The difference between the maximum value and the minimum value of each sample obtained was divided by each average value, and those expressed as percentages were designated as Re unevenness and Rth unevenness. The thickness unevenness was also measured for each sample, and the difference between the maximum and minimum values in the MD and TD directions was divided by the average value, and the percentage was determined as the thickness unevenness.
[0214] (セルロース混合エステルの置換度） [0214] (Degree of substitution of cellulose mixed ester)
セルロースの水酸基に対するァシル基の置換度は、 Carbohydr. Res. 273 (199 The substitution degree of the acyl group with respect to the hydroxyl group of cellulose is Carbohydr. Res. 273 (199
5) 83- 91 (手塚他）に記載の方法で13 C— NMRにより求めた。 5) 13 C-NMR was determined by the method described in 83-91 (Tezuka et al.).
[0215] (セルロース混合エステルの重合度） [0215] (Polymerization degree of cellulose mixed ester)
絶乾したセルロース混合エステル約 0. 2gを精秤して、メチレンクロリド:エタノール Weigh accurately about 0.2g of dry-dried cellulose mixed ester, methylene chloride: ethanol
= 9 : 1 (質量比）の混合溶剤 100mlに溶解した。これをォストワルド粘度計にて 25°C で落下秒数を測定し、重合度を以下の式により求めた。 It was dissolved in 100 ml of a mixed solvent of 9: 1 (mass ratio). This was measured with an Ostwald viscometer at the falling temperature of 25 ° C., and the degree of polymerization was determined by the following equation.
η rel =τ/τ 0  η rel = τ / τ 0
[ 7? ] =ln ( r?  [7?] = Ln (r?
rel )/C  rel) / C
DP= [ r? ]/Km  DP = [r?] / Km
[式中、 Tは測定試料の落下秒数、 Τは溶剤単独の落下秒数、 Inは自然対数、 ま  [Where T is the number of seconds the sample is dropped, Τ is the number of seconds the solvent is dropped, In is the natural logarithm, or
0  0
濃度 (gZL)、 Kmは 6 X 10— 4である。 ] Concentration (gZL), Km is 6 X 10- 4. ]
[0216] (ヘイズ） [0216] (Haze)
試料 40mm X 80mmを、 25°C ·相対湿度 60%でヘイズメーター（HGM— 2DP、 スガ試験機社製)を用いて JIS K— 6714に従って測定した。  A sample 40 mm X 80 mm was measured according to JIS K-6714 using a haze meter (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.) at 25 ° C and 60% relative humidity.
[0217] (透明度） [0217] (Transparency)
試料 20mm X 70mm〖こつ!/、て、 25°C ·相対湿度 60%で透明度測定器 (AKA光電 管比色計、 KOTAKI製作所)を用いて可視光 (615nm)の透明度を測定した。  Sample 20 mm X 70 mm cocoon! /, The transparency of visible light (615 nm) was measured using a transparency measuring device (AKA photoelectric tube colorimeter, KOTAKI Seisakusho) at 25 ° C and 60% relative humidity.
[0218] (軸ズレ） [0218] (Axis misalignment)
自動複屈折計 (KOBRA— 21ADH、王子計測機器 (株)製)を用いて、試料 70m m X 100mmの軸ズレ角度を測定した。幅方向に全幅にわたって等間隔で 20点測 定し、絶対値の平均値を求めた。また、遅相軸角度 (軸ズレ）のレンジとは、幅方向全 域にわたって等間隔に 20点測定し、軸ズレの絶対値の大きいほうから 4点の平均と 小さいほう力も 4点の平均の差をとつたものである。 [0219] (傷つき） Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.), the axial misalignment angle of the sample 70 mm × 100 mm was measured. Twenty points were measured at equal intervals across the entire width in the width direction, and the average absolute value was determined. Also, the slow axis angle (axis deviation) range is measured at 20 points at equal intervals over the entire width direction. It is a difference. [0219] (Scratched)
キシミ値を評価したフィルムを目視で観察し、以下に従って評価した。  The film for which the kimimi value was evaluated was visually observed and evaluated according to the following.
A: 傷つきは全く認められな力つた。  A: The wound was completely unacceptable.
B: 傷つきがわずかに認められた。  B: Slight damage was observed.
C : 傷つきがかなり認められた。  C: A lot of damage was observed.
D: 傷つきが著しく認められた。  D: Significant damage was observed.
[0220] (アルカリ加水分解性） [0220] (Alkaline hydrolyzable)
試料 100mm X 100mmを、自動アルカリケン化処理装置 (新東科学 (株)製）にて 、 60°C, 2molZL水酸ィ匕ナトリウム水溶液にて 3分間ケン化し、 4分間水洗した後、 3 0°C, 0. OlmolZL希硝酸にて 4分間中和し、 4分間水洗した。その後、 100°Cで 3 分間乾燥し、さらに自然乾燥を 1時間行って、下記の目視基準とケン化処理前後の ヘイズ値カゝらアルカリ加水分解性を評価した（25°C ·相対湿度 60%)。  Sample 100mm X 100mm was saponified with 60 ° C, 2molZL sodium hydroxide and sodium hydroxide aqueous solution for 3 minutes with an automatic alkali saponification treatment device (manufactured by Shinto Kagaku Co., Ltd.) ° C, 0. Neutralized with OlmolZL dilute nitric acid for 4 minutes and washed with water for 4 minutes. Then, it was dried at 100 ° C for 3 minutes, and then naturally dried for 1 hour. The following visual standard and haze value before and after saponification treatment were evaluated for alkali hydrolyzability (25 ° C · relative humidity 60 %).
A: 白化は全く認められな力つた。  A: Whitening was an unacceptable force.
B: 白化がわずかに認められた。  B: Slight whitening was observed.
C : 白化がかなり認められた。  C: Fair whitening was observed.
D: 白化が著しく認められた。  D: Significant whitening was observed.
[0221] (カール値） [0221] (Curl value)
試料 35mm X 3mmを、カール調湿槽（HEIDON (No. YG53— 168)、新東科学 (株)製)で相対湿度 25%、 55%、 85%で 24時間調湿し、曲率半径をカール板で測 定した。またウエットでのカールは、水温 25°Cの水中に 30分静置した後に、そのカー ル値を測定した。  Sample 35mm X 3mm was conditioned for 24 hours at 25%, 55% and 85% relative humidity with a curl humidity chamber (HEIDON (No. YG53-168), manufactured by Shinto Kagaku Co., Ltd.), and the radius of curvature was curled. Measured with a plate. Wet curl was measured after standing for 30 minutes in water at a water temperature of 25 ° C.
[0222] (含水率） [0222] (Water content)
試料 7mm X 35mmを水分測定器と試料乾燥装置（CA— 03、 VA—05、共に三 菱ィ匕学 (株) )を用いてカールフィッシャー法で測定した。水分量 (g)を試料質量 (g) で除して算出した。  A 7 mm X 35 mm sample was measured by the Karl Fischer method using a moisture analyzer and a sample drying apparatus (CA-03, VA-05, both manufactured by Mitsubishi Ryogaku Co., Ltd.). It was calculated by dividing the amount of water (g) by the sample mass (g).
[0223] (残留溶剤量） [0223] (Residual solvent amount)
ガスクロマトグラフィー（GC—18A、島津製作所 (株)製)を用いて、試料 7mm X 35 mmのベース残留溶剤量を測定した。 [0224] (熱収縮率） Using a gas chromatography (GC-18A, manufactured by Shimadzu Corporation), the amount of the base residual solvent of the sample 7 mm × 35 mm was measured. [0224] (Heat shrinkage)
試料 30mm X 120mmを 90°C'相対湿度 5%で 24時間、 120時間経時させ、自動 ピンゲージ (新東科学 (株)製）にて、両端に 6mm φの穴を 100mm間隔に開けて、 間隔の原寸 (L1)を最小目盛り lZlOOOmmまで測定した。さらに 90°C ·相対湿度 5 %にて 24時間、 120時間熱処理してパンチ間隔の寸法 (L2)を測定した。熱収縮率 を { (L1 -L2) /L1} X 100により求めた。  Specimen 30mm X 120mm is aged at 90 ° C 'relative humidity 5% for 24 hours and 120 hours, and automatic pin gauge (manufactured by Shinto Kagaku Co., Ltd.) is used to open 6mmφ holes at both ends at intervals of 100mm. The original size (L1) was measured to the minimum scale lZlOOOmm. Further, the dimension (L2) of the punch interval was measured by heat treatment for 24 hours and 120 hours at 90 ° C and 5% relative humidity. The thermal contraction rate was determined by {(L1 -L2) / L1} X 100.
[0225] (透湿度、透湿係数）  [0225] (moisture permeability, permeability coefficient)
試料 70mm φを 25°C'相対湿度 90%および 40°C'相対湿度 90%でそれぞれ 24 時間調湿し、透湿試験装置 (KK— 709007、東洋精機 (株)製）にて、 JIS Z-020 8に従って、単位面積あたりの水分量 (g/m2)を算出した。そして、透湿度を調湿後 質量 調湿前質量により求めた。さらに強制的評価として、 60°C，相対湿度 95%に て 24時間調室後に測定し、透湿係数とした。 Sample 70mm φ was conditioned at 25 ° C 'relative humidity 90% and 40 ° C' relative humidity 90% for 24 hours respectively, and using a moisture permeation tester (KK-709007, manufactured by Toyo Seiki Co., Ltd.), JIS Z According to -020 8, the amount of water per unit area (g / m 2 ) was calculated. And moisture permeability was calculated | required by the mass before moisture conditioning mass before moisture conditioning. Furthermore, as a compulsory evaluation, the moisture permeability coefficient was measured after conditioning for 24 hours at 60 ° C and 95% relative humidity.
[0226] (異物検査）  [0226] (Foreign substance inspection)
試料の全幅 X lmの範囲に反射光をあて、膜中異物を目視にて検出した後、偏光 顕微鏡で異物（リント）を確認して評価した。  Reflected light was applied in the range of the total width X lm of the sample, and foreign matter in the film was visually detected. Then, the foreign matter (lint) was confirmed and evaluated with a polarizing microscope.
[0227] (弾性率） [0227] (Elastic modulus)
東洋ボールドウィン製の万能引っ張り試験機 STM T50BPを用いて、 23°C、相対 湿度 70%雰囲気中、引っ張り速度 10%Z分で 0. 5%伸びにおける応力を測定し、 弾性率を求めた。  Using an all-purpose tensile tester STM T50BP manufactured by Toyo Baldwin, the stress at 0.5% elongation was measured at 23% C and 70% relative humidity at a tensile rate of 10% Z, and the elastic modulus was determined.
[0228] (輝点異物の測定） [0228] (Measurement of bright spot foreign matter)
直交状態 (クロスニコル）に二枚の偏光板を配置して透過光を遮断し、二枚の偏光 板の間に各試料を置いた。偏光板はガラス製保護板のものを使用した。片側から光 を照射し、反対側から光学顕微鏡 (50倍)で lcm2当たりの直径に応じた輝点数を力 ゥントした。 Two polarizing plates were placed in an orthogonal state (crossed Nicols) to block the transmitted light, and each sample was placed between two polarizing plates. The polarizing plate used was a glass protective plate. Light was irradiated from one side, and the number of bright spots corresponding to the diameter per lcm 2 was counted with an optical microscope (50x) from the other side.
[0229] (Tgの測定） [0229] (Measurement of Tg)
DSCの測定パンに試料を 20mg入れた。これを窒素気流中で、 10°CZ分で 30°C 〜250°Cまで昇温した後、 30°Cまで 10°CZ分で冷却した。この後、再度 30°C〜2 50°Cまで昇温してベースラインが低温側力 偏奇し始める温度を Tgとした。 実施例 20 mg of sample was placed in the DSC measurement pan. This was heated in a nitrogen stream to 30 ° C to 250 ° C in 10 ° CZ minutes, and then cooled to 30 ° C in 10 ° CZ minutes. After this, the temperature was raised again from 30 ° C to 250 ° C, and the temperature at which the baseline began to deviate from the low temperature side force was defined as Tg. Example
[0230] 以下に実施例と比較例とを挙げて本発明の特徴をさらに具体的に説明する。以下 の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を 逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す 具体例により限定的に解釈されるべきものではない。  [0230] The features of the present invention will be described more specifically with reference to Examples and Comparative Examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
[0231] [実施例 1]  [0231] [Example 1]
(1 1)セルロース混合エステルフィルムの製膜  (1 1) Production of cellulose mixed ester film
(1)セルロース混合エステルペレットの調製  (1) Preparation of cellulose mixed ester pellets
セルロース混合エステルとして、セルロース混合エステル A (ァセチル置換度 1. 00 、プロピオ-ル置換度 1. 90、トータル置換度 2. 90、粘度平均重合度 180、含水率 0 . 1質量％、ジクロロメタン溶液中 6質量％の粘度 140mPa' s、平均粒子サイズ 1. 4 mmであって標準偏差 0. 4mmである粉体)を用いた。なお、セルロース混合エステ ル Aは、残存酢酸量が 0. 05質量％、残留プロピオン酸が 0.03質量％であり、 Ca含 有量が 51ppm、 Mg含有量が 15ppm、 Fe含有量が 0. 45ppmであり、さらに硫酸基 としてのィォゥ量を 0. 16ppm含むものであった。  As cellulose mixed ester, cellulose mixed ester A (acetyl substitution degree 1.00, propiole substitution degree 1.90, total substitution degree 2.90, viscosity average polymerization degree 180, water content 0.1 mass%, in dichloromethane solution A 6% by weight viscosity of 140 mPa's, an average particle size of 1.4 mm and a standard deviation of 0.4 mm was used. Cellulose mixed ester A has a residual acetic acid content of 0.05 mass%, a residual propionic acid content of 0.03 mass%, a Ca content of 51 ppm, an Mg content of 15 ppm, and an Fe content of 0.45 ppm. In addition, it contained 0.16 ppm of sulfur as sulfate group.
[0232] また 6位ァセチル基の置換度は 0. 31、 6位プロピオ-ル基の置換度は 0. 66であり 全ァセチル中の 33. 5%であった。また、重量平均分子量 Z数平均分子量比は 2. 7 であった。得られたセルロース混合エステル Aを、メチレンクロライド Zメタノール = 90 /10 (質量比）を用いてガラス板上に溶液製膜し、 80 μ mの厚さのフィルムを得た。 このセルロース混合エステル Aのみからなるフィルムのイェローインデックスは 0. 86 であり、ヘイズは 0. 1、透明度は 93. 9%であり、 Tg (ガラス転移温度； DSCにより測 定）は 125°Cであった。このセルロース混合エステル Aは、綿花リンターから採取した セルロースを原料として合成した。  [0232] The substitution degree of the 6-position acetyl group was 0.31, and the substitution degree of the 6-position propiol group was 0.66, which was 33.5% of the total acetyl group. The weight average molecular weight Z number average molecular weight ratio was 2.7. The obtained cellulose mixed ester A was formed into a solution on a glass plate using methylene chloride Zmethanol = 90/10 (mass ratio) to obtain a film having a thickness of 80 μm. The cellulose index A has a yellow index of 0.86, a haze of 0.1, a transparency of 93.9%, and a Tg (glass transition temperature; measured by DSC) of 125 ° C. there were. This cellulose mixed ester A was synthesized using cellulose collected from cotton linter as a raw material.
[0233] このセルロース混合エステル Aを 105°C、 5時間乾燥し、含水率を 0. 07質量％にし た後に、紫外線吸収剤として 2— (2，一ヒドロキシ一 3，， 5，一ジ一 t—ァミル）一ベン ゾトリアゾール（TINUVIN238)、 2 ヒドロキシ一 4— n—ドデシ口キシ一ベンゾフエ ノン（シーソープ 103)、 2 ェチルへキシル 2 シァノ 3, 3，一ジフエ-ルーァク リレー HUVNUL N 539)および 2 (2，一ヒドロキシ一 3，， 5，一ジ一 tert—アミノレ フエ-ル） 5—クロ口べンゾトリアゾールをセルロース混合エステル Aに対してそれぞ れ 0. 3質量％添加し、さらに安定剤および微粒子を表 1に従って添加した。また、へ キサァセチルソルビトールをセルロース混合エステルに対して 5質量0 /0添カ卩した。こ れらを混合して 2軸混練押し出し機のホッパーに投入し、さらに 150〜200°Cでスクリ ユー回転数 300rpm、滞留時間 40秒で混練して融解した。さらに、 50°Cの水浴中で 直径 3mmのストランド状に 200kgZ時間でダイ力も押し出し、 1分間浸漬した後 (スト ランド固化）、 10°Cの水中を 30秒間通過させて温度を下げ、長さ 5mmに裁断してぺ レットを得た。得られたセルロース混合エステル Aからなるペレットを、 105°Cで 120分 間乾燥し、しかる後にアルミニウムを有するラミネートフィルム力もなる防湿袋に袋詰 めして保管した。 [0233] This cellulose mixed ester A was dried at 105 ° C for 5 hours to adjust the water content to 0.07% by mass, and then 2— (2,1hydroxy-1,3,5,1 t-amyl) monobenzotriazole (TINUVIN238), 2-hydroxy-l 4-n-dodecoxy benzophenone (Seethorpe 103), 2-ethyl hexyl 2 cyano 3, 3, 1 diphenyl-luke relay HUVNUL N 539) and 2 (2, 1 hydroxy 1, 3, 5, 1 di tert-amino (Fuel) 5-Black benzotriazole was added in an amount of 0.3% by mass with respect to cellulose mixed ester A, and stabilizers and fine particles were further added according to Table 1. Further, the hexa § cetyl sorbitol was 5 mass 0/0 添Ka卩the cellulose mixed ester to. These were mixed and put into a hopper of a twin-screw kneading extruder, and further kneaded at 150 to 200 ° C. with a screw speed of 300 rpm and a residence time of 40 seconds to be melted. Furthermore, in a 50 ° C water bath, the die force was also extruded into a strand with a diameter of 3 mm in 200 kgZ time, soaked for 1 minute (strand solidification), then passed through 10 ° C water for 30 seconds to reduce the temperature and length. A pellet was obtained by cutting to 5 mm. The obtained pellets of cellulose mixed ester A were dried at 105 ° C. for 120 minutes, and then packed in a moisture-proof bag having aluminum laminate film strength and stored.
[0234] (2)ろ過 [0234] (2) Filtration
前記セルロース混合エステルを直径 3mm、長さ 5mmの円柱状のペレットに成形し たものを、 110°Cの真空乾燥機で 3時間乾燥した。これをホッパーに投入し 215°Cで 溶融した後、口径 5 mの焼結金属フィルターを用いて、 lOMPaで速度 0. lmZ分 にて加圧ろ過した。得られたろ過物は、透明かつ均質な組成であることを確認した。  The cellulose mixed ester formed into a cylindrical pellet having a diameter of 3 mm and a length of 5 mm was dried with a vacuum dryer at 110 ° C. for 3 hours. This was put into a hopper, melted at 215 ° C, and then filtered under pressure at a speed of 0.1 lmZ with lOMPa using a sintered metal filter having a diameter of 5 m. It was confirmed that the obtained filtrate had a transparent and homogeneous composition.
[0235] (3)溶融製膜 [0235] (3) Melt film formation
つぎに 107°C (Tg— 10°C)になるように調整したホッパーに投入し、上流側溶融温 度 195°C、中間溶融温度 210°C、下流側溶融温度 225°C、圧縮比 14、 T ダイ温度 が Tg— 7°C、 T—ダイおよびキャスティングドラム間距離 8cm、固化速度 30°CZ秒、 キャスティングドラム温度は第一ロール (上流）（Tg— 10)°Cで第二ロール (上流）（Tg 11) °Cでかつ第三ロール (上流）（Tg— 12)°Cであり、冷却速度は 15°CZ秒で あった。そして 10分間かけてメルトを溶融押出しした。この際、各水準静電印加法（1 OkVのワイヤーをメルトのキャスティングドラムへの着地点から 10cmのところに設置） を用いた。固化したメルトを剥ぎ取り、 -ップロールを介して、巻き取り張力 6kg/cm2 で巻き取った。なお、巻き取り直前に両端 (全幅の各 3%)をトリミングした後、両端に 幅 10mm、高さ 50 mの厚みだしカ卩ェ (ナーリング）をつけた後、巻き取った。各水 準とも、幅は 1. 5mで 30mZ分で 500m巻き取った。フィルムの膜厚は、表 1に従つ て作製した。 [0236] (4)評価 Next, it is put into a hopper adjusted to 107 ° C (Tg—10 ° C), and has an upstream melting temperature of 195 ° C, an intermediate melting temperature of 210 ° C, a downstream melting temperature of 225 ° C, and a compression ratio of 14 , T die temperature is Tg—7 ° C, T—die and casting drum distance is 8cm, solidification speed is 30 ° CZ seconds, casting drum temperature is first roll (upstream) (Tg—10) ° C and second roll ( Upstream (Tg 11) ° C and the third roll (upstream) (Tg-12) ° C, and the cooling rate was 15 ° CZ seconds. The melt was melt extruded over 10 minutes. At this time, each level electrostatic application method (1 OkV wire was placed 10 cm from the point where the melt was cast on the casting drum) was used. The solidified melt was peeled off, and taken up at a take-up tension of 6 kg / cm 2 via a roll. In addition, after trimming both ends (each 3% of the total width) just before winding, the both ends were thickened with a thickness of 10 mm and a height of 50 m (knurling), and then wound. For each level, the width was 1.5m, and 500m was rolled up for 30mZ. The film thickness was prepared according to Table 1. [0236] (4) Evaluation
(ダイスジ）  (Daisy)
流延方向にスジ状に発生するダイスジの評価は、反射光源のもとでフィルムを目視 で観察し、以下に従って実施した。  The evaluation of die streaks generated in the form of streaks in the casting direction was carried out in accordance with the following, by visually observing the film under a reflected light source.
A: ダイスジは見られなかった。  A: I didn't see Daisuji.
B: ダイスジが微かに見られた。  B: Dice lines were slightly visible.
C： ダイスジがはつきりと認められた。  C: Dice lines were recognized.
D: ダイスジが全面に著しく発生した。  D: Dice lines were noticeably generated on the entire surface.
[0237] (ダンムラ） [0237] (Danmura)
流延方向と直交する方向に認められるダン状のムラ (ダンムラ）を、反射光源のもと 目視で観察し、以下に従って評価した。  Dan-shaped unevenness (danmura) observed in a direction perpendicular to the casting direction was visually observed under a reflected light source and evaluated according to the following.
A: ダンムラは見られなかった。  A: I didn't see Danmura.
B: ダンムラが微かに見られた。  B: Danmura was slightly seen.
C : ダンムラがはっきりと認められた。  C: Danmura was clearly recognized.
D: ダンムラが全面に著しく発生した。  D: Dammura was noticeably generated on the entire surface.
[0238] (微粒子粉落ち） [0238] (Particulate powder falling)
得られた試料フィルム 20cm X 30cmを 25°C、相対湿度 60%で 3時間調湿した後、 フィルムの溶融製膜時のキャスティングドラム面をガラス板に両面テープで貼り合せ、 表を黒紙 10cm X 10cmに lkgの荷重をかけて、 10往復した。その後、黒紙の表面 を目？見観察し粉状の異物を下記に従って判断した。  The resulting sample film 20cm x 30cm was conditioned at 25 ° C and relative humidity 60% for 3 hours, and then the casting drum surface was melt bonded to the glass plate with double-sided tape. X 10cm, lkg load, 10 round trips. Then look at the black paper surface? Observation was made and powdery foreign matters were judged according to the following.
A: 粉上異物は見られな力つた。  A: The foreign matter on the powder was unseen.
B: 粉上異物が微かに見られた。  B: Foreign matter on the powder was slightly seen.
C : 粉上異物がかなり認められた。  C: Foreign matter on the powder was considerably observed.
D: 粉上異物が全面に著しく発生した。  D: Fine particles on the entire surface were generated.
[0239] (接着性） [0239] (Adhesiveness)
得られた試料フィルム 5cm X 5cmを 25°C、相対湿度 80%で 3時間調湿した後、フィ ルムの溶融製膜時のキャスティングドラム面とエアー面を重ね合わせ、防湿袋に封じ 込んだ後に、フィルム全体に 10kgの荷重をかけた。さらに、 60°Cで 3日間経時させ 2 5°C、相対湿度 60%に戻し 2時間後にフィルム同士の接着跡を目視確認し、下記に 従って判断した。 The resulting sample film 5cm x 5cm was conditioned at 25 ° C and relative humidity 80% for 3 hours, and then the casting drum surface and the air surface were overlaid and sealed in a moisture-proof bag. A 10 kg load was applied to the entire film. Furthermore, let it age for 3 days at 60 ° C. 2 After returning to 5 ° C and relative humidity of 60%, the adhesion marks between the films were visually confirmed after 2 hours, and judged according to the following.
A: 接着跡は見られなかった。  A: There was no adhesion mark.
B: 接着跡が微かに見られた。  B: Slight adhesion marks were observed.
C: 接着跡がかなり認められた。  C: Adhesion marks were considerably observed.
D: 接着跡が全面に著しく発生した。  D: Adhesion marks were remarkably generated on the entire surface.
[0240] (面状変化） [0240] (Surface change)
得られた試料フィルム 20cmX 30cmを 150°Cで 24時間加熱した後、 25°C、相対湿 度 60%に戻して 2時間後に、フィルム表面を目視確認し、下記に従って判断した。  The obtained sample film 20 cm × 30 cm was heated at 150 ° C. for 24 hours, then returned to 25 ° C. and the relative humidity 60%, and after 2 hours, the film surface was visually confirmed and judged according to the following.
A: 表面の面状に変化は見られなかった。  A: There was no change in the surface shape.
B: 表面に微かに油状の泣き出しムラが見られた。  B: Slightly oily crying unevenness was observed on the surface.
C: 表面に油状の泣き出しムラがかなり認められた。  C: Oily crying unevenness was noticeable on the surface.
D: 表面に油状の泣き出しムラが全面に著しく発生した。  D: Oily crying unevenness occurred on the entire surface.
[0241] (熱耐候性） [0241] (Thermal weather resistance)
セルロース混合エステル試料を、まず以下に従ってケン化処理した。すなわち、 K OHを 1. 5molZLとなるように溶解した後に、 60°Cに調温したものをケン化液として 用い、 1分間ケン化した。この後、水洗 2分間、 0. ImolZLの硫酸水で 20秒中和し、 さらに水で 2分水洗して洗浄した。その後、 110°Cの乾燥風を風速 15mZ秒で送り、 5分間で乾燥した。つぎに、このケンィ匕済みのフィルムに偏光膜の両面に貼り合わせ て、偏光膜を作製した。偏光膜の延伸方向とセルロース混合エステルの流延方向が 一致するように貼り合せた。偏光膜の作成は、特開平 2001— 141926号公報の実 施例 1に従い、 2対のニップロール間に周速差を与え、長手方向に延伸し、厚み 20 mの偏光膜を調製した。このようにして得た偏光板を 2対用意し、偏光膜同士が直 交するように配置した後、 90°Cで加熱（20日）を実施した。そして、 25°C、相対湿度 6 0%の条件で 3時間経時させた後に、直交した偏光板の偏光度の低下率 (％)で評価 した。  The cellulose mixed ester sample was first saponified as follows. That is, saponification was carried out for 1 minute using a saponification solution prepared by dissolving KOH to 1.5 molZL and then adjusting the temperature to 60 ° C. Thereafter, the mixture was washed with water for 2 minutes, neutralized with 0.1 Imol ZL of sulfuric acid for 20 seconds, and further washed with water for 2 minutes. Thereafter, a drying air of 110 ° C was sent at a wind speed of 15 mZ seconds and dried in 5 minutes. Next, the polarizing film was prepared by pasting the queried film on both sides of the polarizing film. Bonding was performed so that the stretching direction of the polarizing film and the casting direction of the cellulose mixed ester coincided. The polarizing film was prepared in accordance with Example 1 of JP-A-2001-141926 by giving a peripheral speed difference between two pairs of nip rolls and stretching in the longitudinal direction to prepare a polarizing film having a thickness of 20 m. Two pairs of polarizing plates obtained in this way were prepared, arranged so that the polarizing films intersected each other, and then heated at 90 ° C. (20 days). Then, after aging for 3 hours under the conditions of 25 ° C. and 60% relative humidity, the degree of polarization reduction (%) of the orthogonal polarizing plates was evaluated.
[0242] (光耐候性）  [0242] (Light weather resistance)
上の熱耐候性評価における方法と同様にして調製した偏光膜を 2対用意し、偏光 膜同士が直交するように配置した後、 40°C下でキセノンランプにて両面力 照射（5 万ルクス、 30日）した。そして、 25°C、相対湿度 60%に戻して 2時間後に、直交した 偏光板の偏光度の低下率 (％)を、キセノン照射前の低下率で評価した。 Prepare two pairs of polarizing films prepared in the same way as in the thermal weather resistance evaluation above. After the membranes were placed so that they were orthogonal to each other, double-sided force irradiation (50,000 lux, 30 days) was performed with a xenon lamp at 40 ° C. Then, after returning to 25 ° C. and relative humidity 60%, 2 hours later, the reduction rate (%) of the polarization degree of the orthogonal polarizing plate was evaluated by the reduction rate before xenon irradiation.
[0243] このようにして得た未延伸セルロース混合エステルフィルムの物性を、前記の方法 で測定し表 1に記載した。紫外線吸収剤および微粒子を含有しな ヽコントロール試料 1—1は、キシミ値が大きぐ Raは小さぐダイスジ、ダンムラ、傷付き、接着性および 熱耐候性が著しく悪いものであった。また、安定剤のみを含有する比較試料 1—2は 、熱耐候性は改良されるもののダイスジ、ダンムラ、傷付き、接着性は問題となるレべ ルであった。さらに、微粒子のみを含有する比較試料 1—3は、キシミ値は改良される ものの、ダイスジ、ダンムラ、傷付き、接着性の悪化に加え微粒子粉落ち、面状変化 および熱耐候性に劣るものであった。これに対し、本発明の微粒子および微粒子を 含有した本発明の試料 1—4〜1— 9は、キシミ値が小さく Raも適度に付与されており 、ダイスジ、ダンムラ、ヘイズ、透過率、傷付き、微粒子粉落ち、接着性、面状変化お よび熱耐候性の全てを満足するものであった。特に、ダイスジ、ダンムラや微粒子粉 落ちは従来の知見では予測できない驚くべき効果であり、本発明の予想外の効果が 確認できたものである。 [0243] The physical properties of the unstretched cellulose mixed ester film thus obtained were measured by the above-mentioned method and listed in Table 1. The control sample 1-1 containing no UV absorber and fine particles had a large Kishimi value, a small Ra, and a dice line, dangling, scratched, adhesiveness and heat resistance that were extremely poor. In addition, Comparative Sample 1-2 containing only the stabilizer was improved in the weather resistance, but had a problem of die streak, dangling, scratching, and adhesion. In addition, Comparative Sample 1-3, which contains only fine particles, is improved in crease, but is inferior to die lines, dangling, scratches, poor adhesion, in addition to fine particles falling off, surface change, and heat resistance. there were. On the other hand, the microparticles of the present invention and the samples 1-4 to 1-9 of the present invention containing the microparticles have small Kishimi values and moderately imparted Ra, and they have die lines, dangling, haze, transmittance, and scratches. In addition, the fine powder powder, adhesion, surface change and heat resistance were all satisfied. In particular, die stripes, danmura and fine particle fall are surprising effects that cannot be predicted by conventional knowledge, and the unexpected effects of the present invention have been confirmed.
[0244] また、微粒子および安定剤を含有するが、その量が本発明の範囲外である比較試 料 1— 10〜1— 13は、ダイスジ、ダンムラ、ヘイズ、透過率、傷付き、微粒子粉落ち、 接着性、面状変化および熱耐候性の全てを満足することはできなカゝつた。さら〖こ、下 流溶融温度が本発明外であるである比較試料 1— 14、 1— 15も、ダイスジ、ダンムラ 、ヘイズ、透過率、傷付き、微粒子粉落ち、接着性、面状変化および熱耐候性の全 てを満足することはできな力つた。特に、特許文献 2 (特開 2000— 352620号公報） の実施例に挙がられて ヽる溶融温度である 245°Cで溶融製膜した比較試料 1— 15 は、安定剤および微粒子を含有するにもかかわらずキシミ値が大きぐヘイズも大きく 、透過率低下、接着性、面状が悪いものであった。また、微粒子の平均一次粒子サイ ズが大きく本発明の範囲外である比較試料 1 16は、微粒子二次粒子サイズも大き くなり、ヘイズアップ、透過率低下、傷付き悪化、微粒子粉落ちなどの問題を含むも のであった。 [0245] 以上から、本発明にしたがって微粒子と安定剤を適切に含有させ適切な温度で溶 融製膜を実施することにより優れた光学用フィルムを作製できることが確認された。な お、本発明の試料 1 4〜試料 1 9は、残存酢酸量が 0. 01質量％未満であり、 Ca 含有量が 0. 05質量％未満、 Mg含有量が 0. 01質量％未満であった。また、フィル ムの縦横平均熱収縮 (80°CZ相対湿度 90%Z48時間）は 0. 04%であり、熱収 縮が生じ難いフィルムが得られた。さらに、本発明の試料 1—4〜試料 1—9は、光耐 候性も 0. 2%以下であり、コントロール試料 1 1が 0. 15であるのに対して優れてい ることを確認した。 [0244] Comparative Samples 1-10 to 1-13, which contain fine particles and a stabilizer but are outside the scope of the present invention, are die lines, danmura, haze, transmittance, scratches, fine particle powder. It was not possible to satisfy all of the drop, adhesion, surface change and thermal weather resistance. Sarayoko, Comparative Samples 1-14 and 1-15 whose downstream melt temperature is outside the scope of the present invention are also used for die lines, danmura, haze, transmittance, scratches, fine particle falling off, adhesion, surface change and It was impossible to satisfy all of the heat resistance. In particular, Comparative Sample 1-15 melt-formed at 245 ° C., which is the melting temperature listed in the examples of Patent Document 2 (Japanese Patent Laid-Open No. 2000-352620), contains a stabilizer and fine particles. Nevertheless, the haze with a large kishimi value was large, and the transmittance, adhesiveness, and surface condition were poor. In addition, Comparative Sample 116, which has a large average primary particle size outside the scope of the present invention, has a large secondary particle size, resulting in increased haze, reduced transmittance, worsening of scratches, falling off of fine particles, etc. It was a problem. [0245] From the above, it was confirmed that an excellent optical film can be produced by appropriately containing fine particles and a stabilizer according to the present invention and performing melt film formation at an appropriate temperature. Samples 14 to 19 of the present invention have a residual acetic acid content of less than 0.01% by mass, a Ca content of less than 0.05% by mass, and a Mg content of less than 0.01% by mass. there were. In addition, the film's vertical and horizontal average heat shrinkage (80 ° CZ, relative humidity 90%, Z48 hours) was 0.04%, and a film that hardly caused heat shrinkage was obtained. Furthermore, Samples 1-4 to 1-9 of the present invention also have a light weather resistance of 0.2% or less, confirming that the control sample 11 is superior to 0.15. .
[0246] ここで本発明のフィルム試料の代表として試料 1 4は、傾斜幅は 19. 4nm、限界 波長は 389. 4nm、吸収端は 376. 5nm、 380nmの吸収は 1. 4%であり、軸ズレ（ 分子配向軸）は 0. 15° 、弾性率は長手方向が 2. 95GPa、幅方向が 2. 94GPa、抗 張力は長手方向が 119MPa、幅方向が 108MPa、伸長率は長手方向が 66%,幅 方向が 64%であり、アルカリ加水分解性は Aであり、カール値は相対湿度 25%で 0. 3,ウエットでは 1. 0であった。また、含水率は 1. 7質量％であり、熱収縮率は長手 方向が 0. 05%であり幅方向が 0. 07%であった。異物はリントが 5個 Zm未満 であった。また、輝点は、 0. 02mm以下が 10個 Z3m未満、 0. 02〜0. 05mmが 4 個 Z3m未満、 0. 05mm以上はなかった。これらは、光学用途に対しては優れた特 性を有するものであった。また、塗布後の接着も見られず、透湿度も良好であった。 その他の本発明の試料も試料 1—4とほぼ同等の特性値を示すものであった。  [0246] Here, as a representative of the film sample of the present invention, the sample 14 has a slope width of 19.4 nm, a limit wavelength of 389.4 nm, an absorption edge of 376.5 nm, and an absorption at 380 nm of 1.4%. Axial misalignment (molecular orientation axis) is 0.15 °, elastic modulus is 2.95 GPa in the longitudinal direction, 2.94 GPa in the width direction, tensile strength is 119 MPa in the longitudinal direction, 108 MPa in the width direction, and elongation is 66 in the longitudinal direction. %, The width direction was 64%, the alkali hydrolyzability was A, and the curl value was 0.3 at a relative humidity of 25% and 1.0 at wet. The moisture content was 1.7% by mass, and the heat shrinkage was 0.05% in the longitudinal direction and 0.07% in the width direction. The foreign object was lint less than 5 Zm. Also, the bright spot was less than 10 mm less than 0.02 mm, less than Z3m, and less than 4 mm from 0.02 to 0.05 mm, and less than 0.05 mm. These had excellent properties for optical applications. Further, no adhesion after application was observed, and the moisture permeability was good. The other samples of the present invention also showed almost the same characteristic values as Sample 1-4.
[0247] [表 1] [0247] [Table 1]
Figure imgf000086_0001
Figure imgf000086_0001
Figure imgf000086_0002
Figure imgf000086_0002
一 one
実施例 1の本発明の試料 1 4におけるセルロース混合エステル Aをセルロース混 合エステル B (ァセチル置換度 1. 40、プロピオ-ル置換度 1. 50、トータル置換度 2 . 90、粘度平均重合度 130、含水率 0. 1質量％、ジクロロメタン溶液中 6質量％の粘 度 52mPa's、平均粒子サイズ 1. 5mmであって標準偏差 0. 5mmである粉体）に変 更した以外は、実施例 1の試料 1 4と全く同様にして本発明の試料 2 - 1を作製した 。さらに、セルロース混合エステル Aをセルロース混合エステル C (ァセチル置換度 1 . 80、プロピオニル置換度 1. 05、トータル置換度 2. 85、粘度平均重合度 250、含 水率 0. 2質量％、ジクロロメタン溶液中 6質量％の粘度 125mPa's、平均粒子サイズ 1. 4mmであって標準偏差 0. 5mmである粉体）に変更した以外は、実施例 1の試料 1 4と全く同様にして本発明の試料 2— 2を作製した。結果を表 1に示す。 Cellulose mixed ester A in sample 14 of the present invention of Example 1 was mixed with cellulose mixed ester B (acetyl substitution degree 1.40, propiol substitution degree 1.50, total substitution degree 2.90, viscosity average polymerization degree 130. Example 1 except that the water content was changed to 0.1% by weight, 6% by weight in dichloromethane solution, 52 mPa's viscosity, average particle size 1.5 mm and standard deviation 0.5 mm. Sample 2-1 of the present invention was prepared in exactly the same manner as Sample 14. In addition, cellulose mixed ester A was mixed with cellulose mixed ester C (acetyl substitution degree 1.80, propionyl substitution degree 1.05, total substitution degree 2.85, viscosity average polymerization degree 250, water content 0.2 mass%, dichloromethane solution. Sample 2 of the present invention in exactly the same manner as Sample 14 of Example 1 except that the powder was changed to 6% by weight of a viscosity of 125 mPa's, an average particle size of 1.4 mm and a standard deviation of 0.5 mm. — 2 was made. The results are shown in Table 1.
[0249] 本発明の試料 2— 1は、重合度は少し小さめである力 フィルム中での微粒子の平 均 2次粒子サイズも小さぐキシミ値も小さくかつ Raも小さくダイスジも良好であり、光 学特性 (Reムラ、 Rthムラ）、ダイスジ、ダンムラ、ヘイズ、透過率、傷付き、微粒子粉 落ち、接着性、面状変化および熱耐候性の全てで優れたものであった。本発明の試 料 2— 2は、プロピオ-ル基が小さいセルロース混合エステルである力 ダイスジも良 好であり、キシミ値が小さぐ光学特性 (Reムラ、 Rthムラ）、ダイスジ、ダンムラ、ヘイ ズ、透過率、傷付き、微粒子粉落ち、接着性、面状変化および熱耐候性の全てで優 れたものであった。以上から本発明にお 、てはセルロース混合エステルの重合度、 置換基は、その実用許容幅が広いことが確認された。  [0249] Sample 2-1 of the present invention has a slightly lower degree of polymerization. Average of fine particles in film. Secondary particle size is small. Kishimi value is small. Ra is small. Good die streak is good. It was excellent in all of the chemical properties (Re unevenness, Rth unevenness), die streak, damp unevenness, haze, transmittance, scratches, fine particle falling off, adhesion, surface change, and heat resistance. Sample 2-2 of the present invention is a cellulose mixed ester having a small propiol group, and has a good force die squeeze, optical characteristics (Re unevenness, Rth unevenness), dice stripes, dam unevenness, and haze with small kishimi values. In addition, it was excellent in all of transmittance, scratches, fine particle falling off, adhesion, surface change and heat resistance. From the above, it was confirmed in the present invention that the degree of polymerization of the cellulose mixed ester and the substituents have a wide practical tolerance.
[0250] [実施例 3]  [0250] [Example 3]
実施例 1にお ヽて本発明の試料 1—4を、下記の条件でアルカリケンィ匕処理を実施 した。 3molZLの NaOH水溶液を 60°Cに加温した液中でフィルムを 2分間浸漬した 後、 25°Cの水で 30秒間洗浄し、しかる後に 0. 05molZLの硫酸水溶液（25°C)で 1 分間処理し、再度 25°Cの水で水洗した。得られたアルカリケン化済みフィルムの接 触角（対純水）を測定したところ、 28° であり濡れ性は良好のものであった。なお、ァ ルカリケン化処理前の接触角は 62° であり、本発明の試料は優れた表面処理性を 有することが判る。これらのフィルム上に PVAZダルタルアルデヒド（5質量0/ oZO. 2 質量0 /0) )水溶液を lOmlZm2塗布し、さらに市販の偏光膜 (HLC2 ? 5618、サンリツ ツネ土製)を貼り付けて、 70°CZl時間処理し、さらに 30°Cで 6日放置した。得られたセ ルロース混合エステルフィルム付の膜をセルロース混合エステルフィルム側にカツタ 一ナイフで 45° の角度で深さ 200 mの碁盤目状の切り傷を 11本ずつ直角に付与 した。この傷跡部に-チバン製セロテープ No.405 (セロテープ:登録商標）および日 東テープ (PETテープ)を全面に強く付着し 30分放置して、その端部を直角に勢!ヽ よく剥離した。その結果、未ケンィ匕処理セルロース混合エステルフィルムは、すべて の碁盤目状セルロース混合エステルフィルムが剥離した力 ケンィ匕処理したセルロー ス混合エステルフィルムを付与した偏光膜は、セルロース混合エステルフィルムの剥 離はいずれのテープに対しても全く見られな力つた。以上から、本発明のセルロース 混合エステルフィルムは優れた偏光膜特性を有する事がわ力る。 In Example 1, Sample 1-4 of the present invention was subjected to an alkali cane treatment under the following conditions. Immerse the film in a solution of 3molZL NaOH aqueous solution at 60 ° C for 2 minutes, then wash it with 25 ° C water for 30 seconds, and then use 0.05 molZL sulfuric acid aqueous solution (25 ° C) for 1 minute. Treated and washed again with 25 ° C water. When the contact angle (relative to pure water) of the obtained alkali saponified film was measured, it was 28 ° and the wettability was good. The contact angle before the alkaline saponification treatment is 62 °, and it can be seen that the sample of the present invention has an excellent surface treatment property. These films on PVAZ dull glutaraldehyde (5 mass 0 / Ozo. 2 mass 0/0)) aqueous solution LOmlZm 2 was applied, further commercial polarizing film (HLC2? 5618, Sanritsu Tsune earth) was affixed and treated at 70 ° CZl for an additional 6 days at 30 ° C. The resulting membrane with cellulose mixed ester film was subjected to a cut at a 45 ° angle and a 200-m depth grid pattern on the cellulose mixed ester film side by 11 at a right angle. -Chiban cello tape No. 405 (cello tape: registered trademark) and Nitto tape (PET tape) adhered firmly to the entire surface and left for 30 minutes, and the edges were peeled off at right angles. As a result, the unmixed cellulose-treated ester mixed film was peeled off by all the grid-like cellulose mixed ester films. The polarizing film provided with the ken-treated cellulose mixed ester film was not peeled off from the cellulose mixed ester film. It was a force not seen at all for any tape. From the above, it is remarkable that the cellulose mixed ester film of the present invention has excellent polarizing film characteristics.
[0251] [実施例 4]  [0251] [Example 4]
次に、セルロース混合エステルフィルムを偏光板等に応用した実施例を記載する。 (4 1)偏光板の作製  Next, the Example which applied the cellulose mixed ester film to the polarizing plate etc. is described. (4 1) Preparation of polarizing plate
(1)セルロース混合エステルフィルムのケン化  (1) Saponification of cellulose mixed ester film
本発明のセルロース混合エステルフィルム試料 1 4、および別途溶液流延方法に より作製した N, Ν' , Ν，， トリ— m—トルィル— 1, 3, 5—トリァジン— 2, 4, 6 トリア ミンを対セルロースエステルに対して 4質量％添加し、幅方向に残留溶媒の存在する 乾燥中に 1. 32倍延伸したセルローストリアセテート（Reは 60nm、 Rthは 200nm、 膜厚 80 μ m) )を以下の方法でケンィ匕を実施した。すなわち、 KOHを 1. 5molZLと なるように溶解した後に、 60°Cに調温したものをケンィ匕液として用いた。そして、 60°C のセルロース混合エステルフィルム上に 10g/m2塗布し、 1分間ケン化した。この後、 50°Cの温水をスプレーにより、 10リットル/ m2'分で 1分間吹きかけ洗浄した。その後 、 110°Cの乾燥風を風速 15mZ秒で送り、 5分間で乾燥した。これらのケンィ匕は、口 ール状のフィルムを速度 45mZ分で実施した。得られた本発明のセルロース混合ェ ステルフィルムのケン化フィルムを試料 4 1、セルローストリアセテートフィルムのケン 化フィルムを試料 4 - 2とした。 Cellulose mixed ester film sample 14 of the present invention, and N, Ν ′, Ν, tri-m-tolyl-1, 3, 5-triazine-2, 4, 6 triamine prepared by a separate solution casting method Of cellulose triacetate (Re is 60 nm, Rth is 200 nm, film thickness is 80 μm)) The method was carried out. That is, after dissolving KOH to 1.5 molZL and adjusting the temperature to 60 ° C, it was used as the Kenyaku solution. Then, 10 g / m 2 was applied onto a cellulose mixed ester film at 60 ° C. and saponified for 1 minute. Thereafter, hot water at 50 ° C. was sprayed at 10 liter / m 2 ′ minute for 1 minute for washing. Thereafter, a drying air of 110 ° C. was sent at a wind speed of 15 mZ seconds and dried for 5 minutes. These kennels carried out a round film at a speed of 45 mZ. The obtained saponified film of the cellulose mixed ester film of the present invention was designated as Sample 41, and the saponified film of the cellulose triacetate film was designated as Sample 4-2.
[0252] (2)偏光層の作製 [0252] (2) Preparation of polarizing layer
特開 2001— 141926号公報の実施例 1に従い、 2対の-ップロール間に周速差を 与え、長手方向に延伸し、厚み 20 mの偏光層を調製した。 According to Example 1 of Japanese Patent Laid-Open No. 2001-141926, the peripheral speed difference between two pairs of rolls A polarizing layer having a thickness of 20 m was prepared.
(3)貼り合わせ  (3) Bonding
このようにして得た偏光層を、前記ケンィ匕処理したセルロース混合エステルフィルム 試料 4— 1、およびおよび延伸'ケン化したセルローストリアセテートフィルム試料 4— 2で挟んだ後、 PVA ( (株)クラレ製、 PVA— 117H) 3%水溶液を接着剤として、偏光 軸とセルロース混合エステルフィルム試料 4 1および 4 2の長手方向とが 90° とな るように張り合わせた。このうち本発明のセルロース混合エステルフィルム試料 4 1と 、延伸'ケン化したセルローストリアセテートフィルム試料 4— 2を特開 2000— 15426 1号公報の図 2〜9に記載の 20インチ VA型液晶表示装置液晶表示装置に 25°C，相 対湿度 60%下で取り付けた後、これを 25°C *相対湿度 10%の中に持ち込み、 目視 で色調変化の大小を 10段階評価 (大き 、ものほど変化が大き!/、)で評価し、表示ムラ の発生して!/、る領域を目視で評価し、それが発生して 、る割合（％)を求めたところ、 本発明のセル口ース混合エステルフィルムの色調変化は 1であり、非常に優れたもの であった。また、特開平 2002— 86554号公報の実施例 1に従い、テンターを用い延 伸軸が吸収軸に対して 45° の角度となるように延伸した偏光板についても同様に本 発明のセルロース混合エステルフィルムを用い作製したが、前記同様良好な結果が 得られた。  The polarizing layer thus obtained was sandwiched between the Ken-treated cellulose mixed ester film sample 4-1 and the stretched saponified cellulose triacetate film sample 4-2, and then PVA (manufactured by Kuraray Co., Ltd.). , PVA-117H) 3% aqueous solution was used as an adhesive, and the polarizing axis and the longitudinal direction of cellulose mixed ester film samples 41 and 42 were laminated to 90 °. Among them, the cellulose mixed ester film sample 41 of the present invention and the stretched and saponified cellulose triacetate film sample 4-2 are shown in FIGS. 2 to 9 of JP-A-2000-154261, as shown in FIGS. After mounting on a liquid crystal display device at 25 ° C and relative humidity 60%, bring it into 25 ° C * 10% relative humidity, and visually evaluate the change in color tone in 10 levels (larger and larger) The area where the display unevenness is generated is visually evaluated, and the ratio (%) at which it is generated is determined. The cell mouth of the present invention The color change of the mixed ester film was 1, which was excellent. The cellulose mixed ester film of the present invention is similarly applied to a polarizing plate stretched using a tenter so that the stretching axis is at an angle of 45 ° with respect to the absorption axis according to Example 1 of JP-A-2002-86554. As described above, good results were obtained.
[0253] (4 2)光学補償フィルムの作製  [0253] (4 2) Preparation of optical compensation film
特開平 11— 316378号公報の実施例 1の液晶層を塗布したセルロースアセテート フィルムの代わりに、本発明のケン化済みのセルロース混合エステルフィルム 4 1を 使用し、これを、特開 2002— 62431号公報の実施例 9に記載のベンド配向液晶セ ルに 25°C ·相対湿度 60%下で取り付けた後、これを 25°C ·相対湿度 10%の中に持 ち込み、コントラストの変化を目視評価し、色変化の大小を 10段階評価 (大きいもの ほど変化が大きい）して 2のマークを得た。本発明を実施したことにより良好な性能が 得られた。  Instead of the cellulose acetate film coated with the liquid crystal layer of Example 1 of JP-A-11-316378, the saponified cellulose mixed ester film 41 of the present invention was used, and this was used as JP-A-2002-62431. After mounting on the bend-aligned liquid crystal cell described in Example 9 of the publication at 25 ° C and 60% relative humidity, bring it into 25 ° C and 10% relative humidity, and visually observe the change in contrast. The color change was evaluated on a 10-point scale (the larger the change, the greater the change), and a mark of 2 was obtained. Good performance was obtained by carrying out the present invention.
[0254] (4- 3)低反射フィルムの作製  [0254] (4- 3) Preparation of low reflection film
本発明のセルロース混合エステルフィルムを発明協会公開技報 (公技番号 2001 — 1745、 2001年 3月 15日発行、発明協会）の実施例 47に従い本発明の延伸、未 延伸セルロース混合エステルフィルム試料 1 3を用いて低反射フィルムを作製した ところ、良好な光学性能が得られた。 The cellulose mixed ester film of the present invention was stretched according to Example 47 of the Technical Journal of the Invention Association (Public Technical Number 2001 — 1745, published on March 15, 2001, Invention Association). When a low reflection film was produced using the stretched cellulose mixed ester film sample 13, good optical performance was obtained.
[0255] [実施例 5] [0255] [Example 5]
実施例 1にお 、て作製した本発明のセルロース混合エステルフィルム 1— 5を、特 開 2002— 265636号公報記載の実施 f列 13において、セノレローストリアセテートフィ ルム試料 1301の代わりに用いた。そして、特開 2002— 265636号公報記載の実施 例 13と全く同様にして、光学異方性層、偏光板試料の作製によりベンド配向液晶セ ルを作製した。得られた液晶セルは、優れた視野角特性を有するものであった。  The cellulose mixed ester film 1-5 of the present invention produced in Example 1 was used in place of the senorelose triacetate film sample 1301 in Example f row 13 described in JP 2002-265636 A. A bend-aligned liquid crystal cell was prepared in the same manner as in Example 13 described in JP-A-2002-265636 by preparing an optically anisotropic layer and a polarizing plate sample. The obtained liquid crystal cell had excellent viewing angle characteristics.
[0256] [実施例 6] [0256] [Example 6]
実施例 1において作製した本発明のセルロース混合エステルフィルム試料 1—8を 用いて、このフィルムを特開 2002— 265636号公報記載の実施例 14において、セ ルローストリアセテートフィルム試料 1401の代わりに用いた。そして、特開 2002— 26 5636号公報記載の実施例 14と全く同様にして、光学異方性層、偏光板試料の作製 により ΤΝ型液晶セルを作製した。得られた液晶セルは、優れた視野角特性を有する ものであった。  Using the cellulose mixed ester film sample 1-8 of the present invention produced in Example 1, this film was used in place of the cellulose triacetate film sample 1401 in Example 14 described in JP-A-2002-265636. A vertical liquid crystal cell was produced in the same manner as in Example 14 described in JP-A-2002-265636 by producing an optically anisotropic layer and a polarizing plate sample. The obtained liquid crystal cell had excellent viewing angle characteristics.
[0257] [実施例 7]  [0257] [Example 7]
(1)VAパネルへの実装  (1) Mounting on VA panel
本発明の実施例 4で作製した偏光板を、視認側偏光板は 26"ワイドのサイズで偏光 子の吸収軸が長辺となるように、バックライト側偏光板は偏光子の吸収軸が短辺とな るように長方形に打抜いた。 VAモードの液晶 TV (ソニー (株)製、 KDL— L26RX2) の、表裏の偏光板および位相差板を剥し、表と裏側とに本発明の試料 4— 3で作製し た偏光板を組合せで貼り付け、液晶表示装置を作製した。偏光板貼り付け後、 50°C 、 5kgZcm2で 20分間保持し、接着させた。この際、視認側の偏光板の吸収軸をパ ネル水平方向に、バックライト側の偏光板の吸収軸をパネル鉛直方向となり、粘着材 面が液晶セル側となるように配置した。 The polarizing plate produced in Example 4 of the present invention is such that the viewing side polarizing plate has a 26 "wide size and the polarizer has a long absorption axis, and the backlight side polarizing plate has a short polarizing axis. The VA mode LCD TV (manufactured by Sony Corporation, KDL—L26RX2) was stripped of the front and back polarizing plates and retardation plate, and the sample of the present invention was applied to the front and back sides. A liquid crystal display device was fabricated by pasting together the polarizing plates prepared in 4-3, and after holding the polarizing plate, held at 50 ° C and 5 kgZcm 2 for 20 minutes and adhered. The polarizing plate was arranged such that the absorption axis of the polarizing plate was in the horizontal direction of the panel, the absorption axis of the polarizing plate on the backlight side was in the vertical direction of the panel, and the adhesive surface was on the liquid crystal cell side.
[0258] プロテクトフィルムを剥した後、測定機（ELDIM社製、 EZ— Contrast 160D)を 用いて、黒表示および白表示の輝度測定から視野角（コントラスト比が 10以上の範 囲）を算出した。いずれの偏光板を使用した場合も、全方位で極角 80° 以上の良好 な視野角特性が得られた。さらに、耐久試験による光漏れおよび偏光板剥がれテスト を実施し問題な 、ことを確認した。耐久性テスト条件は以下の通りである。 [0258] After removing the protective film, the viewing angle (range of contrast ratio of 10 or more) was calculated from the luminance measurement of black display and white display using a measuring machine (ELDIM, EZ-Contrast 160D). . Regardless of which polarizing plate is used, the polar angle is 80 ° or better in all directions. Viewing angle characteristics were obtained. In addition, light leakage and polarizing plate peeling tests were carried out in a durability test, and it was confirmed that there were no problems. The durability test conditions are as follows.
[0259] 1) 60°C *相対湿度 90%の環境に 200時間保持し、 25°C *相対湿度 60%環境に取り 出し 24時間後に液晶表示装置を黒表示させ、光漏れ強度および偏光板の液晶パネ ルからの剥がれの有無を評価した。  [0259] 1) Hold in an environment of 60 ° C * 90% relative humidity for 200 hours, take out in an environment of 25 ° C * 60% relative humidity, and display the liquid crystal display in black after 24 hours. The presence or absence of peeling from the liquid crystal panel was evaluated.
[0260] 2) 80°Cdryの環境に 200時間保持し、 25°C *相対湿度 60%環境に取り出し 1時間 後に液晶表示装置を黒表示させ、光漏れ強度および偏光板の液晶パネルからの剥 がれの有無を評価した。 [0260] 2) Hold in an 80 ° C dry environment for 200 hours, take out to 25 ° C * relative humidity 60% environment. After 1 hour, display the liquid crystal display in black, light leakage intensity and peeling of the polarizing plate from the liquid crystal panel. The presence or absence of peeling was evaluated.
[0261] [実施例 8] [0261] [Example 8]
本発明の試料を所望の光学特性を示す光学異方性フィルムに作製し、以下の異な る液晶モードの巿販モニターある 、はテレビの位相差膜を剥ぎ取り、本発明の位相 差膜を貼り付けてその視野角特性を調べたところ、優れた広い視野角特性と色味を 得て、本発明のセルロース混合エステルが有用であることを確認した。  The sample of the present invention is prepared on an optically anisotropic film exhibiting desired optical characteristics, and the following liquid crystal mode sales monitor is peeled off the phase difference film of the television and the phase difference film of the present invention is pasted. In addition, when the viewing angle characteristics were investigated, excellent wide viewing angle characteristics and colors were obtained, and it was confirmed that the cellulose mixed ester of the present invention was useful.
[0262] (TNモード） [0262] (TN mode)
視認側偏光板、バックライト側偏光板共に、 17"のサイズで打抜き後の偏光板の長 辺に対して吸収軸が 45° 長辺となるように、長方形に打抜いた。 TNモードの液晶モ 二ター (サムソン社製、 SyncMaster 172X)の表裏の偏光板および位相差板を剥 し、表と裏側に、本発明のセルロース混合エステルからなる偏光板を組合せで貼り付 け、液晶表示装置を作製した。偏光板貼り付け後、 50°C、 5kgZcm2で 20分間保持 し、接着させた。この際、偏光板の光学異方性層がセル基板に対面し、液晶セルのラ ビング方向とそれに対面する光学異方性層のラビング方向とが反平行となるように配 し 7こ。 Both the viewing-side polarizing plate and the backlight-side polarizing plate were punched into a rectangle so that the absorption axis was 45 ° long with respect to the long side of the polarizing plate after punching at a size of 17 ". TN mode liquid crystal Remove the polarizing plates and retardation plates on the front and back of the monitor (Samsson, SyncMaster 172X), and attach the polarizing plate made of the cellulose mixed ester of the present invention on the front and back sides in combination to attach the liquid crystal display device. After applying the polarizing plate, it was held for 20 minutes at 50 ° C, 5 kgZcm 2 and adhered, with the optically anisotropic layer of the polarizing plate facing the cell substrate and the rubbing direction of the liquid crystal cell. Arrange it so that the rubbing direction of the optically anisotropic layer facing it is antiparallel.
[0263] (IPSパネル） [0263] (IPS panel)
本発明の偏光板を、視認側偏光板は 32"ワイドのサイズで偏光子の吸収軸が長辺 となるように、バックライト側偏光板は偏光子の吸収軸が短辺となるように長方形に打 抜いた。 IPSモードの液晶 TV(日立製作所 (株)製、 W32— L5000)の表裏の偏光 板および位相差板を剥し、表と裏側に本発明のセルロース混合エステル力 作製さ れた偏光板を組合せで貼り付け、液晶表示装置を作製した。偏光板貼り付け後、 50 °C、 5kg/cm2で 20分間保持し、接着させた。この際、視認側の偏光板の吸収軸を パネル水平方向に、バックライト側の偏光板の吸収軸をパネル鉛直方向となり、粘着 層表面が液晶セル側となるように配置した。 The polarizing plate of the present invention is such that the viewing side polarizing plate is 32 "wide and the absorption axis of the polarizer is long, and the backlight side polarizing plate is rectangular so that the absorption axis of the polarizer is short. IPS mode LCD TV (W32—L5000, manufactured by Hitachi, Ltd.) The front and back polarizing plates and retardation plates were peeled off, and the cellulose mixed ester force of the present invention was prepared on the front and back sides. The plates were pasted together to make a liquid crystal display device. It was held for 20 minutes at 5 ° C / cm 2 and adhered. In this case, the absorption axis of the polarizing plate on the viewing side is in the horizontal direction of the panel, the absorption axis of the polarizing plate on the backlight side is in the vertical direction of the panel, and the adhesive layer surface is on the liquid crystal cell side.
[0264] [実施例 9] [Example 9]
実施例 1の本発明の試料 1 4における（1 1)セルロース混合エステルフィルムの 製膜の（1)セルロース混合エステルペレットの調製において、予め微粒子を添加せ ずに（3)溶融製膜工程において本発明の微粒子をセルロース混合エステルと共にホ ッパーに投入して、本発明のセルロース混合エステルフィルム 1 4と全く同様にして 、本発明の試料 9—1を作製した。微粒子の平均二次粒子サイズが少し大きいもので あり、キシミ値が少しアップした力 全ての特性で許容範囲内を示すものであった。し たがって、本発明では、微粒子の平均二次粒子サイズを適度にコントロールすること も重要であることが判明した。  In the preparation of (1) cellulose mixed ester pellets in (1 1) cellulose mixed ester film production of sample 14 of the present invention in Example 1, without adding fine particles in advance (3) in the melt film forming step Samples 9-1 of the present invention were prepared in the same manner as the cellulose mixed ester film 14 of the present invention by putting the fine particles of the present invention into a hopper together with the cellulose mixed ester. The average secondary particle size of the fine particles was slightly larger, and the force with a slight increase in the kishimi value was within the allowable range for all characteristics. Therefore, in the present invention, it has been found that it is also important to appropriately control the average secondary particle size of the fine particles.
[0265] [実施例 10] [0265] [Example 10]
実施例 1の本発明の試料 1 4における（1 1)セルロース混合エステルフィルムの 製膜（1)セルロース混合エステルペレットの調製において、フッ素系剥離剤（ヘプタ デカフルォロォクチルーエチルアルコール ポリ（重合度 7)ォキシエチレン エーテ ル)をセルロース混合エステル Aに対して 0.1質量％、および前述のフッ素原子を有 する重合体 PF— 8を 0. 1質量％添加する以外は、試料 1 4と全く同様にして、本発 明の試料 10— 1を作製した。フィルム中での微粒子の平均 2次粒子サイズも小さぐ キシミ値も小さくかつ Raも小さくダイスジ、ダンムラ、ヘイズ、透過率、傷付き、微粒子 粉落ち、接着性、面状変化および熱耐候性、さらに光学特性 (Re、 Rth、 Reムラ、 Rt hムラ）の全ての点で優れたものであった。特に、剥ぎ取り時の荷重が剥ぎ取り剤を添 カロしない試料 1—4に対して、約 1Z2となり優れた製膜安定性のさらなる向上が見ら れた。従って、剥離剤としてフッ素系化合物特に重合度物を含有させることが、有効 であることが確証された。  (11) Film formation of cellulose mixed ester film in sample 14 of the present invention of Example 1 (1) In preparation of cellulose mixed ester pellets, a fluorine-based release agent (heptadecafluorooctyl-ethyl alcohol poly (polymerization) 7) Oxyethylene ether) 0.1% by mass with respect to cellulose mixed ester A and 0.1% by mass of the above-mentioned fluorine atom-containing polymer PF-8 was added in exactly the same manner as Sample 14. Thus, Sample 10-1 of the present invention was produced. Average secondary particle size in film is small Small Kishimi value is small and Ra is small Dice, Danmura, Haze, Transmittance, Scratched, Fine particles Powder fall, Adhesion, Surface change and Thermal resistance The optical characteristics (Re, Rth, Re unevenness, Rth unevenness) were all excellent. In particular, the load at the time of stripping was about 1Z2 for Sample 1-4, where no stripping agent was added, and the film formation stability was further improved. Therefore, it has been confirmed that it is effective to contain a fluorine-based compound, particularly a polymerized product, as a release agent.
[0266] [実施例 11] [Example 11]
(11 - 1)セルロース混合エステルのペレツトイ匕  (11-1) Peretto toy of cellulose mixed ester
表 2に記載される合成セルロース混合エステルを 120°Cで 3時間送風乾燥し、含水 率を 0. 1質量％にした。これに、表 2に記載の可塑剤、および SiO粒子（ァエロジル The synthetic cellulose mixed ester listed in Table 2 was blown and dried at 120 ° C for 3 hours to contain water. The rate was 0.1% by mass. To this, the plasticizer described in Table 2 and SiO particles (Aerosil
2  2
R972V) 0. 05質量％、紫外線吸収剤 2, 4 ビス一（n—ォクチルチオ）ー6—（4一 ヒドロキシ一 3, 5 ジ一 tert—ブチルァニリノ）一 1, 3, 5 トリアジン 0.8質量0 /0、別 の紫外線吸収剤 2 (2，—ヒドロキシ— 3，， 5，—ジ— tert—ブチルフエ-ル）—5—クロ 口べンゾトリアゾール 0. 25質量％を添カ卩し、さらに安定剤トリス一 3, 5 ジー t—ブチ ルー 4 ヒドロキシフエ-ル)イソシァヌレート 0. 15質量部、テトラキス（2, 4 ジ一 t —ブチルフエ-ル）一 4, 4，ビフエ-レンジフォスファイト 0. 15質量部、ビス [ (1, 2, 2 , 6, 6、一ペンタメチル一 4—ピベリジ-ル） 2— (3, 5—ジ一 t ブチル 4—ヒドロキ シベンジル） 2— n ブチル マロネート 0. 15質量部からなる混合物（重量部はセ ルロース混合エステルに対する重量部である）を、 2軸混練押出し機を用いて 190°C で溶融混練した。なお、この 2軸混練押出し機には真空ベントを設け、真空排気 (0. 3気圧に設定）を行った。水浴中に直径 3mmのストランド状に押出し、長さ 5mmに裁 断した。 R972V) 0. 05 wt%, UV absorber 2, 4-bis one (n- Okuchiruchio) over 6- (4 primary hydroxy one 3, 5-di one tert- Buchiruanirino) one 1, 3, 5-triazine 0.8 mass 0/0 , Another UV absorber 2 (2, -hydroxy-3,5, -di-tert-butylphenol) -5-chloro benzotriazole 0.25% by weight, and a stabilizer Tris 1,3 G tert-butyl 4-hydroxyphenol) isocyanurate 0.15 parts by mass, tetrakis (2,4 di-t-butylphenol) 1,4,4 Bibi-range phosphite 0.15 mass Parts, bis [(1, 2, 2, 6, 6, monopentamethyl mono-4-piberidyl) 2- (3,5-di-tert-butyl 4-hydroxybenzyl) 2-n-butyl malonate 0.15 parts by mass The mixture consisting of (parts by weight are parts by weight relative to the cellulose mixed ester) was melted at 190 ° C using a twin-screw kneading extruder. Kneaded. The twin-screw kneading extruder was provided with a vacuum vent and evacuated (set to 0.3 atm). It was extruded into a strand with a diameter of 3 mm in a water bath and cut to a length of 5 mm.
[0267] (11 2)溶融製膜  [0267] (11 2) Melt film formation
上記方法で調製したセルロース混合エステルペレットを、 100°Cの真空乾燥機で 3 時間乾燥した。これを (Tg— 10) °Cになるように調整したホッパーに投入し、単軸押 出機を用いて、圧縮比 3. 0のスクリューを用い、上流供給部（195°C)、中間圧縮部（ 210°C)、下流計量部 (228°C)でセルロース混合エステルを溶融押出した。次に、溶 融したセルロース混合エステルをギアポンプに通し、押出機の脈動を除去した後、 3 mフィルターでろ過し、 230°Cのダイを通してキャストドラムに流延した。この時、 3k Vの電極をメルトから 5cm離した所に設置し、両端 5cmずつ静電印加処理を行った。 (Tg— 5) °C、 Tg、（Tg— 10) °Cに設定した直径 60cmの 3本キャスティングドラムを通 し固化させ、表 2に記載の厚みのセルロース混合エステルフィルムを得た。両端 5cm トリミングした後、両端に幅 10mm、高さ 50 mの厚みだし加工 (ナーリング）をつけ、 各水準とも、幅が 1. 5m、製膜速度が 30m/分、 2000m巻きのサンプルを取った。 キシミ値が小さくかつ傷付きもなぐダイスジ、ヘイズ、透過率、微粒子粉落ち、接着 性、面状および光耐候性の全てで優れたものであった。  The cellulose mixed ester pellets prepared by the above method were dried in a 100 ° C vacuum dryer for 3 hours. Put this in a hopper adjusted to (Tg-10) ° C, and use a single screw extruder with a screw with a compression ratio of 3.0, upstream supply (195 ° C), intermediate compression The cellulose mixed ester was melt-extruded in a part (210 ° C) and a downstream metering part (228 ° C). Next, the melted cellulose mixed ester was passed through a gear pump to remove the pulsation of the extruder, filtered through a 3 m filter, and cast onto a cast drum through a 230 ° C die. At this time, a 3 kV electrode was placed at a distance of 5 cm from the melt, and electrostatic application treatment was performed at 5 cm on both ends. (Tg-5) ° C, Tg, and (Tg-10) The cellulose mixed ester film having the thickness shown in Table 2 was solidified through three casting drums having a diameter of 60 cm set at C. After trimming 5cm at both ends, 10mm wide and 50m high thickness processing (knurling) was applied to both ends. Samples with a width of 1.5m, film forming speed of 30m / min, and 2000m winding were taken for each level. . The die lines, haze, transmittance, fine particle fall off, adhesiveness, surface condition, and light weather resistance were all excellent because of their small squeegee value and no damage.
[0268] (11 3)偏光板の作製 (11 - 3- 1)セルロース混合エステルフィルムの鹼化 [0268] (11 3) Preparation of polarizing plate (11-3-1) Hatching of cellulose mixed ester film
得られたセルロース混合エステルフィルムを次の浸漬鹼ィ匕法で鹼ィ匕した。即ち、 2. 5molZLの NaOH水溶液を鹼化液として用いた。これを 60°Cに調温して、セルロー ス混合エステルフィルムを 2分間浸漬した。この後、 0. 05molZLの硫酸水溶液に 3 0秒浸漬し、水洗した。  The obtained cellulose mixed ester film was prepared by the following immersion method. That is, a 2.5 mol ZL NaOH aqueous solution was used as an incubation solution. The temperature was adjusted to 60 ° C., and the cellulose mixed ester film was immersed for 2 minutes. Thereafter, it was immersed in a 0.05 mol ZL sulfuric acid aqueous solution for 30 seconds and washed with water.
(11 3— 2)偏光層の作製  (11 3-2) Preparation of polarizing layer
特開平 2001— 141926号公報の実施例 1に従い、 2対のニップロール間に周速差 を与え、長手方向に延伸し、厚み 20 mの偏光層を作製した。  According to Example 1 of Japanese Patent Laid-Open No. 2001-141926, a circumferential speed difference was given between two pairs of nip rolls and stretched in the longitudinal direction to prepare a polarizing layer having a thickness of 20 m.
[0269] (11 4)貼り合わせ [0269] (11 4) Bonding
このようにして得た偏光層と、上記酸ィ匕処理したセルロース混合エステルフィルムな らびに酸ィ匕処理したトリアセテートフィルム（富士写真フィルム (株)製フジタック）を、 P VA ( (株)クラレ製 PVA— 117H) 3%水溶液を接着剤として、偏光膜の延伸方向と セルロース混合エステルの製膜方向（長手方法）に下記組み合わせで張り合わせた 偏光板 A：セルロース混合エステルフィルム Z偏光層 Zフジタック（富士タック TD80 UF)  The thus obtained polarizing layer and the above-mentioned acid-treated cellulose mixed ester film and acid-treated triacetate film (Fuji Photo Film Co., Ltd. Fujitac) were combined with PVA (manufactured by Kuraray Co., Ltd.). PVA—117H) 3% aqueous solution as an adhesive, and bonded together in the following combination in the stretching direction of the polarizing film and the film-forming direction of the cellulose mixed ester (longitudinal method) Polarizing plate A: Cellulose mixed ester film Z Polarizing layer Z Fujitac (Fuji (Tack TD80 UF)
偏光板 B：セルロース混合エステルフィルム Z偏光層 Zセルロース混合エステルフ イノレム  Polarizing plate B: Cellulose mixed ester film Z Polarizing layer Z Cellulose mixed ester vinyl
[0270] (11 5)実装評価  [0270] (11 5) Mounting evaluation
VA型液晶セルを使用した 26インチおよび 40インチの液晶表示装置 (シャープ (株 )製）に液晶層を挟んで設置されている 2対の偏光板のうち、観察者側の片面の偏光 板を剥がし、粘着剤を用い、代わりに上記偏光板 Aまたは Bを貼り付けた。観察者側 の偏光板の透過軸とバックライト側の偏光板の透過軸が直交するように配置して、液 晶表示装置を作成した。得られた液晶表示装置が、黒表示状態で発生する光漏れと 色ムラ、面内の均一性を観察した。本発明のセルロース混合エステルフィルムの色調 変化が無ぐ非常に優れたものであった。  Among two pairs of polarizing plates installed with a liquid crystal layer sandwiched between 26-inch and 40-inch liquid crystal displays (made by Sharp Corporation) using VA-type liquid crystal cells, a polarizing plate on one side on the viewer side is used. It peeled off and the said polarizing plate A or B was affixed instead using the adhesive. A liquid crystal display device was prepared by arranging the transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side to be orthogonal to each other. The obtained liquid crystal display device was observed for light leakage, color unevenness and in-plane uniformity generated in a black display state. The cellulose mixed ester film of the present invention was very excellent with no color tone change.
[0271] (11— 6)低反射フィルムの作成  [0271] (11— 6) Creation of low reflection film
本発明のセルロース混合エステルフィルムを発明協会公開技報 (公技番号 2001 — 1745、 2001年 3月 15日発行、発明協会）の実施例 47に従い、低反射フィルムを 作成したところ、良好な光学性能を有するものであった。 The cellulose mixed ester film of the present invention is disclosed in the Technical Report of the Society of Inventions (Public Technical Number 2001) — A low reflection film was produced according to Example 47 of 1745, published on March 15, 2001, Invention Association), and had good optical performance.
[0272] (11 - 7)光学補償フィルムの作成 [0272] (11-7) Creation of optical compensation film
本発明のセル口ース混合エステルフィルムを特開平 11 316378号の実施例 1に従 い、液晶層を塗布し、良好な光学補償フィルムが得られた。  The cell mouth mixed ester film of the present invention was coated with a liquid crystal layer according to Example 1 of JP-A-11 316378, and a good optical compensation film was obtained.
[0273] [表 2] [0273] [Table 2]
Figure imgf000096_0001
Figure imgf000096_0001
産業上の利用可能性 Industrial applicability
本発明の製造方法によれば、ダイスジ、ダンムラ、厚さムラおよび光学特性のムラを 大幅に軽減したセルロース混合エステルフィルムを提供することができる。また、ハン ドリング中のフィルム面同士のこすれによる傷つきを大幅に低減でき、ヘイズ、透過率 、微粒子粉落ち、接着性、面状および熱耐候性の全てで優れたものである。さらに、 本発明のセルロース混合エステルフィルムを液晶表示装置に組み込めば、従来から 問題になっていた表示ムラや湿度による視認性の変化を大幅に抑えることができる。 したがって、本発明のセルロース混合エステルフィルムは産業上の利用可能性が高 い。 According to the manufacturing method of the present invention, die stripes, dangling irregularities, thickness irregularities, and irregularities in optical characteristics are reduced. It is possible to provide a cellulose mixed ester film that is greatly reduced. In addition, scratches caused by rubbing between the film surfaces during handling can be greatly reduced, and all of haze, transmittance, fine powder fall off, adhesion, surface condition, and heat resistance are excellent. Furthermore, if the cellulose mixed ester film of the present invention is incorporated into a liquid crystal display device, it is possible to greatly suppress changes in visibility due to display unevenness and humidity, which have been problematic in the past. Therefore, the cellulose mixed ester film of the present invention has high industrial applicability.

Claims

請求の範囲 The scope of the claims
[1] セルロース混合エステルを溶融製膜して膜厚 20 μ m〜200 μ mのセルロース混合 エステルフィルムを製造するセルロース混合エステルフィルムの製造方法であって、 前記セルロース混合エステル力 下記式 ー1)〜（3— 3)を満たし、且つ、平均一 次粒子サイズが 0. 005 μ m〜2 μ mである微粒子を前記セルロース混合エステルに 対して 0. 005〜1. 0質量％含有するとともに、フエノール系安定剤、リン系安定剤、 チォエーテル系安定剤、スズ系安定剤およびアミン系安定剤からなる群より選択され る 1種類以上の安定剤をセルロース混合エステルに対して 0. 01〜3質量％含有して おり、  [1] A method for producing a cellulose mixed ester film in which a cellulose mixed ester film having a film thickness of 20 μm to 200 μm is produced by melt-casting a cellulose mixed ester, wherein the cellulose mixed ester force is represented by the following formula 1) Containing 0.005 to 1.0 mass% of fine particles satisfying (3-3) and having an average primary particle size of 0.005 μm to 2 μm with respect to the cellulose mixed ester, One or more stabilizers selected from the group consisting of phenol stabilizers, phosphorus stabilizers, thioether stabilizers, tin stabilizers, and amine stabilizers in an amount of 0.01 to 3 mass based on the cellulose mixed ester. % Content,
更に、前記セルロース混合エステルを 180〜230°Cで溶融してダイ力も押し出し、 溶融製膜してセルロース混合エステルフィルムを得る溶融製膜工程を含むことを特 徴とするセルロース混合エステルフィルムの製造方法。  Furthermore, the cellulose mixed ester is melted at 180 to 230 ° C. to extrude the die force, and includes a melt film-forming step of melt-forming to obtain a cellulose mixed ester film. .
式（S— 1) 2. 5≤A+B≤3. 0  Formula (S— 1) 2. 5≤A + B≤3.0
式（S— 2) 0≤A≤2. 2  Formula (S—2) 0≤A≤2. 2
式（S— 3) 0. 8≤B≤3. 0  Formula (S—3) 0. 8≤B≤3.0
(式中、 Aはセルロースの水酸基に対するァセチル基の置換度を表し、 Bはセルロー スの水酸基に対する炭素数 3〜22のァシル基の置換度を表す。）  (In the formula, A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose, and B represents the degree of substitution of the acyl group having 3 to 22 carbon atoms with respect to the hydroxyl group of cellulose.)
[2] 前記微粒子が、 SiO、 ZnO、 TiO、 SnO、 Al O、 ZrO、 In O、 MgO、 BaO、 M [2] The fine particles are SiO, ZnO, TiO, SnO, Al 2 O, ZrO, In 2 O, MgO, BaO, M
2 2 2 2 3 2 2 3  2 2 2 2 3 2 2 3
oOおよび V Oの少なくとも一種力 選ばれることを特徴とする請求項 1に記載のセ The cell according to claim 1, wherein at least one force of oO and V O is selected.
2 2 5 2 2 5
ルロース混合エステルフィルムの製造方法。  A method for producing a mixed cellulose ester film.
[3] 前記セルロース混合エステル中のセルロースの水酸基に対して置換して 、る炭素 数 3〜22のァシル基力 プロピオ-ル基およびブチリル基力 選択される 1以上のァ シル基であることを特徴とする請求項 1または 2に記載のセルロース混合エステルフィ ルムの製造方法。  [3] Substituting with respect to the hydroxyl group of cellulose in the cellulose mixed ester, the acyl group having 3 to 22 carbon atoms is a propiol group and a butyryl group having at least one acyl group selected. The method for producing a cellulose mixed ester film according to claim 1 or 2, wherein
[4] 前記溶融製膜工程にお!、て溶融製膜されたフィルムを、少なくとも 1方向に— 10% 〜50%延伸する延伸工程を含むことを特徴とする請求項 1〜3のいずれか 1項に記 載のセルロース混合エステルフィルムの製造方法。  [4] The process according to any one of claims 1 to 3, wherein the melt film-forming step includes a stretching step of stretching the melt-formed film in at least one direction by 10% to 50%. A method for producing a cellulose mixed ester film according to item 1.
[5] セルロース混合エステルを溶融製膜した膜厚 20 μ m〜200 μ mのセルロース混合 エステルフィルムであって、 [5] Cellulose mixture with a film thickness of 20 μm to 200 μm formed by melt-forming cellulose mixed ester An ester film,
前記セルロース混合エステル力 下記式 ー1)〜（3— 3)を満たし、且つ、平均一 次粒子サイズが 0. 005 μ m〜2 μ mである微粒子を前記セルロース混合エステルに 対して 0. 005〜1. 0質量％含有するとともに、フエノール系安定剤、リン系安定剤、 チォエーテル系安定剤、スズ系安定剤およびアミン系安定剤からなる群より選択され る 1種類以上の安定剤をセルロース混合エステルに対して 0. 01〜3質量％含有して おり、  Cellulose mixed ester force Fine particles satisfying the following formulas (1) to (3-3) and having an average primary particle size of 0.005 μm to 2 μm are added to the cellulose mixed ester to 0.005. ˜1.0% by mass and mixed with one or more stabilizers selected from the group consisting of phenol stabilizers, phosphorus stabilizers, thioether stabilizers, tin stabilizers and amine stabilizers Contained in an amount of 0.01 to 3% by mass relative to the ester,
更に、前記セルロース混合エステルを 180〜230°Cで溶融してダイ力も押し出し、 溶融製膜されて形成されることを特徴とするセルロース混合エステルフィルム。  Further, the cellulose mixed ester film is formed by melting the cellulose mixed ester at 180 to 230 ° C., extruding the die force, and forming a melt.
式（S— 1) 2. 5≤A+B≤3. 0  Formula (S— 1) 2. 5≤A + B≤3.0
式（S— 2) 0≤A≤2. 2  Formula (S—2) 0≤A≤2. 2
式（S— 3) 0. 8≤B≤3. 0  Formula (S—3) 0. 8≤B≤3.0
(式中、 Aはセルロースの水酸基に対するァセチル基の置換度を表し、 Bはセルロー スの水酸基に対する炭素数 3〜22のァシル基の置換度を表す。）  (In the formula, A represents the degree of substitution of the acetyl group with respect to the hydroxyl group of cellulose, and B represents the degree of substitution of the acyl group having 3 to 22 carbon atoms with respect to the hydroxyl group of cellulose.)
[6] 正面レターデーシヨン（Re) 1S 0〜： LOnmであり、且つ、厚さ方向のレターデーショ ン (Rth)の絶対値が 0〜60nmであることを特徴とする請求項 5に記載のセルロース 混合エステルフィルム。 [6] The cellulose according to claim 5, wherein the front-face letter-deposition (Re) 1S 0 is LOnm and the absolute value of the thickness-direction letter-thickness (Rth) is 0 to 60 nm. Mixed ester film.
[7] ヘイズが 0. 1〜1. 2%であり、可視光の透過率が 91%以上であり、 25°C '相対湿 度 60%環境下で波長 590nmにおける面内方向の固有複屈折が 0〜0. 001であり 、厚さ方向の固有複屈折の絶対値が 0〜0. 003であることを特徴とする請求項 5また は 6に記載のセルロース混合エステルフィルム。  [7] Inherent birefringence in the in-plane direction at a wavelength of 590 nm in a 25 ° C 'relative humidity 60% environment with a haze of 0.1-1.2%, a visible light transmittance of 91% or more The cellulose mixed ester film according to claim 5 or 6, wherein the absolute value of intrinsic birefringence in the thickness direction is 0 to 0.003.
[8] 波長 400nmおよび 700nmにおけるそれぞれの正面レターデーシヨン (Re)および 厚さ方向のレターデーシヨン (Rth)が下記式 (A— 1)および (A— 2)を満たすことを 特徴とする請求項 5〜 7のいずれ力 1項に記載のセルロース混合エステルフィルム。 式 (A— 1) 0≤ I Re (700) -Re (400) | ≤15nm  [8] The front-face letter-deposition (Re) and thickness-direction letter-deposition (Rth) at wavelengths of 400 nm and 700 nm satisfy the following formulas (A—1) and (A—2), respectively: The cellulose mixed ester film according to any one of Items 5 to 7, Formula (A— 1) 0≤ I Re (700) -Re (400) | ≤15nm
式 (A— 2) 0≤ I Rth (700) -Rth (400) | ≤35nm  Formula (A— 2) 0≤ I Rth (700) -Rth (400) | ≤35nm
(式中、 Re (400)および Re (700)は、波長 400nmおよび 700nmにおける正面レタ 一デーシヨン（Re)を表し、 Rth (400)および Rth (700)は、波長 400nmおよび 700 nmにおける厚さ方向のレターデーシヨン (Rth)を表す。） (Where Re (400) and Re (700) represent frontal retardation (Re) at wavelengths of 400 nm and 700 nm, and Rth (400) and Rth (700) represent wavelengths of 400 nm and 700 nm. Represents the thickness direction letter thickness (Rth) in nm. )
[9] フィルム表面の水の接触角（25°C .相対湿度 60%)が 45° 以下であることを特徴と する請求項 5〜8のいずれ力 1項に記載のセルロース混合エステルフィルム。 [9] The cellulose mixed ester film according to any one of [5] to [8], wherein the water contact angle (25 ° C., relative humidity 60%) on the film surface is 45 ° or less.
[10] 前記セルロース混合エステルフィルムの動的および静的キシミ値が共に 0. 2〜1. [10] Both the dynamic and static kimi values of the cellulose mixed ester film are 0.2 to 1.
5であり、前記セルロース混合エステルフィルム中に存在する前記微粒子の平均二次 粒子サイズが 0. 01 μ m〜5 μ mであることを特徴とする請求項 5〜9のいずれ力 1項 に記載のセルロース混合エステルフィルム。  10. The force according to claim 5, wherein an average secondary particle size of the fine particles present in the cellulose mixed ester film is 0.01 μm to 5 μm. Cellulose mixed ester film.
[11] 偏光膜に、請求項 5〜 10のいずれ力 1項に記載のセルロース混合エステルフィル ムを少なくとも 1層積層したことを特徴とする偏光板。 [11] A polarizing plate comprising at least one layer of the cellulose mixed ester film according to any one of claims 5 to 10 laminated on a polarizing film.
[12] 請求項 5〜 10のいずれ力 1項に記載のセルロース混合エステルフィルムを基材に 用いたことを特徴とする光学補償フィルム。 [12] An optical compensation film using the cellulose mixed ester film according to any one of claims 5 to 10 as a substrate.
[13] 請求項 5〜 10のいずれ力 1項に記載のセルロース混合エステルフィルムを基材に 用いたことを特徴とする反射防止フィルム。 [13] An antireflection film comprising the cellulose mixed ester film according to any one of claims 5 to 10 as a substrate.
[14] 請求項 11に記載の偏光板、請求項 12の光学補償フィルム、および、請求項 13に 記載の反射防止フィルムの少なくとも一つを用いたことを特徴とする液晶表示装置。 [14] A liquid crystal display device using at least one of the polarizing plate according to claim 11, the optical compensation film according to claim 12, and the antireflection film according to claim 13.
PCT/JP2006/310529 2005-05-26 2006-05-26 Cellulose mixed ester film, method for producing same, polarizing plate, optical compensation film, antireflection film and liquid crystal display WO2006126666A1 (en)

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JP2004272234A (en) * 2003-02-19 2004-09-30 Konica Minolta Holdings Inc Substrate for optical compensation film, optical compensation film, viewing angle compensatation integrated integrated polarizer, and liquid crystal display device
JP2005104148A (en) * 2003-09-11 2005-04-21 Fuji Photo Film Co Ltd Cellulose acylate film and solution film forming method
JP2005104149A (en) * 2003-09-11 2005-04-21 Fuji Photo Film Co Ltd Cellulose acylate film, solution film forming method thereof and film product

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JP2004272234A (en) * 2003-02-19 2004-09-30 Konica Minolta Holdings Inc Substrate for optical compensation film, optical compensation film, viewing angle compensatation integrated integrated polarizer, and liquid crystal display device
JP2005104148A (en) * 2003-09-11 2005-04-21 Fuji Photo Film Co Ltd Cellulose acylate film and solution film forming method
JP2005104149A (en) * 2003-09-11 2005-04-21 Fuji Photo Film Co Ltd Cellulose acylate film, solution film forming method thereof and film product

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JP2008230061A (en) * 2007-03-20 2008-10-02 Fujifilm Corp Manufacturing method of cellulose resin film, cellulose resin film and optical film

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