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WO2011001700A1 - Film d'ester de cellulose, plaque polarisante l'utilisant et dispositif d'affichage à cristaux liquides - Google Patents

Film d'ester de cellulose, plaque polarisante l'utilisant et dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2011001700A1
WO2011001700A1 PCT/JP2010/050693 JP2010050693W WO2011001700A1 WO 2011001700 A1 WO2011001700 A1 WO 2011001700A1 JP 2010050693 W JP2010050693 W JP 2010050693W WO 2011001700 A1 WO2011001700 A1 WO 2011001700A1
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Prior art keywords
cellulose ester
acid
ester film
film
cellulose
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English (en)
Japanese (ja)
Inventor
泰宏 渡辺
隆裕 高木
英幸 佐藤
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Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • 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
    • C08L1/12—Cellulose acetate

Definitions

  • the present invention relates to a cellulose ester film, a polarizing plate using the same, and a liquid crystal display device.
  • Liquid crystal display devices are widely used as image display devices because of their low power consumption and space-saving merit.
  • the VA mode liquid crystal display device has a merit that the contrast is higher than that of other liquid crystal display modes, but has a problem that the contrast and the color change greatly depending on the viewing angle.
  • an improved method using an optical compensation film and a combination thereof has been proposed. For example, a method of disposing two biaxial films on both sides so as to sandwich a liquid crystal cell is disclosed (Patent Document 1).
  • Cellulose ester films are widely used in optical applications such as polarizing plate protective films and optical compensation films because they are excellent in transparency and can produce films having controlled refractive index anisotropy.
  • cellulose esters having a low degree of substitution such as diacetyl cellulose
  • optical films such as ⁇ / 4 plates for a long time
  • Patent Document 2 cellulose esters having a low degree of substitution
  • a viewing angle widening effect such as improvement in polarization unevenness and suppression of the above-mentioned tint due to high expression of retardation in the in-plane direction.
  • the cellulose ester having a low degree of substitution has a low heat-and-moisture resistance, the protective property of the polarizer is low and the application range is limited.
  • Patent Document 3 As a cellulose ester plasticizer, a technique using a compound having an octanol-water partition coefficient (log P) of 0 to 12 has been proposed (Patent Document 3). However, when this method is applied to a cellulose ester having a low degree of substitution, the plasticizer bleed-out and the heat-and-moisture resistance of the film are improved, but there is a problem of white turbidity, and further improvement has been demanded.
  • log P octanol-water partition coefficient
  • the present invention has excellent retardation development and high optical compensation effect.
  • a film using a low substitution degree cellulose ester suppresses haze, improves heat and humidity resistance, and is used particularly for a VA mode liquid crystal display device. It is an object of the present invention to obtain a cellulose ester film having high contrast and excellent viewing angle characteristics.
  • Relational expression (1) 4 ⁇ (logP (A)) ⁇ (logP (B)) ⁇ 12 (However, log P (A): octanol-water partition coefficient of the hydrolysis inhibitor (A), log P (B): octanol-water partition coefficient of the phase difference adjusting agent (B)) Relational expression (2) 2.5 ⁇ (W (A) / W (B)) ⁇ (1 / DR) ⁇ 8.5 (However, W (A): Mass contained in the cellulose ester film of the hydrolysis inhibitor (A), W (B): Mass contained in the cellulose ester film of the retardation adjusting agent (B), DR: Cellulose (Represents the residual hydroxyl group of acetate.) 2. 2. The cellulose ester film as described in 1 above, wherein an internal haze of the cellulose ester film is 0.05 or less.
  • Relational expression (3) 1 ⁇ (acetic acid amount (ppm)) / (total amount of calcium and magnesium (ppm)) ⁇ 30 4). 4. The cellulose ester film as described in any one of 1 to 3 above, wherein the log P (A) is 7 or more and less than 11, and the log P (B) is 0 or more and less than 7.
  • the hydrolysis inhibitor (A) is an ester compound in which at least one pyranose structure or furanose structure is 1 to 12, and a part of the OH group in the structure is esterified. 5.
  • the cellulose ester film as described in any one of 1 to 4 above.
  • B- (GA) n-GB (Wherein B is a hydroxy group or carboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms)
  • A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.) 7).
  • a cellulose ester film comprising:
  • R1 and R2 each represents an alkyl group which may have a linear or branched substituent having 8 to 22 carbon atoms.
  • A represents an alkylene group having 2 to 4 carbon atoms, and n represents 0 or 1 to 1.
  • M is a hydrogen atom, an alkali metal atom or an ammonium group, and L is a divalent linking group.
  • Q represents carboxylic acid or a salt thereof, sulfonic acid or a salt thereof, sulfate ester or a salt thereof.
  • a polarizing plate wherein the cellulose ester film according to any one of 1 to 10 is bonded to at least one side of a polarizer composed of polyvinyl alcohol.
  • a liquid crystal display device comprising the polarizing plate according to 11 above on at least one surface of a liquid crystal cell.
  • the present inventor has applied a plurality of compounds each having an octanol-water partition coefficient (log P value) in a specific range to a cellulose ester having a low degree of substitution.
  • log P value octanol-water partition coefficient
  • a cellulose ester film having a low haze, excellent heat-and-moisture resistance, particularly high contrast and excellent viewing angle characteristics for use in a VA mode liquid crystal display device and
  • the polarizing plate which used this for the polarizing plate protective film, and the liquid crystal display device which has this polarizing plate can be provided.
  • the cellulose ester film of the present invention contains a compound in which the difference in octanol-water partition coefficient (log P) between the hydrolysis inhibitor (A) and the retardation adjusting agent (B) is within a certain range. .
  • a compound with a high log P value improves the water resistance of the cellulose ester film, but because of its low compatibility with the cellulose ester, it tends to cause white turbidity and precipitation, while a compound with a low log P value improves the transparency of the cellulose ester film. But the improvement in water resistance is insufficient.
  • the cellulose ester having a high residual hydroxyl group used in the present invention can be compatible only with a compound having an extremely low log P value, and it has not been possible to achieve both improvement of the white turbidity and water resistance of the cellulose ester film.
  • the cellulose ester film of the present invention satisfies the following relational expressions (1) and (2), thereby making it possible to improve water resistance without causing cloudiness of the film.
  • Relational expression (1) 4 ⁇ (logP (A)) ⁇ (logP (B)) ⁇ 12 (However, log P (A): octanol-water partition coefficient of the hydrolysis inhibitor (A), log P (B): octanol-water partition coefficient of the phase difference adjusting agent (B)) Relational expression (2) 2.5 ⁇ (W (A) / W (B)) ⁇ (1 / DR) ⁇ 8.5 (However, W (A), W (B): the hydrolysis inhibitor (A), the mass contained in the cellulose ester film of the retardation adjusting agent (B), DR: represents the residual hydroxyl group of cellulose acetate.) The reason is considered as follows.
  • phase difference adjusting agent (B) having a difference in the log P value as shown in the relational expression (1) when included, the compatibility of the cellulose ester and the hydrolysis inhibitor (A) is aided, and the hydrolysis inhibitor (A). Can exist uniformly in the cellulose ester.
  • the difference between logP (A) and logP (B) when the difference between logP (A) and logP (B) is smaller than 4, the water resistance cannot be improved, and the difference between logP (A) and logP (B) exceeds 12. When it is large, the compatibility of the compound cannot be improved.
  • relational expression (2) shows the relationship between the mass contained in the cellulose ester film of the hydrolysis inhibitor (A) and the retardation adjusting agent (B) and the hydroxyl group residual degree (DR) of cellulose acetate. If it is less than .5, the water resistance cannot be improved, and if it exceeds 8.5, the compatibility is not improved sufficiently.
  • the octanol-water partition coefficient (log P value) can be measured by a flask soaking method described in JIS Z-7260-107 (2000). Further, the octanol-water partition coefficient (log P value) can be estimated by a computational chemical method or an empirical method instead of the actual measurement.
  • Crippen's fragmentation method J. Chem. Inf. Comput. Sci.”, 27, p21 (1987)
  • Viswanadhan's fragmentation method J. Chem. Inf. Comput. Sci.”
  • Broto's fragmentation method Eur. J. Med. Chem.-Chim. Theor. ", 19, p71 (1984)
  • CLogP method references
  • Leo, A., Jow, PYC, Silipo, C., Hansch, C., J. Med. Chem., 18, 865, 1975 are preferably used, but the Crippen's fragmentation method ( “JC em.Inf.Comput.Sci.”, 27 volumes, p21 (1987 years)) is more preferable.
  • the cellulose ester according to the present invention is a cellulose acetate having a hydroxyl group residual degree (DR) of 0.5 to 1.0, and the hydroxyl group residual degree (DR) is more preferably 0.5 to 0.8.
  • the substitution degree of cellulose ester is determined by using the degree of acetylation.
  • Degree of substitution degree of acetylation ⁇ 162 / (6006 ⁇ degree of acetylation ⁇ 42)
  • the average degree of acetylation of the cellulose ester represents the amount of bound acetic acid per unit mass of cellulose, and can be determined by calculation according to ASTM: D-817-96 (testing method for cellulose acetate, etc.).
  • the number average molecular weight (Mn) of the cellulose ester according to the present invention is preferably in the range of 30000 to 300000, since the mechanical strength of the resulting film is strong. Further, those having 50000-200000 are preferably used.
  • the ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose ester is preferably 1.4 to 3.0.
  • the weight average molecular weight Mw and number average molecular weight Mn of the cellulose ester were measured using gel permeation chromatography (GPC).
  • the measurement conditions are as follows.
  • the cellulose used as the raw material for the cellulose ester of the present invention is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively.
  • the cellulose ester according to the present invention can be produced by a known method. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.
  • the total amount (ppm) of calcium and magnesium and the amount of acetic acid (ppm) contained in the cellulose ester film according to the present invention preferably satisfy the following relational expression (3).
  • Relational expression (3) 1 ⁇ (acetic acid amount (ppm)) / (total amount of calcium and magnesium (ppm)) ⁇ 30 Calcium and magnesium are contained in the cellulose ester used as the raw material for the cellulose ester film, but metal oxides and metal hydroxides are used to neutralize and stabilize the acid catalyst (especially sulfuric acid) added to the cellulose ester production process. , And may be added as a metal salt (inorganic acid salt, organic acid salt). Moreover, you may add as a metal oxide, a metal hydroxide, and a metal salt (inorganic acid salt, organic acid salt) at the time of film forming of a cellulose ester film.
  • the total amount (ppm) of calcium and magnesium contained in the cellulose ester film referred to in the present invention refers to the total amount thereof.
  • acetic anhydride and acetic acid are used as reaction solvents and esterifying agents. Unreacted acetic anhydride is hydrolyzed by a reaction stopper (water, alcohol, acetic acid, etc.) to produce acetic acid.
  • a reaction stopper water, alcohol, acetic acid, etc.
  • the amount of acetic acid (ppm) contained in the cellulose ester film referred to in the present invention refers to the total amount of residual acetic acid and free acetic acid.
  • the total amount of calcium and magnesium (ppm) / acetic acid amount (ppm) is preferably 1 or more and 30 or less.
  • it indicates that the amount of acetic acid is small relative to the amount of calcium and magnesium, but light scattering due to calcium and magnesium metal salts occurs, which lowers the contrast, which is not preferable.
  • it is larger than 30, it indicates that the acetic acid is in an excessive amount with respect to the amounts of calcium and magnesium.
  • the cellulose ester is bonded to the polarizer, the deterioration of the polarizer is accelerated by acetic acid.
  • the total amount of calcium and magnesium contained in the cellulose ester film is preferably 5 to 130 ppm, more preferably 5 to 80 ppm, and still more preferably 5 to 50 ppm.
  • the amount of acetic acid contained in the cellulose ester film is preferably 20 to 500 ppm, more preferably 25 to 250 ppm, and still more preferably 30 to 150 ppm.
  • a known method can be used for the determination of calcium and magnesium contained in the cellulose ester film. For example, after the dried cellulose ester is completely burned, a pretreatment in which ash is dissolved in hydrochloric acid is performed. It can be measured by atomic absorption method. The measured value is obtained in units of ppm as the calcium and magnesium contents in 1 g of the completely dry cellulose ester.
  • acetic acid contained in the cellulose ester film For quantification of acetic acid contained in the cellulose ester film, a known method can be used. For example, the following method can be used. The film is dissolved in methylene chloride, and methanol is added to perform reprecipitation. The amount of acetic acid can be obtained by filtering the supernatant and measuring the supernatant with gas chromatography.
  • the cellulose ester film of the present invention preferably has an internal haze of 0.05 or less, more preferably 0.03 or less, and still more preferably 0.01 or less.
  • the internal haze is a haze generated by a scattering factor inside the film, and the internal is a portion of 5 ⁇ m or more from the film surface.
  • This internal haze is measured by a haze meter by dropping a solvent having a refractive index of ⁇ 0.05 on the film interface to make the haze on the film surface negligible as much as possible.
  • Haze meter (turbidity meter) (model: NDH 2000, manufactured by Nippon Denshoku Co., Ltd.)
  • the light source uses a 5V9W halogen bulb, and the light receiving unit uses a silicon photocell (with a relative visibility filter).
  • the present invention is characterized in that the value is 0.05 or less in the haze measurement of a film when a solvent having a refractive index of ⁇ 0.05 is dropped on the film with this apparatus.
  • the measurement was performed according to JIS K-7136.
  • the blank haze 1 of a measuring instrument other than a film is measured.
  • the haze 2 including the sample is measured by the following procedure. 4). Glycerol is dropped on the slide glass. (0.05ml) (See Fig. 1) 5. A sample film to be measured is placed thereon so that no air bubbles enter. (See Figure 2) 6). Glycerol is dropped on the sample film. (0.05ml) (See Fig. 3) 7). Place the cover glass on top of it. (See Figure 4) 8).
  • the cellulose ester film was prepared after being conditioned at 23 ° C. and 55% RH for 5 hours or more, and all the above haze measurements were performed at 23 ° C. and 55% RH.
  • the glass and glycerin used in the above measurement are as follows.
  • the hydrolysis inhibitor (A) according to the present invention is not particularly limited, but the octanol-water partition coefficient (logP (A)) is preferably 7 or more and less than 11. When logP (A) is smaller than 7, the hydrolysis-preventing effect is small, and when logP (A) is 11 or more, the compatibility with the cellulose ester is low and bleeding out is caused by wet heat, which is not preferable.
  • hydrolysis inhibitor (A) for example, a mixture of ester compounds in which at least one of the pyranose structure or furanose structure is 1 to 12 and a part of the OH group of the structure is esterified is preferably used. Can do.
  • the ratio of esterification of an ester compound in which at least one of the pyranose structure or furanose structure is 1 to 12 and all or part of the OH groups in the structure is esterified is present in the pyranose structure or furanose structure. It is preferable that it is 70% or more of the OH group.
  • ester compounds are collectively referred to as sugar ester compounds.
  • ester compound used in the present invention examples include the following, but the present invention is not limited to these.
  • Glucose galactose, mannose, fructose, xylose or arabinose, lactose, sucrose, nystose, 1F-fructosyl nystose, stachyose, maltitol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose or kestose .
  • gentiobiose gentiotriose
  • gentiotetraose gentiotetraose
  • xylotriose galactosyl sucrose
  • sucrose for example, sucrose, kestose, nystose, 1F-fructosyl nystose, stachyose and the like are preferable, and sucrose is more preferable.
  • the monocarboxylic acid used for esterifying all or part of the OH group in the pyranose structure or furanose structure is not particularly limited, and is a known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic A monocarboxylic acid or the like can be used.
  • the carboxylic acid used may be one type or a mixture of two or more types.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid , Saturated fatty acids such as tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, Examples include unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and oc
  • Examples of preferable alicyclic monocarboxylic acids include acetic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include aromatic monocarboxylic acids having an alkyl group or alkoxy group introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, cinnamic acid, benzylic acid, biphenylcarboxylic acid, and naphthalene.
  • aromatic monocarboxylic acids having two or more benzene rings such as carboxylic acid and tetralin carboxylic acid, or derivatives thereof.
  • Oligosaccharide ester compounds can be applied as compounds having 1 to 12 at least one of the pyranose structure or furanose structure according to the present invention.
  • Oligosaccharides are produced by allowing an enzyme such as amylase to act on starch, sucrose, etc.
  • examples of oligosaccharides that can be applied to the present invention include maltooligosaccharides, isomaltoligosaccharides, fructooligosaccharides, galactooligosaccharides, xylooligos. Sugar.
  • the said ester compound is a compound which condensed 1 or more and 12 or less of at least 1 sort (s) of the pyranose structure or furanose structure represented with the following general formula (A).
  • R 11 to R 15 and R 21 to R 25 each represents an acyl group having 2 to 22 carbon atoms or a hydrogen atom, m and n each represents an integer of 0 to 12, and m + n represents an integer of 1 to 12.
  • R 11 to R 15 and R 21 to R 25 are preferably a benzoyl group or a hydrogen atom.
  • the benzoyl group may further have a substituent R 26 , and examples thereof include an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group have a substituent. May be. Oligosaccharides can also be produced in the same manner as the ester compound according to the present invention.
  • ester compound according to the present invention will be given below, but the present invention is not limited thereto.
  • the cellulose ester film according to the present invention preferably contains 0.5 to 30% by mass of the hydrolysis inhibitor (A), particularly 2 to 15% by mass of the cellulose ester film.
  • the retardation adjusting agent (B) according to the present invention is not particularly limited, but a compound having an octanol-water partition coefficient (logP (B)) of 0 or more and less than 7 is preferable.
  • the phase difference adjusting agent needs to have an appropriate solubility corresponding to the resin, but in the cellulose ester according to the present invention, when logP (B) is less than 0, the compound has high water solubility, resulting in disordered orientation. Further, when logP (B) is 7 or more, a desired phase difference cannot be obtained because the orientation of the compound is low, which is not preferable.
  • phase difference adjusting agent (B) for example, an ester compound represented by the following general formula (1) can be preferably used.
  • B- (GA) n-GB (Wherein B is a hydroxy group or carboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms)
  • A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.
  • Examples of the carboxylic acid component of the ester compound represented by the general formula (1) include acetic acid, propionic acid, butyric acid, benzoic acid, p-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, and dimethylbenzoic acid , Ethyl benzoic acid, normal propyl benzoic acid, aminobenzoic acid, acetoxybenzoic acid, aliphatic acid and the like, and these can be used as one kind or a mixture of two or more kinds, respectively.
  • alkylene glycol component having 2 to 12 carbon atoms of the ester compound represented by the general formula (1) examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, , 3-butanediol, 1,2-propanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol ( Neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane) ), 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl 1,3-pentanedio And
  • alkylene glycols having 2 to 12 carbon atoms are particularly preferable because of excellent compatibility with cellulose esters.
  • Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the ester compound represented by the general formula (1) include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. Yes, these glycols can be used as one or a mixture of two or more.
  • alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the ester compound represented by the general formula (1) examples include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecane. There exist dicarboxylic acid etc., and these are each used as a 1 type, or 2 or more types of mixture.
  • Examples of the arylene dicarboxylic acid component having 6 to 12 carbon atoms include phthalic acid, terephthalic acid, isophthalic acid, 1,5 naphthalene dicarboxylic acid, and 1,4 naphthalene dicarboxylic acid.
  • the ester compound represented by the general formula (1) has a number average molecular weight of preferably 300 to 1500, more preferably 400 to 1000.
  • the acid value is 0.5 mgKOH / g or less, the hydroxyl value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl value is 15 mgKOH / g or less.
  • the cellulose ester film according to the present invention preferably contains the retardation adjusting agent (B) in an amount of 0.1 to 30% by mass, particularly 0.5 to 10% by mass of the cellulose ester film.
  • the cellulose ester film of the present invention contains a hydrolysis inhibitor (A) and preferably a retardation adjusting agent (B).
  • A hydrolysis inhibitor
  • B retardation adjusting agent
  • the cellulose ester film has a high temperature. When left for a long time in high humidity, there was a case where a slight bleedout of these additives and a slight increase in haze accompanying the bleedout were observed.
  • anionic surfactant functions as a dispersant for the additive and prevents the aggregation of the additive.
  • the cellulose-ester film of this invention contains a hydrolysis inhibiting agent (A) and a phase difference adjusting agent (B), it is preferable to satisfy
  • the anionic surfactant according to the present invention is not particularly limited.
  • Formula (I) [R1O (AO) n] pP ( O) (OM) q
  • Formula (II) R2-LQ R1 and R2 each represent a linear or branched alkyl group having 8 to 22 carbon atoms, and particularly preferably an alkyl group having 10 to 18 carbon atoms.
  • the alkyl group may have a substituent.
  • substituents include a halogen atom, an aryl group, a heterocyclic group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a hydroxyl group, and an acyloxy group.
  • A represents an alkylene group having 2 to 4 carbon atoms, and n is 0 or an integer of 1 to 20.
  • M represents a hydrogen atom, an alkali metal atom, or an ammonium group.
  • L represents a divalent linking group, and Q represents carboxylic acid or a salt thereof, sulfonic acid or a salt thereof, sulfate ester or a salt thereof.
  • RZ-5 ⁇ C 12 H 25 O (CH 2 CH 2 O) 5 ⁇ 2 -P ( O) -OH
  • the addition method is not particularly limited, it is preferably added to the cellulose acetate solution as it is as a liquid or solid, or as a solution dissolved in a solvent.
  • the cellulose ester film of the present invention can contain a plasticizer as necessary to obtain the effects of the present invention.
  • the plasticizer is not particularly limited, but is preferably a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer, a polyhydric alcohol ester plasticizer, or a polyester plasticizer. Agent, acrylic plasticizer and the like.
  • At least one is preferably a polyhydric alcohol ester plasticizer.
  • the polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
  • a divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
  • the polyhydric alcohol preferably used in the present invention is represented by the following general formula (a).
  • R1- (OH) n represents an n-valent organic group
  • n represents a positive integer of 2 or more
  • the OH group represents an alcoholic and / or phenolic hydroxyl group.
  • Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these.
  • triethylene glycol triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.
  • monocarboxylic acid used for polyhydric alcohol ester there is no restriction
  • Preferred examples of the monocarboxylic acid include the following, but the present invention is not limited to this.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used.
  • the number of carbon atoms is more preferably 1-20, and particularly preferably 1-10.
  • acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
  • Examples of preferable alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which 1 to 3 alkoxy groups such as alkyl group, methoxy group or ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.
  • the molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.
  • the carboxylic acid used in the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
  • the glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
  • alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl
  • phthalate ester plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
  • citrate plasticizer examples include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.
  • fatty acid ester plasticizers examples include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
  • phosphate ester plasticizer examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.
  • the polyvalent carboxylic acid ester compound is composed of an ester of a divalent or higher, preferably a divalent to 20valent polyvalent carboxylic acid and an alcohol.
  • the aliphatic polyvalent carboxylic acid is preferably divalent to 20-valent, and in the case of an aromatic polyvalent carboxylic acid or alicyclic polyvalent carboxylic acid, it is preferably trivalent to 20-valent.
  • the polyvalent carboxylic acid is represented by the following general formula (b).
  • R2 (COOH) m (OH) n
  • R2 is an (m + n) -valent organic group
  • m is a positive integer of 2 or more
  • n is an integer of 0 or more
  • a COOH group is a carboxyl group
  • an OH group is an alcoholic or phenolic hydroxyl group
  • preferred polyvalent carboxylic acids include the following, but the present invention is not limited to these.
  • Trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, tetrahydrophthal
  • An aliphatic polyvalent carboxylic acid such as an acid, an oxypolyvalent carboxylic acid such as tartaric acid, tartronic acid, malic acid and citric acid can be preferably used.
  • the alcohol used in the polyvalent carboxylic acid ester compound that can be used in the present invention is not particularly limited, and known alcohols and phenols can be used.
  • an aliphatic saturated alcohol or aliphatic unsaturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • alicyclic alcohols such as cyclopentanol and cyclohexanol or derivatives thereof
  • aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, or derivatives thereof can be preferably used.
  • the alcoholic or phenolic hydroxyl group of the oxypolycarboxylic acid may be esterified with a monocarboxylic acid.
  • monocarboxylic acids include the following, but the present invention is not limited thereto.
  • aliphatic monocarboxylic acid a straight-chain or side-chain fatty acid having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
  • Examples of preferable alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid.
  • benzoic acid and toluic acid examples include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid.
  • the aromatic monocarboxylic acid which has, or those derivatives can be mentioned.
  • Particularly preferred are acetic acid, propionic acid, and benzoic acid.
  • the molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750.
  • the larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.
  • the alcohol used for the polyvalent carboxylic acid ester that can be used in the present invention may be one kind or a mixture of two or more kinds.
  • the acid value of the polyvalent carboxylic acid ester compound that can be used in the present invention is preferably 1 mgKOH / g or less, and more preferably 0.2 mgKOH / g or less. Setting the acid value in the above range is preferable because the environmental fluctuation of the retardation is also suppressed.
  • the acid value refers to the number of milligrams of potassium hydroxide necessary to neutralize the acid (carboxyl group present in the sample) contained in 1 g of the sample.
  • the acid value is measured according to JIS K0070.
  • tributyl trimellitic acid and tetrabutyl pyromellitic acid.
  • the cellulose ester film of the present invention can also contain an ultraviolet absorber.
  • the ultraviolet absorber is intended to improve durability by absorbing ultraviolet light having a wavelength of 400 nm or less, and the transmittance at a wavelength of 370 nm is particularly preferably 10% or less, more preferably 5% or less. Preferably it is 2% or less.
  • the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.
  • the UV absorbers preferably used in the present invention are benzotriazole UV absorbers, benzophenone UV absorbers, and triazine UV absorbers, particularly preferably benzotriazole UV absorbers and benzophenone UV absorbers. .
  • a discotic compound such as a compound having a 1,3,5 triazine ring is also preferably used as an ultraviolet absorber.
  • the cellulose ester film of the present invention preferably contains two or more ultraviolet absorbers.
  • a polymeric ultraviolet absorber can be preferably used, and in particular, a polymer type ultraviolet absorber described in JP-A-6-148430 is preferably used.
  • the method of adding the UV absorber can be added to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane or a mixed solvent thereof. Or you may add directly in dope composition.
  • an alcohol such as methanol, ethanol or butanol
  • an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane or a mixed solvent thereof.
  • inorganic powders that do not dissolve in organic solvents use a dissolver or sand mill in the organic solvent and cellulose ester to disperse them before adding them to the dope.
  • the amount of the UV absorber used is not uniform depending on the type of UV absorber, the operating conditions, etc., but when the dry film thickness of the polarizing plate protective film is 30 to 200 ⁇ m, the amount used is 0.5 to the polarizing plate protective film. Is preferably 10 to 10% by mass, and more preferably 0.6 to 4% by mass.
  • Antioxidant are also referred to as deterioration inhibitors.
  • a liquid crystal image display device or the like is placed in a high humidity and high temperature state, the cellulose ester film may be deteriorated.
  • the antioxidant has a role of delaying or preventing the cellulose ester film from being decomposed by, for example, a residual solvent amount of halogen in the cellulose ester film or phosphoric acid of a phosphoric acid plasticizer. It is preferable to make it contain in a film.
  • a hindered phenol compound is preferably used.
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oct Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred.
  • hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
  • the amount of these compounds added is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the cellulose derivative.
  • Fine particles In order to impart slipperiness to the cellulose ester film of the present invention, it is preferable to add fine particles.
  • the primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm.
  • These fine particles preferably form secondary particles having a particle size of 0.1 to 5 ⁇ m and are contained in the retardation film, and the preferable average particle size is 0.1 to 2 ⁇ m, more preferably 0.2 to 0.6 ⁇ m.
  • irregularities having a height of about 0.1 to 1.0 ⁇ m are formed on the film surface, thereby providing appropriate slipperiness to the film surface.
  • the primary average particle diameter of the fine particles used in the present invention is measured by observing the particles with a transmission electron microscope (magnification of 500,000 to 2,000,000 times), observing 100 particles, measuring the particle diameter, and measuring the average. The value was taken as the primary average particle size.
  • the apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter.
  • a larger apparent specific gravity makes it possible to make a high-concentration dispersion, which improves haze and agglomerates, and is preferable when preparing a dope having a high solid content concentration as in the present invention.
  • the medialess disperser there are an ultrasonic type, a centrifugal type, a high pressure type, and the like.
  • a high pressure disperser is preferable.
  • the high pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube.
  • the maximum pressure condition inside the apparatus is preferably 9.807 MPa or more in a thin tube having a tube diameter of 1 to 2000 ⁇ m.
  • high-pressure dispersing apparatus examples include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other manton gorin type high-pressure dispersing apparatuses such as homogenizer manufactured by Izumi Food Machinery. And UHN-01 manufactured by Sanwa Machinery Co., Ltd.
  • ultra-high pressure homogenizer trade name: Microfluidizer
  • nanomizer manufactured by Nanomizer
  • UHN-01 manufactured by Sanwa Machinery Co., Ltd.
  • casting a dope containing fine particles so as to be in direct contact with the casting support is preferable because a film having high slip properties and low haze can be obtained.
  • a functional thin film such as a hard coat layer or an antireflection layer may be provided.
  • packaging is usually performed in order to protect the product from dirt, static electricity, and the like.
  • the packaging material is not particularly limited as long as the above purpose can be achieved, but preferably does not hinder volatilization of the residual solvent from the film.
  • Specific examples include polyethylene, polyester, polypropylene, nylon, polystyrene, paper, various non-woven fabrics, and the like.
  • a fiber having a mesh cloth shape is more preferably used.
  • the cellulose ester film of the present invention can be preferably used regardless of whether it is a film produced by a solution casting method or a film produced by a melt casting method.
  • the cellulose ester film of the present invention is prepared by dissolving a cellulose ester and an additive in a solvent to prepare a dope, and casting the dope onto an endless metal support that moves infinitely. It is performed by a step of drying the cast dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.
  • the concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become.
  • the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
  • the solvent used in the dope may be used alone or in combination of two or more, but it is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester in terms of production efficiency, and there are many good solvents. This is preferable from the viewpoint of the solubility of the cellulose ester.
  • a preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
  • the good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetoacetate. Particularly preferred is methylene chloride or methyl acetate.
  • the poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used.
  • the dope preferably contains 0.01 to 2% by mass of water.
  • the solvent used for dissolving the cellulose ester is used by collecting the solvent removed from the film by drying in the film-forming process and reusing it.
  • the recovery solvent may contain trace amounts of additives added to the cellulose ester, such as plasticizers, UV absorbers, polymers, monomer components, etc., but even if these are included, they are preferably reused. Can be purified and reused if necessary.
  • additives added to the cellulose ester such as plasticizers, UV absorbers, polymers, monomer components, etc., but even if these are included, they are preferably reused. Can be purified and reused if necessary.
  • a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure.
  • a method in which a cellulose ester is mixed with a poor solvent and wetted or swollen, and then a good solvent is added and dissolved is also preferably used.
  • Pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside.
  • a jacket type is preferable because temperature control is easy.
  • the heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates.
  • the preferred heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C.
  • the pressure is adjusted so that the solvent does not boil at the set temperature.
  • a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.
  • the cellulose ester solution is filtered using an appropriate filter medium such as filter paper.
  • an appropriate filter medium such as filter paper.
  • the filter medium it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but there is a problem that the filter medium is likely to be clogged if the absolute filtration accuracy is too small.
  • a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.
  • the material of the filter medium there are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable.
  • Bright spot foreign matter means that when two polarizing plates are placed in a crossed Nicol state, an optical film or the like is placed between them, light is applied from one polarizing plate side, and observation is performed from the other polarizing plate side. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm 2 or less.
  • it is 100 pieces / cm 2 or less, still more preferably 50 pieces / m 2 or less, still more preferably 0 to 10 pieces / cm 2 . Further, it is preferable that the number of bright spots of 0.01 mm or less is small.
  • the dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration.
  • the increase in the difference (referred to as differential pressure) is small and preferable.
  • the preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.
  • the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be 1 ⁇ 4m.
  • the surface temperature of the metal support in the casting step is ⁇ 50 ° C. to less than the boiling point of the solvent, and a higher temperature is preferable because the web drying speed can be increased. May deteriorate.
  • the preferred support temperature is 0 to 55 ° C, more preferably 25 to 50 ° C.
  • the method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When warm air is used, wind at a temperature higher than the target temperature may be used.
  • the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Particularly preferred is 20 to 30% by mass or 70 to 120% by mass.
  • the amount of residual solvent is defined by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
  • the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Particularly preferred is 0 to 0.01% by mass or less.
  • a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method in which the web is dried while being conveyed by a tenter method are employed.
  • the cellulose ester film of the present invention it is particularly preferable to perform stretching in the width direction (lateral direction) by a tenter method in which both ends of the web are held with clips or the like. Peeling is preferably performed at a peeling tension of 300 N / m or less.
  • the means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but is preferably performed with hot air in terms of simplicity.
  • drying temperature in the web drying process is increased stepwise from 40 to 200 ° C.
  • the film thickness of the cellulose ester film is not particularly limited, but 10 to 200 ⁇ m is used.
  • the film thickness is particularly preferably 10 to 100 ⁇ m. More preferably, it is 20 to 60 ⁇ m.
  • the cellulose ester film of the present invention is formed with a width of 1 to 4 m, particularly preferably 1.4 to 4 m, and particularly preferably 1.6 to 3 m. If it exceeds 4 m, conveyance becomes difficult.
  • the cellulose ester film has the configuration of the present invention, and the refractive index is controlled by controlling the transport tension and stretching.
  • the retardation value can be changed by lowering or increasing the tension in the longitudinal direction.
  • biaxial stretching or uniaxial stretching sequentially or simultaneously with respect to the longitudinal direction (film forming direction) of the film and the direction orthogonal to the longitudinal direction of the film, that is, the width direction.
  • the draw ratios in the biaxial directions perpendicular to each other are preferably in the range of 0.8 to 1.5 times in the casting direction and 1.1 to 2.5 times in the width direction, respectively. It is preferable to carry out in the range of 0.8 to 1.0 times in the direction and 1.2 to 2.0 times in the width direction.
  • the stretching temperature is preferably 120 ° C. to 200 ° C., more preferably 150 ° C. to 200 ° C., more preferably more than 150 ° C. and 190 ° C. or less.
  • the residual solvent in the film is preferably 20 to 0%, more preferably 15 to 0%.
  • the residual solvent is stretched by 11% at 155 ° C., or the residual solvent is stretched by 2% at 155 ° C. Alternatively, it is preferable that the residual solvent is stretched at 11% at 160 ° C, or the residual solvent is stretched at less than 1% at 160 ° C.
  • the method of stretching the web For example, a method in which a circumferential speed difference is applied to a plurality of rolls, and the roll circumferential speed difference is used to stretch the rolls in the vertical direction. Both ends of the web are fixed with clips and pins, and the interval between the clips and pins is increased in the traveling direction And a method of stretching in the vertical direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions, and the like. Of course, these methods may be used in combination.
  • a tenter it may be a pin tenter or a clip tenter.
  • the slow axis or the fast axis of the cellulose ester film of the present invention exists in the film plane, and ⁇ 1 is preferably ⁇ 1 ° or more and + 1 ° or less, assuming that the angle formed with the film forming direction is ⁇ 1. It is more preferably from 5 ° to + 0.5 °, and further preferably from ⁇ 0.1 ° to + 0.1 °.
  • This ⁇ 1 can be defined as an orientation angle, and ⁇ 1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
  • KOBRA-21ADH Oji Scientific Instruments
  • the moisture permeability of the cellulose ester film of the present invention is preferably 300 to 1800 g / m 2 ⁇ 24 h at 40 ° C. and 90% RH, more preferably 400 to 1500 g / m 2 ⁇ 24 h, and 40 to 1300 g / m 2 ⁇ 24 h. Particularly preferred.
  • the moisture permeability can be measured according to the method described in JIS Z 0208.
  • the breaking elongation of the cellulose ester film of the present invention is preferably 5 to 80%, more preferably 10 to 50%.
  • the visible light transmittance of the cellulose ester film of the present invention is preferably 90% or more, and more preferably 93% or more.
  • the haze of the cellulose ester film of the present invention is preferably less than 1%, particularly preferably 0 to 0.1%.
  • the in-plane retardation value (Ro) and the retardation value (Rt) in the thickness direction of the cellulose ester film of the present invention are preferably 0 ⁇ Ro and Rt ⁇ 70 nm when used as a polarizer protective film. More preferably, 0 ⁇ Ro ⁇ 30 nm and 0 ⁇ Rt ⁇ 50 nm, and more preferably 0 ⁇ Ro ⁇ 10 nm and 0 ⁇ Rt ⁇ 30 nm.
  • the cellulose ester film of the present invention is preferably used as a retardation film, in which case 30 ⁇ Ro ⁇ 100 nm and 70 ⁇ Rt ⁇ 400 nm, more preferably 35 ⁇ Ro ⁇ 65 nm and 90 ⁇ Rt ⁇ 180 nm. is there. Further, the variation of Rt and the width of the distribution are preferably less than ⁇ 50%, preferably less than ⁇ 30%, and preferably less than ⁇ 20%. Further, it is preferably less than ⁇ 15%, preferably less than ⁇ 10%, preferably less than ⁇ 5%, particularly preferably less than ⁇ 1%. Most preferably, there is no variation in Rt.
  • the retardation values Ro and Rt can be obtained by the following equations.
  • d is the thickness (nm) of the film
  • the refractive index nx also referred to as the maximum refractive index in the plane of the film, the refractive index in the slow axis direction
  • ny in the direction perpendicular to the slow axis in the film plane.
  • Retardation values (Ro) and (Rt) can be measured using an automatic birefringence meter. For example, it can be obtained at a wavelength of 590 nm under an environment of 23 ° C. and 55% RH using KOBRA-21ADH (Oji Scientific Instruments).
  • the cellulose ester film of the present invention can be subjected to a surface activation treatment.
  • the surface activation treatment is an alkali saponification treatment, a corona discharge treatment, a flame treatment on the side of the cellulose ester film on which at least a polarizer is present.
  • UV treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, ozone oxidation treatment and the like are performed.
  • the surface free energy of this cellulose-ester film can be raised, and the contact angle to a pure water can be lowered
  • a method for adjusting the surface free energy a method of coating a hydrophilic layer on the side where the polarizer is present can be raised.
  • an alkali saponification treatment is preferable because the surface free energy can be easily controlled.
  • the alkali saponification treatment is preferably performed using sodium hydroxide or potassium hydroxide solution.
  • ⁇ Contact angle> As a method for measuring the contact angle, for example, in a clean room using pure water as a liquid for contact angle measurement and adjusted to 23 ° C. and 55% RH, a drop of pure water is placed on the surface of the film to be measured from a syringe and contacted. Using an angle measuring instrument (manufactured by FIBLO), the angle 3 seconds after dropping can be measured to obtain the contact angle.
  • FIBLO angle measuring instrument
  • the cellulose ester film of the present invention can be used for a polarizing plate as a polarizing plate protective film and for a liquid crystal display device using the polarizing plate.
  • the polarizing plate of the present invention is preferably a polarizing plate bonded to at least one surface of a polarizer using the cellulose ester film of the present invention as a polarizing plate protective film.
  • the polarizing plate of the present invention is bonded to at least one liquid crystal cell surface via an adhesive layer.
  • the polarizing plate of the present invention can be produced by a general method.
  • the cellulose ester film of the present invention is preferably bonded to at least one surface of a polarizer prepared by subjecting the polarizer side to alkali saponification treatment and immersion drawing in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution.
  • cellulose ester films for example, Konica Minoltack KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC8UX-RHA, KC8UX-RHA, KC8UX KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.
  • cellulose ester films for example, Konica Minoltack KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC8UX-RHA, KC8UX-RHA, KC8UX KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.
  • the polarizing plate protective film used on the surface side of the liquid crystal display device preferably has an antireflection layer, an antistatic layer, an antifouling layer, and a backcoat layer.
  • a polarizer which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass.
  • a typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol.
  • iodine is dyed on a system film and one in which dichroic dye is dyed.
  • the polarizer is formed by forming a polyvinyl alcohol aqueous solution into a film and dyeing the film by uniaxial stretching or dyeing or uniaxially stretching, and then performing a durability treatment with a boron compound.
  • the film thickness of the polarizer is preferably 5 to 30 ⁇ m, particularly preferably 10 to 20 ⁇ m.
  • the ethylene unit content described in JP-A-2003-248123, JP-A-2003-342322, etc. is 1 to 4 mol%
  • the degree of polymerization is 2000 to 4000
  • the degree of saponification is 99.0 to 99.99 mol%.
  • Ethylene-modified polyvinyl alcohol is also preferably used.
  • an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 66 to 73 ° C. is preferably used.
  • a polarizer using this ethylene-modified polyvinyl alcohol film is excellent in polarization performance and durability performance and has few color spots, and is particularly preferably used for a large liquid crystal display device.
  • the polarizer obtained as described above is usually used as a polarizing plate with a protective film bonded to both sides or one side.
  • the adhesive used for pasting include a PVA-based adhesive and a urethane-based adhesive. Among them, a PVA-based adhesive is preferably used.
  • the cellulose ester film and polarizing plate of the present invention can be used for liquid crystal display devices of various driving systems such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB and the like.
  • a VA (MVA, PVA) type liquid crystal display device is preferable.
  • liquid crystal display device with a 30-inch screen or more can obtain a liquid crystal display device with excellent visibility such as uneven coloring and front contrast with little environmental fluctuation, reduced light leakage.
  • Example 1 Preparation of cellulose ester CE-1> To 100 parts by mass of cellulose, 16 parts by mass of sulfuric acid, 260 parts by mass of acetic anhydride and 420 parts by mass of acetic acid were added, and the temperature was raised from room temperature to 60 ° C. over 60 minutes while stirring, and the temperature was maintained for 15 minutes. An acetylation reaction was performed. Next, a mixed solution of magnesium acetate and calcium acetate in acetic acid-water was added to neutralize the sulfuric acid, and then steam was introduced into the reaction system and maintained at 60 ° C. for 120 minutes for saponification aging treatment. Thereafter, it was washed with a large amount of water and further dried to obtain cellulose ester CE-1.
  • the residual hydroxyl group (DR), calcium content, magnesium content, acetic acid content, and molecular weight were determined according to the methods described above.
  • ⁇ Creation of cellulose esters CE-2 to CE-18> The cellulose ester was similarly modified except that the production conditions of the cellulose ester CE-1 were appropriately changed so that the hydroxyl group residual degree (DR), calcium amount, magnesium amount and acetic acid amount of the cellulose ester were changed as shown in Table 1.
  • DR hydroxyl group residual degree
  • CE-2 to CE-18 were produced.
  • ⁇ Fine particle additive solution Cellulose ester CE-1 was added to a dissolution tank containing methylene chloride and heated to completely dissolve, and this was then added to Azumi filter paper No. 3 manufactured by Azumi Filter Paper Co., Ltd. Filtered using 244. The fine particle dispersion was slowly added thereto while sufficiently stirring the filtered cellulose ester solution. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.
  • Methylene chloride 99 parts by weight Cellulose ester CE-1 4 parts by weight Fine particle dispersion 11 parts by weight Cellulose ester CE-1 was used to prepare a main dope liquid having the following composition.
  • a cellulose ester film 101 of the present invention having a film thickness of 40 ⁇ m having a width of 1.5 m, a knurling having a width of 1 cm at the end and a height of 8 ⁇ m was produced.
  • TPP Triphenyl phosphate BDP: Biphenyl diphenyl phosphate PETB: Pentaerythritol tetrabenzoate EPEG: Ethyl phthalyl ethyl glycolate
  • d is the film thickness (nm), the refractive index nx (the refractive index in the slow axis direction), ny (the refractive index in the direction perpendicular to the slow axis in the film plane), nz (the film thickness in the thickness direction). Refractive index).
  • Retardation values (Ro) and (Rt) were determined using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) at 23 ° C. and 55% RH at a wavelength of 590 nm.
  • the blank haze 1 of a measuring instrument other than a film is measured.
  • the haze 2 including the sample is measured by the following procedure. 4). Glycerol is dropped on the slide glass. (0.05ml) (See Fig. 1) 5. A sample film to be measured is placed thereon so that no air bubbles enter. (See Figure 2) 6). Glycerol is dropped on the sample film. (0.05ml) (See Fig. 3) 7). Place the cover glass on top of it. (See Figure 4) 8).
  • the glass and glycerin used in the above measurement are as follows.
  • Haze value fluctuation is less than 10%
  • the prepared cellulose ester film was conditioned for 5 hours or more in an environment of 23 ° C. and 55% RH and 50 ° C. and 20% RH, and then the ratio of the retardation value (Rt) measured in the same environment was taken to obtain the retardation value. Variation was evaluated.
  • Phase difference fluctuation is less than 5%
  • Phase difference fluctuation is 5% or more and less than 15%
  • Phase difference fluctuation is 15% or more and less than 24%
  • Phase difference fluctuation is 25% or more
  • a polyvinyl alcohol film having a thickness of 120 ⁇ m was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizer.
  • a polarizer, the cellulose ester films 101 to 137, and Konica Minolta Op KC8UY manufactured by Konica Minolta Opto Co., Ltd. were bonded as a polarizing plate protective film on the back surface side to produce a polarizing plate.
  • Step 1 Cellulose ester films 101 to 137 were immersed in a 2 mol / l potassium hydroxide solution at 50 ° C. for 30 seconds, then washed with water and dried to obtain a cellulose ester film having a saponified surface.
  • Step 2 The polarizer was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
  • Step 3 Excess adhesive adhered to the polarizer in Step 2 was lightly wiped off, and this was placed on the cellulose ester film treated in Step 1, and further placed on the back side cellulose ester film.
  • Step 4 The cellulose ester films 101 to 137 laminated in Step 3 were bonded together with the polarizer and the back side cellulose ester film at a pressure of 20 to 30 N / cm 2 and a conveying speed of about 2 m / min.
  • Step 5 A sample obtained by bonding the polarizer prepared in Step 4 with the cellulose ester films 101 to 137 and the back side cellulose ester film in a drier at 80 ° C. was dried for 2 minutes to prepare a polarizing plate.
  • the cellulose ester film of the present invention has a sufficient retardation value, low internal haze, excellent retardation value fluctuation, haze fluctuation, bleed-out performance, and polarization of the present invention. It is clear that the plate is also excellent in uneven polarization.
  • a liquid crystal panel for viewing angle measurement was produced as follows, and the characteristics as a liquid crystal display device were evaluated.
  • each of the liquid crystal display devices was manufactured by performing the absorption axis in the same direction as the polarizing plate bonded in advance.
  • Example 2 ⁇ Production of Cellulose Ester Films 105A to 107A, 106B, 133A to 136A> (Preparation of cellulose ester film 105A)
  • a cellulose ester film 105A was produced in the same manner except that the main dope solution was changed to the following main dope solution A.
  • the cellulose ester film 106A was prepared in the same manner as the production of the cellulose ester film 105A, except that the main dope solution was adjusted by adding an anionic surfactant shown in Table 5.
  • -107A, 106B, 133A-136A were produced.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur un film d'ester de cellulose qui a une résistance à l'eau et une aptitude à protéger un polariseur extrêmement améliorées, sur une plaque polarisante utilisant le film d'ester de cellulose et sur un dispositif d'affichage à cristaux liquides. Le film d'ester de cellulose est caractérisé en ce qu'il contient un acétate de cellulose ayant un degré de groupes hydroxy restants (DR) de 0,5-1,0, un inhibiteur d'hydrolyse (A) et un agent d'ajustemnt du retard (B) et en ce qu'il satisfait aux relations (1) et (2) suivantes. Relation (1) : 4 < logP(A)) - (logP(B)) < 12 (Dans la formule, logP(A) et logP(B) représentent respectivement les coefficients de distribution octanol-eau de l'inhibiteur d'hydrolyse (A) et de l'agent d'ajustement du retard (B).) Relation (2) : 2,5 < (W(A)/W(B)) × (1/DR) < 8,5 (Dans la formule, W(A) et W(B) représentent respectivement les masses de l'inhibiteur d'hydrolyse (A) et de l'agent d'ajustement du retard (B) contenues dans le film d'ester de cellulose et DR représente le degré de groupes hydroxy restants de l'acétate de cellulose.)
PCT/JP2010/050693 2009-06-30 2010-01-21 Film d'ester de cellulose, plaque polarisante l'utilisant et dispositif d'affichage à cristaux liquides Ceased WO2011001700A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2009-154864 2009-06-30
JP2009154864 2009-06-30
JP2009210202 2009-09-11
JP2009-210202 2009-09-11

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011227274A (ja) * 2010-04-20 2011-11-10 Konica Minolta Opto Inc 偏光板
JP2011242433A (ja) * 2010-05-14 2011-12-01 Konica Minolta Opto Inc 位相差フィルム、位相差フィルムの製造方法及びそれを用いた偏光板、液晶表示装置
JP2012002981A (ja) * 2010-06-16 2012-01-05 Konica Minolta Opto Inc 偏光板、液晶表示装置及びセルロースアセテートフィルムの製造方法
JPWO2013038829A1 (ja) * 2011-09-13 2015-03-26 コニカミノルタ株式会社 偏光板及び液晶表示装置
WO2015137367A1 (fr) * 2014-03-11 2015-09-17 コニカミノルタ株式会社 Corps de rouleau de film optique et son procédé de fabrication, plaque polarisante, et dispositif d'affichage à cristaux liquides
WO2015166971A1 (fr) * 2014-05-02 2015-11-05 コニカミノルタ株式会社 Rouleau de film à différence de phase, son procédé de fabrication, polariseur et dispositif d'affichage à cristaux liquides

Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2007326265A (ja) * 2006-06-07 2007-12-20 Konica Minolta Opto Inc 光学フィルム及びその製造方法、偏光板、液晶表示装置
WO2008136266A1 (fr) * 2007-04-26 2008-11-13 Konica Minolta Opto, Inc. Film de compensation optique, plaque de déviation utilisant celui-ci et dispositif d'affichage à cristaux liquides
WO2009004998A1 (fr) * 2007-07-05 2009-01-08 Konica Minolta Opto, Inc. Plaque de polarisation et affichage à cristaux liquides
JP2009001696A (ja) * 2007-06-22 2009-01-08 Konica Minolta Opto Inc セルロースエステルフィルム、それを用いた偏光板及び液晶表示装置

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2007326265A (ja) * 2006-06-07 2007-12-20 Konica Minolta Opto Inc 光学フィルム及びその製造方法、偏光板、液晶表示装置
WO2008136266A1 (fr) * 2007-04-26 2008-11-13 Konica Minolta Opto, Inc. Film de compensation optique, plaque de déviation utilisant celui-ci et dispositif d'affichage à cristaux liquides
JP2009001696A (ja) * 2007-06-22 2009-01-08 Konica Minolta Opto Inc セルロースエステルフィルム、それを用いた偏光板及び液晶表示装置
WO2009004998A1 (fr) * 2007-07-05 2009-01-08 Konica Minolta Opto, Inc. Plaque de polarisation et affichage à cristaux liquides

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011227274A (ja) * 2010-04-20 2011-11-10 Konica Minolta Opto Inc 偏光板
JP2011242433A (ja) * 2010-05-14 2011-12-01 Konica Minolta Opto Inc 位相差フィルム、位相差フィルムの製造方法及びそれを用いた偏光板、液晶表示装置
JP2012002981A (ja) * 2010-06-16 2012-01-05 Konica Minolta Opto Inc 偏光板、液晶表示装置及びセルロースアセテートフィルムの製造方法
JPWO2013038829A1 (ja) * 2011-09-13 2015-03-26 コニカミノルタ株式会社 偏光板及び液晶表示装置
WO2015137367A1 (fr) * 2014-03-11 2015-09-17 コニカミノルタ株式会社 Corps de rouleau de film optique et son procédé de fabrication, plaque polarisante, et dispositif d'affichage à cristaux liquides
CN106068299A (zh) * 2014-03-11 2016-11-02 柯尼卡美能达株式会社 光学膜的卷体及其制造方法、偏振片和液晶显示装置
WO2015166971A1 (fr) * 2014-05-02 2015-11-05 コニカミノルタ株式会社 Rouleau de film à différence de phase, son procédé de fabrication, polariseur et dispositif d'affichage à cristaux liquides

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