WO2015098546A1 - バーティカルアライメント用位相差フィルム - Google Patents

バーティカルアライメント用位相差フィルム Download PDF

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WO2015098546A1
WO2015098546A1 PCT/JP2014/082847 JP2014082847W WO2015098546A1 WO 2015098546 A1 WO2015098546 A1 WO 2015098546A1 JP 2014082847 W JP2014082847 W JP 2014082847W WO 2015098546 A1 WO2015098546 A1 WO 2015098546A1
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Prior art keywords
acid
retardation film
retardation
group
ring
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PCT/JP2014/082847
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English (en)
French (fr)
Japanese (ja)
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佐々木　謙一
由紀 金子
崇 南條
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コニカミノルタ株式会社
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    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis
    • 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
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/01—Number of plates being 1

Definitions

  • the present invention relates to a retardation film for vertical alignment.
  • LCDs liquid crystal display devices
  • various optical films such as a polarizing film and a retardation film are used.
  • the demand for LCDs is increasing, and there is a demand for thinner, lighter, and more productive polarizing plates that are used in line with this demand.
  • it is required to reduce the thickness and area of polarizing plate protective films and retardation films as members.
  • 4K has been developed that has both a large screen and a high-definition image.
  • CCFLs cold cathode fluorescent lamps
  • CCFLs cold cathode fluorescent lamps
  • They contain mercury, have poor temperature characteristics, high power consumption, and high-speed flashing.
  • drawbacks such as inability to do so, and in order to solve these problems, the use of backlights as LEDs has been studied.
  • the white LED has a configuration in which a yellow phosphor is mixed with a blue LED, and a configuration in which a green phosphor and a red phosphor are combined in a blue LED, and pseudo white reproduction is performed.
  • the power consumption can be suppressed by using the LED as the backlight, and high contrast can be achieved in the initial stage.
  • color tone fluctuation is a big problem.
  • the screen is enlarged, variations in brightness and color occur in various parts of the screen.
  • the life of the phosphor in the backlight under high temperature and high humidity is shortened due to the influence of the thinning of the member, and the result affects the screen (Patent Document 1).
  • the retardation film used in the liquid crystal display device as described above may contain a retardation increasing agent in order to enlarge the viewing angle.
  • a retardation increasing agent containing a nitrogen-containing heterocycle also has high retardation and can maintain a viewing angle even if the member is thinned (Patent Document 2).
  • the above-described retardation increasing agent has a problem of low stability and decomposition when stored in a high temperature and high humidity environment for a long time, and the retardation of the retardation film decreases. As a result, color unevenness on the screen occurs in various places. In particular, it has been found that variations in brightness and color of the screen become noticeable when the screen is enlarged and the definition is increased.
  • a cellulose acetate film having a low retardation and a high degree of retardation is used, but a cellulose acetate film having a low degree of substitution is generally used.
  • a method of adding a sugar ester compound as a hydrolysis adjusting agent or a phase difference controlling agent to a cellulose acetate film has been disclosed (for example, see Patent Document 3).
  • the present invention is to provide a retardation film capable of improving screen unevenness in a high temperature and high humidity environment.
  • the present invention contains cellulose acylate having a total acyl group substitution degree in the range of 2.80 to 2.95, a disaccharide or a trisaccharide, and a retardation increasing agent.
  • the conceptual diagram which shows an example of a structure of the vertical alignment type
  • the conceptual diagram which shows an example of a structure of a liquid vertical alignment type (vertical alignment type) liquid crystal display device.
  • X to Y indicating a range means “X or more and Y or less”, “weight” and “mass”, “weight%” and “mass%”, “part by weight” and “weight part”. “Part by mass” is treated as a synonym. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%. Moreover, the ratio of drawing may be exaggerated for description.
  • the present invention includes (1) cellulose acylate having a total acyl group substitution degree in the range of 2.80 to 2.95, (2) a disaccharide or a trisaccharide, and (3) a retardation increasing agent. And the hue Y. in a 55% by weight methylene chloride solution of the disaccharide or trisaccharide.
  • the present invention it is possible to provide a retardation film that can improve screen unevenness in a high temperature and high humidity environment.
  • the mechanism capable of providing a retardation film capable of improving screen unevenness under a high temperature and high humidity environment is as follows. That is, as described above, the white LED performs pseudo white reproduction with a configuration in which a “yellow phosphor” is mixed with a blue LED or a configuration in which a “green phosphor and a red phosphor” are combined with a blue LED. ing.
  • LEDs light emitting diodes
  • the lifetime of the phosphors in the backlight (yellow phosphor, green phosphor and red phosphor) is shortened, As a result, it is considered that the color tone fluctuates and affects the screen.
  • the disaccharide or trisaccharide as the yellow colored sugar functions in the direction in which the yellow phosphor or the green phosphor / red phosphor disappears, and the Screen unevenness in a wet environment can be improved.
  • the combination of “green phosphor / red phosphor” may also be simply expressed as “yellow phosphor”.
  • the in-plane retardation value at a wavelength of 589 nm in the retardation film for vertical alignment of the present invention is 30 to 130 nm, and the thickness direction retardation value is 70 to 300 nm. If a retardation film that deviates from these ranges is used, the retardation of the liquid crystal cannot be eliminated, and the visibility deteriorates. As a result, the color shift appears remarkably.
  • the in-plane retardation value at a wavelength of 589 nm in the retardation film for vertical alignment of the present invention is preferably 30 to 110 nm, more preferably 30 to 90 nm from the viewpoint of viewing angle compensation. Further, the thickness direction retardation value is preferably 70 to 280 nm, more preferably 70 to 260 nm from the viewpoint of viewing angle compensation.
  • the cellulose acylate of the present invention has a total acyl group substitution degree in the range of 2.80 to 2.95.
  • the total acyl group substitution degree represents the total of the ratio of esterification at the 2-position, 3-position and 6-position of the repeating unit of cellulose. Therefore, when all of the 2nd, 3rd and 6th positions of cellulose are 100% esterified, the degree of substitution is 3 at the maximum.
  • the total substitution degree of acyl group deviates from the range of 2.80 to 2.95, the compatibility with the sugar ester compound is poor and the color shift is remarkably exhibited.
  • the total acyl group substitution degree can be measured in accordance with ASTM D-817-96.
  • a preferable total acyl group substitution degree is in the range of 2.86 to 2.92. With such a range, the color shift resistance can be further improved.
  • the weight average molecular weight (Mw) of the cellulose acylate of the present invention is preferably in the range of 30000-350,000 from the viewpoint of film forming suitability during casting and the mechanical strength of the resulting film. Further, those within the range of 150,000 to 320,000 are preferably used.
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) of the cellulose acylate of the present invention can be measured using gel permeation chromatography (GPC).
  • the cellulose used as a raw material for the cellulose acylate used in the present invention is not particularly limited, and examples thereof include cotton linter, wood pulp (derived from coniferous tree, derived from broadleaf tree), kenaf and the like. Moreover, the cellulose acylate obtained from them can be mixed and used in arbitrary ratios, respectively.
  • Examples of the acyl group in the cellulose acylate used in the present invention include an acetyl group, a propionyl group, a butyryl group, a pentanate group, and a hexanate group.
  • Examples of the cellulose ester include cellulose acetate, cellulose propionate, and cellulose. Examples include butyrate and cellulose pentanate.
  • the cellulose acylate of the present invention for example, at least selected from cellulose (tri) acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose phthalate
  • cellulose esters include cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate.
  • the cellulose acylate according to the present invention can be produced by a known method. Specifically, it can be synthesized with reference to the methods described in JP-A-10-45804, JP-A-2005-281645, JP-A-2009-161701, and the like.
  • the retardation film of the present invention contains disaccharide or trisaccharide.
  • yellow compounds other than sugar ester compounds are decomposed in a high temperature and high humidity environment, resulting in a large yellow taste and excessively eliminating the disappearance of the yellow phosphor in the backlight.
  • hue Y. I If the material having a value of less than 5 is used, the yellowness is insufficient and the disappearance of the yellow phosphor in the backlight cannot be eliminated. On the other hand, hue Y. I. When the material having a value exceeding 35 is used, the yellowish color becomes excessive and the color shift resistance is deteriorated.
  • a disaccharide or trisaccharide is used, and the hue Y.M. I.
  • a material having a value in the range of 5 to 35 when stored for a long period of time in a high temperature and high humidity environment, the rate of change in hue after storage from the initial stage of manufacture is extremely small, resulting in variations in color tone. Stability and image unevenness resistance can be remarkably improved.
  • the hue Y. in a 55% by mass methylene chloride solution is used. I. Is within the range of 5 to 35, there is no particular limitation.
  • the disaccharide or trisaccharide used in the present invention is preferably a structure having at least one of a pyranose structure or a furanose structure, for example, lactose, nigerotriose, sucrose, gentiotriose, lactulose, melezitose.
  • Gentiobiose cellobiose, xylotriose, galactosyl sucrose, maltose, cellotriose, maltotriose, maltotrirose, theandellose, raffinose or kestose or structural isomers thereof.
  • the disaccharide or trisaccharide used in the present invention is preferably a sugar ester compound obtained by esterifying a part of the OH group of the structure.
  • a sugar ester compound having at least one of a pyranose structure or a furanose structure is preferable.
  • the same thing as the above can be used for the specific example of the disaccharide or trisaccharide which comprises the sugar ester compound.
  • the monocarboxylic acid used for esterifying a part of the OH group is not particularly limited, and a known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, or the like is used. Can do.
  • the carboxylic acid used may be one kind or a mixture of two or more kinds.
  • Preferred aliphatic monocarboxylic acids include, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecyl acid, Saturation of lauric acid, 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, mellicic acid, and laxaric acid
  • unsaturated fatty acids such as fatty acids, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid
  • 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 tetralincarboxylic acid, or derivatives thereof.
  • 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 total mass of the disaccharide or trisaccharide is in the range of 1 to 30% by mass with respect to 100 parts by mass of the cellulose acylate. A color shift can be significantly suppressed by the content in such a range.
  • a sugar ester compound having a total average substitution degree exceeding 6.00 is used as the disaccharide or trisaccharide.
  • the total average substitution degree exceeds 6.00 the compatibility with the cellulose acylate is improved, and the color shift resistance is improved.
  • the disaccharide is preferably 6.5 to 7.8, more preferably 6.8 to 7.4.
  • the trisaccharide is preferably 7 to 11, more preferably 8 to 10.
  • the total average degree of substitution means a substituent other than a hydrogen atom among the eight hydroxy groups of the disaccharide (for example, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group).
  • a number including a group other than a hydrogen atom among R 1 to R 8 is represented. Therefore, in the general formula (1), when all of R 1 to R 8 are substituted with a substituent other than a hydrogen atom, the degree of substitution in the general formula (1) is 8.0, which is the maximum value.
  • the disaccharide or trisaccharide of the present invention it is difficult to synthesize a single type of compound in which the number of hydroxy groups and the number of OR groups are fixed, and the number of hydroxy groups and OR groups in the formula are different. Since it is known that the compound becomes a compound in which several kinds of components are mixed, it is appropriate to use the total average substitution degree as the substitution degree, and the area ratio of the chart showing the substitution degree distribution by high performance liquid chromatography by a conventional method The total average substitution degree can be measured.
  • the specific structures of the disaccharides and trisaccharides of the present invention are not particularly limited, but those having the following structures are preferred from the viewpoint of industrial suitability.
  • R 1 to R 30 are each independently a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group.
  • the alkylcarbonyl group is preferably a carbonyl group having an alkyl group having 1 to 10 carbon atoms, more preferably a carbonyl group having an alkyl group having 1 to 5 carbon atoms.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic.
  • the arylcarbonyl group is preferably a carbonyl group having a phenyl group or a naphthyl group.
  • the substituent in the alkylcarbonyl group and the arylcarbonyl group is not particularly limited, and the alkylcarbonyl group is preferably a substituent such as an aryl group having 6 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
  • the arylcarbonyl group is preferably a substituent such as an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
  • the specific examples of the alkyl group having 1 to 5 carbon atoms are equally applicable, and the specific examples of the alkoxy group having 1 to 5 carbon atoms are also the same.
  • the number of substituents is not particularly limited, but about 1 to 4 is preferable.
  • R represents R 1 to R 30 in the general formula (1), the general formula (2), and the general formula (3).
  • the inside of the Kolben was depressurized to 4 ⁇ 10 2 Pa or less, and after excess pyridine was distilled off at 60 ° C., the inside of the Kolben was depressurized to 1.3 ⁇ 10 Pa or less and the temperature was raised to 120 ° C. Most of the acid and benzoic acid formed were distilled off. Finally, 100 g of water was added to the collected toluene layer, and after washing with water at room temperature for 30 minutes, the toluene layer was collected, and toluene was distilled off at 75 ° C. under reduced pressure (4 ⁇ 10 2 Pa or less). Exemplary compound 1-6 having a degree of substitution of 7.0 was obtained.
  • a mixture of compounds A-1, A-2, A-3, A-4 and A-5 was obtained.
  • the obtained mixture was analyzed by HPLC and LC-MASS.
  • A-1 was 7% by mass
  • A-2 was 58% by mass
  • A-3 was 23% by mass
  • A-4 was 9% by mass
  • A-5 was 3% by mass.
  • the degree of benzoate group substitution can be adjusted by performing an esterification operation of cellulose by appropriately changing the amount of reactant, amount of catalyst, reaction time, and reaction temperature. More specifically, for example, a product having a higher degree of benzoate group substitution can be produced by increasing the reaction time, for example, a product having a higher degree of benzoate group substitution by increasing the reaction temperature. Tend to get. Moreover, there exists a tendency to obtain a thing with higher degree of acetyl group substitution by increasing the quantity of a reaction material and the amount of catalysts. Moreover, the sugar ester compound from which substitution degree differs can be obtained by using an acetic acid, toluic acid, phenylacetic acid, and trimethoxybenzoic acid for a reaction material.
  • disaccharide As an example, but the disaccharide may be produced by a method other than the above, and the trisaccharide may be similarly referred to the above example. Further, it can be produced by utilizing or combining known knowledge.
  • the hue Y. of disaccharide or trisaccharide. I. can be obtained.
  • the retardation film according to the present invention contains a retardation increasing agent.
  • a viewing angle can be expanded by containing a phase difference increasing agent.
  • the inclusion of a retardation increasing agent avoids excessive stretching operation, and suppresses the cause of contrast reduction caused by fine cracks (crazes) in the film generated during stretching for adjusting the retardation and foreign matter arrangement. preferable.
  • the retardation increasing agent is generally decomposed under high temperature and high humidity, the retardation is reduced, and color shift easily occurs.
  • the addition of a specific sugar ester compound as in the present invention has the effect of suppressing the color shift as much as the disappearance of the yellow phosphor in the backlight is eliminated.
  • the retardation increasing agent can be contained, for example, in a proportion of 0.1 to 15% by mass, and further in a proportion of 1.0 to 7.0% by mass with respect to 100% by mass of cellulose acylate. It is preferable to make it. Two or more kinds of phase difference increasing agents may be used in combination.
  • the “aromatic ring” includes an aromatic heterocycle in addition to an aromatic hydrocarbon ring (for example, a benzene ring).
  • the aromatic heterocycle is generally an unsaturated heterocycle.
  • the aromatic heterocycle may be a 5-membered ring, 6-membered ring or 7-membered ring.
  • a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. Therefore, it is preferable that a phase difference increasing agent contains a nitrogen-containing heterocyclic compound.
  • aromatic heterocycle examples include furan ring, diazole ring, oxadiazole ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, Triazole ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring are included.
  • the retardation increasing agent may include two or more aromatic rings, and the bonding relationship between the two or more aromatic rings is (a) when a condensed ring is formed, It can be classified into a case where it is directly linked by a single bond and a case where it is bound via a linking group.
  • the bond relationship may be any of (a) to (c).
  • condensed ring examples include an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a biphenylene ring, a naphthacene ring, Pyrene ring, indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromene ring, quinoline ring, isoquinoline Ring, quinolidine ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthalazine
  • the single bond is preferably a bond between carbon atoms of two aromatic rings.
  • Two aromatic rings may be bonded by two or more single bonds (alkylene group) to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings.
  • the combination of (b) may be a combination of an aromatic ring and an aromatic heterocycle.
  • the linking group is also preferably bonded to carbon atoms of two aromatic rings.
  • the linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, —CO—, —O—, —NH—, —S—, or a combination thereof. Examples of linking groups composed of combinations are shown below. In addition, the relationship between the left and right in the following examples of the linking group may be reversed.
  • the aromatic ring and the linking group may have a substituent.
  • substituents include halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, alkyl group, alkenyl group, alkynyl group, aliphatic acyl group , Aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamido group, aliphatic substituted amino group, aliphatic substituted carbamoyl group, aliphatic Substituted sulfamoyl groups, aliphatic substituted ureido groups and non-aromatic heterocyclic groups are included.
  • the number of carbon atoms in the alkyl group is preferably 1-8.
  • a chain alkyl group is preferable to a cyclic alkyl group, and a linear alkyl group is particularly preferable.
  • the alkyl group may further have a substituent (eg, hydroxy, carboxy, alkoxy group, alkyl-substituted amino group).
  • Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, propyl, n-butyl, t-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl And 2-diethylaminoethyl.
  • the alkenyl group preferably has 2 to 8 carbon atoms.
  • a chain alkenyl group is preferable to a cyclic alkenyl group, and a linear alkenyl group is particularly preferable.
  • the alkenyl group may further have a substituent. Examples of alkenyl groups include vinyl, allyl and 1-hexenyl.
  • the alkynyl group preferably has 2 to 8 carbon atoms.
  • a chain alkynyl group is preferable to a cyclic alkynyl group, and a linear alkynyl group is particularly preferable.
  • the alkynyl group may further have a substituent. Examples of the alkynyl group include ethynyl, 1-butynyl and 1-hexynyl.
  • the number of carbon atoms in the aliphatic acyl group is preferably 1-10.
  • Examples of the aliphatic acyl group include acetyl, propanoyl and butanoyl.
  • the number of carbon atoms in the aliphatic acyloxy group is preferably 1-10.
  • Examples of the aliphatic acyloxy group include acetoxy.
  • the number of carbon atoms of the alkoxy group is preferably 1-8.
  • the alkoxy group may further have a substituent (eg, alkoxy group).
  • Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, butoxy and methoxyethoxy.
  • the number of carbon atoms of the alkoxycarbonyl group is preferably 2-10.
  • alkoxycarbonyl group examples include methoxycarbonyl and ethoxycarbonyl.
  • the number of carbon atoms of the alkoxycarbonylamino group is preferably 2-10.
  • alkoxycarbonylamino group examples include methoxycarbonylamino and ethoxycarbonylamino.
  • the number of carbon atoms of the alkylthio group is preferably 1-12.
  • Examples of the alkylthio group include methylthio, ethylthio and octylthio.
  • the alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include methanesulfonyl and ethanesulfonyl.
  • the number of carbon atoms in the aliphatic amide group is preferably 1-10.
  • Examples of the aliphatic amide group include acetamide.
  • the number of carbon atoms of the aliphatic sulfonamide group is preferably 1-8.
  • Examples of the aliphatic sulfonamido group include methanesulfonamido, butanesulfonamido and n-octanesulfonamido.
  • the number of carbon atoms of the aliphatic substituted amino group is preferably 1-10.
  • Examples of the aliphatic substituted amino group include dimethylamino, diethylamino and 2-carboxyethylamino.
  • the aliphatic substituted carbamoyl group preferably has 2 to 10 carbon atoms.
  • Examples of the aliphatic substituted carbamoyl group include methylcarbamoyl and diethylcarbamoyl.
  • the number of carbon atoms in the aliphatic substituted sulfamoyl group is preferably 1-8.
  • Examples of the aliphatic substituted sulfamoyl group include methylsulfamoyl and diethylsulfamoyl.
  • the number of carbon atoms in the aliphatic substituted ureido group is preferably 2 to 10.
  • Examples of the aliphatic substituted ureido group include methylureido.
  • Examples of non-aromatic heterocyclic groups include piperidino and morpholino.
  • the molecular weight of the retardation increasing agent is preferably 300 to 800 in order to achieve both volatility and compatibility.
  • phase difference increasing agent examples include compounds described in JP-A-2013-137357, JP-A-2000-11914 and JP-A-2000-275434.
  • the retardation film of the present invention includes, for example, silicon dioxide (silica), titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, It is preferable to contain organic fine particles composed of inorganic fine particles such as hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate, or a crosslinked polymer.
  • silicon dioxide (silica) is preferable from the viewpoint of suppressing the haze of the retardation film.
  • These may be dispersed in a solution, and an alcohol such as ethanol is suitable as the solution.
  • the concentration at that time is not particularly limited, but is, for example, about 5 to 20% by mass.
  • the primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably in the range of 5 to 16 nm, and particularly preferably in the range of 5 to 12 nm.
  • These fine particles are preferably included in the retardation film by forming secondary particles having a particle size in the range of 0.1 to 5 ⁇ m.
  • the average particle size as a preferable secondary particle is in the range of 0.1 to 2 ⁇ m. More preferably, it is in the range of 0.2 to 0.6 ⁇ m.
  • the primary average particle size of the fine particles used in the present invention is measured by observing the particles with a transmission electron microscope (magnification 500,000 to 2,000,000 times), observing 100 particles and measuring the particle size. The average value is taken as the primary average particle size.
  • the apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably in the range of 90 to 200 g / liter, and particularly preferably in the range of 100 to 200 g / liter.
  • a larger apparent specific gravity makes it possible to prepare a high-concentration dispersion, which is preferable because haze and agglomerates are improved, and is particularly preferably used when preparing a dope having a high solid content concentration. .
  • the fine particles can be contained, for example, in a proportion of 0.05 to 1.0% by mass, and further in a proportion of 0.1 to 0.5% by mass with respect to 100 parts by mass of cellulose acylate. It is preferable.
  • Silicon dioxide fine particles having an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more are, for example, a mixture of vaporized silicon tetrachloride and hydrogen in a temperature range of 1000 to 1200 ° C. in the air. It can be obtained by burning with.
  • Aerosil 200V, Aerosil R972V, Aerosil R812 are commercially available, and these can also be used.
  • the apparent specific gravity described above is calculated by the following equation by taking a certain amount of silicon dioxide fine particles in a graduated cylinder, measuring the volume and mass at this time.
  • Plasticizer The retardation film of the present invention may contain a plasticizer.
  • a plasticizer By combining the specific saccharide of the present invention and the additive, the plasticizer distribution is improved, and the adhesion is improved on the A and B surfaces described later.
  • the presence of the specific sugar ester compound of the present invention improves the plasticizer distribution and improves the adhesion on the A and B surfaces described below.
  • plasticizers include polyester compounds, polyhydric alcohol ester compounds, polyvalent carboxylic acid ester compounds (including phthalic acid ester compounds), glycolate compounds, and ester compounds (including fatty acid ester compounds and phosphate ester compounds). ) Is included. These may be used alone or in combination of two or more.
  • the polyester compound is a compound containing a repeating unit obtained by reacting a dicarboxylic acid and a diol.
  • the dicarboxylic acid constituting the polyester compound is an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid, preferably an aromatic dicarboxylic acid.
  • the dicarboxylic acid may be one kind or a mixture of two or more kinds.
  • the diol constituting the polyester compound is an aromatic diol, an aliphatic diol or an alicyclic diol, preferably an aliphatic diol, more preferably a diol having 1 to 4 carbon atoms.
  • the diol may be one type or a mixture of two or more types.
  • the polyester compound preferably includes a repeating unit obtained by reacting at least a dicarboxylic acid containing an aromatic dicarboxylic acid and a diol having 1 to 4 carbon atoms; an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid; More preferably, it contains a repeating unit obtained by reacting a dicarboxylic acid containing a diol with 1 to 4 carbon atoms.
  • Both ends of the molecule of the polyester compound may be sealed or not sealed, but are preferably sealed from the viewpoint of reducing the moisture permeability of the film.
  • the polyester compound is preferably a compound represented by the formula (1) or (2).
  • n is an integer of 1 or more.
  • Formula (1) B- (GA) n -GB Formula (2) C- (AG) n -AC A in the formulas (1) and (2) is a divalent group derived from an alkylenedicarboxylic acid having 3 to 20 (preferably 4 to 12) carbon atoms, and has 4 to 20 (preferably 4 to 12) carbon atoms. ) Or a divalent group derived from an aryl dicarboxylic acid having 8 to 20 carbon atoms (preferably 8 to 12 carbon atoms).
  • Examples of the divalent group derived from an alkylenedicarboxylic acid having 3 to 20 carbon atoms in A include 1,2-ethanedicarboxylic acid (succinic acid), 1,3-propanedicarboxylic acid (glutaric acid), 1 Divalent groups derived from 1,4-butanedicarboxylic acid (adipic acid), 1,5-pentanedicarboxylic acid (pimelic acid), 1,8-octanedicarboxylic acid (sebacic acid) and the like are included.
  • Examples of the divalent group derived from alkenylene dicarboxylic acid having 4 to 20 carbon atoms in A include a divalent group derived from maleic acid, fumaric acid and the like.
  • divalent groups derived from aryl dicarboxylic acids having 8 to 20 carbon atoms in A include 1,2-benzenedicarboxylic acid (phthalic acid), 1,3-benzenedicarboxylic acid, 1,4-benzene.
  • divalent groups derived from naphthalenedicarboxylic acid such as dicarboxylic acid and 1,5-naphthalenedicarboxylic acid are included.
  • A may be one type or two or more types may be combined. Among these, A is preferably a combination of an alkylene dicarboxylic acid having 4 to 12 carbon atoms and an aryl dicarboxylic acid having 8 to 12 carbon atoms.
  • G in the formulas (1) and (2) is a divalent group derived from an alkylene glycol having 2 to 20 carbon atoms (preferably 2 to 12 carbon atoms), and has 6 to 20 carbon atoms (preferably 6 to 12 carbon atoms). And a divalent group derived from an oxyalkylene glycol having 4 to 20 carbon atoms (preferably 4 to 12 carbon atoms).
  • Examples of the divalent group derived from an alkylene glycol having 2 to 20 carbon atoms in G include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1, 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-dimethylol) Heptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanedio ,
  • divalent groups derived from aryl glycols having 6 to 20 carbon atoms in G include 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene Divalent groups derived from (hydroquinone) and the like are included.
  • divalent group derived from oxyalkylene glycol having 4 to 12 carbon atoms in G are derived from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and the like. Divalent groups are included.
  • G may be one type or two or more types may be combined. Among these, G is preferably an alkylene glycol having 2 to 12 carbon atoms.
  • B in the formula (1) is a monovalent group derived from an aromatic ring-containing monocarboxylic acid or an aliphatic monocarboxylic acid.
  • the aromatic ring-containing monocarboxylic acid in the monovalent group derived from the aromatic ring-containing monocarboxylic acid is a carboxylic acid containing an aromatic ring in the molecule, and not only those in which the aromatic ring is directly bonded to the carboxyl group, Also included are those in which an aromatic ring is bonded to a carboxyl group via an alkylene group or the like.
  • monovalent groups derived from aromatic ring-containing monocarboxylic acids include benzoic acid, para-tert-butyl benzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethyl benzoic acid, ethyl benzoic acid, and normal propyl benzoic acid. , Monovalent groups derived from aminobenzoic acid, acetoxybenzoic acid, phenylacetic acid, 3-phenylpropionic acid and the like.
  • Examples of monovalent groups derived from aliphatic monocarboxylic acids include monovalent groups derived from acetic acid, propionic acid, butanoic acid, caprylic acid, caproic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid and the like. Is included. Among these, a monovalent group derived from an alkyl monocarboxylic acid having 1 to 3 carbon atoms in the alkyl portion is preferable, and an acetyl group (a monovalent group derived from acetic acid) is more preferable.
  • C in the formula (2) is a monovalent group derived from an aromatic ring-containing monoalcohol or an aliphatic monoalcohol.
  • An aromatic ring-containing monoalcohol is an alcohol containing an aromatic ring in the molecule, and includes not only those in which an aromatic ring is directly bonded to an OH group, but also those in which an aromatic ring is bonded to an OH group via an alkylene group or the like.
  • Examples of the monovalent group derived from an aromatic ring-containing monoalcohol include a monovalent group derived from benzyl alcohol, 3-phenylpropanol and the like.
  • Examples of monovalent groups derived from aliphatic monoalcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol, isohexanol, cyclohexyl alcohol, octanol, isooctanol, Monovalent groups derived from 2-ethylhexyl alcohol, nonyl alcohol, isononyl alcohol, tert-nonyl alcohol, decanol, dodecanol, dodecahexanol, dodecaoctanol, allyl alcohol, oleyl alcohol and the like are included. Of these, monovalent groups derived from alcohols having 1 to 3 carbon atoms such as methanol, ethanol, propanol and isopropanol are preferred.
  • the weight average molecular weight of the polyester compound is preferably 300 to 1500, and more preferably 400 to 1000.
  • a polyester compound having a weight average molecular weight of less than 300 may easily exude from the optical film.
  • polyester compounds are shown below. First, a specific example of a polyester compound in which both ends are sealed with an “aromatic group” is shown.
  • P-1 acetyl esterified product of both ends of a condensate (weight average molecular weight 950) comprising adipic acid / phthalic acid / ethanediol (1/1/2 molar ratio)
  • P-2 succinic acid / phthalic acid / ethane Acetyl esterified compound at both ends of a condensate (weight average molecular weight 2500) consisting of diol / (1/1/2 molar ratio)
  • P-3 glutaric acid / isophthalic acid / 1,3-propanediol (1/1 / Acetyl esterified product at both ends of a condensate (weight average molecular weight 1300) consisting of 2 mole ratio)
  • P-4 Succinic acid / glutaric acid / adipic acid / terephthalic acid / isophthalic acid / ethanediol / 1,2-propan
  • Preferred examples of the aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2- Butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, trimethylolpropane , Pentaerythritol, trimethylolethane, xylitol and the like.
  • triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, xylitol and the like are preferable.
  • the monocarboxylic acid is not particularly limited, and may be an aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, an aromatic monocarboxylic acid, or the like. In order to increase the moisture permeability of the film and make it difficult to volatilize, alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred.
  • One kind of monocarboxylic acid may be used, or a mixture of two or more kinds may be used. Further, all of the OH groups contained in the aliphatic polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
  • the aliphatic monocarboxylic acid is preferably a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms.
  • the number of carbon atoms of the aliphatic monocarboxylic acid is more preferably 1-20, and still more preferably 1-10.
  • 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, and laccelic acid; undecylenic acid, Examples include unsaturated fatty acids such as oleic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. Of these, acetic acid or a mixture of ace
  • Examples of the alicyclic monocarboxylic acid include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid and the like.
  • aromatic monocarboxylic acids examples include benzoic acid; one having 1 to 3 alkyl groups or alkoxy groups (for example, methoxy group or ethoxy group) introduced into the benzene ring of benzoic acid (for example, toluic acid); benzene ring Aromatic monocarboxylic acids having two or more (for example, biphenyl carboxylic acid, naphthalene carboxylic acid, tetralin carboxylic acid, etc.) are included, and benzoic acid is preferred.
  • polyhydric alcohol ester compound examples include the following.
  • divalent alcohol ester compound examples include the following.
  • trivalent or higher alcohol ester compounds examples include the following compounds.
  • the polyvalent carboxylic acid ester compound is an ester compound of a divalent or higher, preferably 2 to 20 valent polycarboxylic acid and an alcohol compound.
  • the polyvalent carboxylic acid is preferably a divalent to 20-valent aliphatic polyvalent carboxylic acid, a 3- to 20-valent aromatic polyvalent carboxylic acid, or a 3- to 20-valent alicyclic polyvalent carboxylic acid. .
  • polyvalent carboxylic acids include 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 Contains aliphatic polycarboxylic acids such as fumaric acid, maleic acid, and tetrahydrophthalic acid, and oxypolycarboxylic acids such as tartaric acid, tartronic acid, malic acid, and citric acid, and suppresses volatilization from the film. For this, oxypolycarboxylic acids are preferred.
  • the alcohol compound examples include an aliphatic saturated alcohol compound having a straight chain or a side chain, an aliphatic unsaturated alcohol compound having a straight chain or a side chain, an alicyclic alcohol compound, or an aromatic alcohol compound.
  • the carbon number of the aliphatic saturated alcohol compound or the aliphatic unsaturated alcohol compound is preferably 1 to 32, more preferably 1 to 20, and still more preferably 1 to 10.
  • Examples of the alicyclic alcohol compound include cyclopentanol, cyclohexanol and the like.
  • the aromatic alcohol compound include benzyl alcohol and cinnamyl alcohol.
  • the molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but is preferably 300 to 1000, and more preferably 350 to 750.
  • the molecular weight of the polyvalent carboxylic acid ester plasticizer is preferably larger from the viewpoint of suppressing bleeding out; it is preferably smaller from the viewpoint of moisture permeability and compatibility with cellulose acetate.
  • polyvalent carboxylic acid ester compounds include triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzoyl tributyl citrate, acetyl triphenyl citrate, acetyl tribenzyl citrate Rate, dibutyl tartrate, diacetyl dibutyl tartrate, tributyl trimellitic acid, tetrabutyl pyromellitic acid and the like.
  • ATEC acetyl triethyl citrate
  • ATBC acetyl tributyl citrate
  • benzoyl tributyl citrate acetyl triphenyl citrate
  • acetyl tribenzyl citrate Rate dibutyl tartrate
  • diacetyl dibutyl tartrate diacetyl dibutyl tartrate
  • tributyl trimellitic acid
  • the polyvalent carboxylic acid ester compound may be a phthalic acid ester compound.
  • the phthalic acid ester compound include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dicyclohexyl terephthalate and the like.
  • glycolate compounds include alkylphthalyl alkyl glycolates.
  • alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl Ethyl glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl Glycolate, butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl
  • the ester compound includes a fatty acid ester compound, a citrate ester compound, a phosphate ester compound, and the like.
  • fatty acid ester compounds include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
  • citrate ester compound include acetyltrimethyl citrate, acetyltriethyl citrate, and acetyltributyl citrate.
  • phosphate ester compounds include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, biphenyl diphenyl phosphate, bisphenol A bis-diphenyl phosphate, trioctyl phosphate, and the like, Triphenyl phosphate is preferred.
  • a ultraviolet absorber in the retardation film of this invention, can also be contained as needed.
  • the ultraviolet absorber is a compound having a characteristic of absorbing ultraviolet rays of 400 nm or less, and is intended to improve durability.
  • the transmittance at a wavelength of 370 nm is preferably 10% or less, more preferably. Is 5% or less, more preferably 2% or less.
  • the ultraviolet absorber that can be used in the present invention is not particularly limited.
  • oxybenzophenone compounds benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex salts Compound, inorganic powder and the like.
  • tinuvins such as tinuvin 109, tinuvin 171, tinuvin 234, tinuvin 326, tinuvin 327, tinuvin 328, tinuvin 928, and these are all manufactured by BASF Japan It is a commercial item and can be preferably used.
  • the UV absorber preferably used in the present invention is a benzotriazole UV absorber, a benzophenone UV absorber, or a triazine UV absorber, and particularly preferably a benzotriazole UV absorber or a benzophenone UV absorber.
  • a discotic compound such as a compound having a 1,3,5-triazine ring is also preferably used as the ultraviolet absorber.
  • the retardation film of the present invention preferably contains two or more kinds of ultraviolet absorbers.
  • a polymeric ultraviolet absorber can also be preferably used, and in particular, a polymer type ultraviolet absorber described in JP-A-6-148430 is preferably used.
  • the UV absorber can be added by dissolving the UV absorber at a desired concentration in alcohols such as methanol, ethanol and butanol, organic solvents such as methylene chloride, methyl acetate, acetone and dioxolane or mixed solvents thereof. It may be added to the dope or added directly into the dope composition.
  • alcohols such as methanol, ethanol and butanol
  • organic solvents such as methylene chloride, methyl acetate, acetone and dioxolane or mixed solvents thereof. It may be added to the dope or added directly into the dope composition.
  • an inorganic powder that does not dissolve in an organic solvent it is preferable to use a dissolver or a sand mill in the organic solvent and cellulose acylate to disperse and then add to the dope.
  • the amount of UV absorber used is not uniform depending on the type of UV absorber, operating conditions, etc., but when the dry film thickness of the retardation film is in the range of 30 to 200 ⁇ m, it is 0 for the retardation film.
  • the addition is preferably within the range of 5 to 10% by mass, and more preferably within the range of 0.6 to 4% by mass.
  • antioxidant can be used.
  • Antioxidants are also referred to as deterioration inhibitors or stabilizers.
  • the effect of delaying or preventing the retardation film from being decomposed by the residual solvent halogen in the retardation film, phosphoric acid of the phosphoric acid plasticizer, etc. It is preferable to contain it.
  • 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 in the range of 1 ppm to 1.0% by mass ratio with respect to cellulose acylate, and more preferably in the range of 10 to 1000 ppm.
  • the yellow index (YI) value of the retardation film referred to in the present invention can be determined by the method described in JIS standard K7105-6.3. As a specific method for measuring the yellow index value in the present invention, as described in the examples, using a spectrophotometer U-3200 manufactured by Hitachi, Ltd. and the attached saturation calculation program, the tristimulus value of the color X, Y, and Z were obtained, and a yellow index value was obtained according to the following formula.
  • the moisture permeability of the retardation film of the present invention is preferably in the range of 300 to 1800 g / m 2 ⁇ 24 h when measured in an environment of 40 ° C. and 90% RH, and more preferably in the range of 400 to 1500 g / m 2 ⁇ It is preferably within the range of 24 h, particularly preferably within the range of 40 to 1300 g / m 2 ⁇ 24 h.
  • the moisture permeability here can be measured according to the method described in JIS Z 0208.
  • the breaking elongation of the retardation film of the present invention is preferably in the range of 10 to 80%, more preferably in the range of 20 to 50%.
  • the breaking elongation was measured by measuring the breaking point stress (MPa) in the direction of the slow axis of the film and in the direction perpendicular thereto by measurement based on JIS K7127-1999, and the film thickness of the film was multiplied by this breaking point stress. The thing is calculated as the elongation at break (N).
  • the visible light transmittance of the retardation film of the present invention is preferably 90% or more, and more preferably 93% or more.
  • the visible light transmittance can be obtained by using a spectrophotometer V-2450 manufactured by Shimadzu Corporation to obtain an average transmittance in the visible light region (400 to 700 nm).
  • the haze of the retardation film of the present invention is preferably less than 1%, particularly preferably in the range of 0 to 0.4%.
  • the haze of the retardation film of the present invention can be measured using, for example, a haze meter (1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the retardation 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 production process of the retardation film of the present invention by a solution casting method mainly includes a step of preparing a dope by dissolving cellulose acylate and an additive in a solvent, on an endless metal support that moves the dope indefinitely. , A process of drying the cast dope as a web, a process of peeling the web from the metal support, a process of stretching or maintaining the width, a process of further drying, and a process of winding up the finished film. .
  • the concentration of cellulose acylate in the dope is preferable in terms of being able to reduce the drying load after casting to a metal support, but if the concentration of cellulose acylate is too high, the load during filtration increases, Filtration accuracy decreases.
  • the concentration that achieves both of these is preferably in the range of 10 to 40% by mass, and more preferably in the range of 15 to 35% by mass.
  • the organic solvent used in the dope may be used alone or in combination of two or more. However, it is preferable in terms of production efficiency that a good solvent and a poor solvent of cellulose acylate are mixed and used. A larger amount is preferable from the viewpoint of the solubility of cellulose acylate.
  • the preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
  • a good solvent and a poor solvent what dissolve
  • the good solvent and the poor solvent change depending on the average acetylation degree (acetyl group substitution degree) of cellulose acylate.
  • 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 cellulose acylate the solvent removed from the film by drying in the film forming process can be recovered and reused.
  • the recovered solvent may contain trace amounts of additives added to the cellulose acylate, such as plasticizers, UV absorbers, polymers, and monomer components. It can be used, or refined if necessary, and can be reused after removing these additives.
  • additives added to the cellulose acylate such as plasticizers, UV absorbers, polymers, and monomer components. It can be used, or refined if necessary, and can be reused after removing these additives.
  • a general method can be used as a method for dissolving cellulose acylate. Combining heating and pressurization is one of the preferred methods because it can be heated above the boiling point at normal pressure.
  • cellulose acylate is mixed with a poor solvent and wetted or swollen, and then a good solvent is added and dissolved is also preferably used.
  • the 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 in terms of easy temperature control.
  • the heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of cellulose acylate, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates.
  • the preferable heating temperature is in the range of 45 to 120 ° C, more preferably in the range of 60 to 110 ° C, and still more preferably in the range of 70 ° C to 105 ° C. Further, the pressure is adjusted so that the solvent used at the set temperature does not boil.
  • a cooling dissolution method is also preferably used as a dope preparation method, whereby cellulose acylate can be dissolved in a low boiling point solvent such as methyl acetate.
  • the cellulose acylate solution prepared as described above is then filtered using an appropriate filter medium such as filter paper.
  • an appropriate filter medium such as filter paper.
  • the filter medium to be used it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is easily clogged.
  • a filter medium having an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium in the range of 0.001 to 0.008 mm is more preferable, and a filter medium in the range of 0.003 to 0.006 mm is more preferable.
  • the material of the filter medium is not particularly limited, and a normal filter medium can be used. However, a plastic filter medium such as polypropylene or Teflon (registered trademark), or a metal filter medium such as stainless steel may cause fibers to fall off. Less preferred.
  • Impurities contained in the raw material cellulose acylate, especially luminescent spots, are removed and reduced by filtration.
  • Bright spot foreign matter is arranged in a crossed Nicol state with two polarizing plates, an optical film or the like is placed between them, and light is applied from one polarizing plate side, and observed from the other polarizing plate side. It is a point (foreign matter) that light from the opposite side sometimes leaks, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 pieces / cm 2 or less. More preferably, it is 100 pieces / cm 2 or less, still more preferably 50 pieces / m 2 or less, and particularly 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 conventionally known method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and at a range where the solvent does not boil under pressure is the filtration before and after the filtration.
  • the increase in pressure difference (referred to as differential pressure) is small and preferable.
  • a preferred temperature is in the range of 45 to 120 ° C, more preferably in the range of 45 to 70 ° C, and still more preferably in the range of 45 to 55 ° C.
  • a smaller filtration pressure is preferred.
  • 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 band, a stainless steel belt, or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width is preferably in the range of 1 to 4 m.
  • the surface temperature of the metal support in the casting step is in the temperature range of ⁇ 50 ° C. to less than the boiling point of the solvent, and a higher temperature is preferable because the web drying rate can be increased. May deteriorate.
  • the support temperature is preferably in the range of 0 to 55 ° C, more preferably in the range of 20 to 50 ° C.
  • it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.
  • the method for controlling the temperature of the metal support is not particularly limited, and examples thereof include a method of blowing hot air or cold air, and a method of bringing hot water into contact with the back side of the metal support. 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, there is a case where wind at a temperature higher than the target temperature is used.
  • the amount of residual solvent when peeling the web from the metal support is preferably in the range of 10 to 150% by weight, more preferably 20 to 40% by weight. And particularly preferably in the range of 70 to 120% by mass.
  • the amount of residual solvent at the start of stretching is preferably in the range of 8 to 30% by mass, more preferably in the range of 10 to 25% by mass, and particularly preferably in the range of 8 to 20% by mass.
  • the amount of residual solvent is defined by the following equation.
  • M is the mass of a sample collected during or after production of the web or film
  • N is the mass after heating M at 115 ° C. for 1 hour.
  • a roller drying method (a method in which webs are alternately passed through a plurality of rollers arranged above and below) and a method of drying while transporting the web by a tenter method are employed.
  • the drying temperature in the web drying step is preferably within the range of 40 to 200 ° C.
  • the width direction also referred to as a transverse direction or a TD direction
  • a tenter method in which both ends of the web are gripped by clips or the like.
  • 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.
  • these methods may be used in combination.
  • driving the clip portion by the linear drive method is preferable from the viewpoint that smooth stretching can be performed and the risk of breakage and the like can be reduced.
  • These width maintenance or lateral stretching in the film forming process is preferably performed by a tenter, and may be a pin tenter or a clip tenter.
  • the stretching temperature is preferably in the range of 80 ° C. to 220 ° C., more preferably in the range of 90 ° C. to 180 ° C.
  • the film thickness of the retardation film is not particularly limited, but is used within a range of 10 to 100 ⁇ m.
  • the film thickness is particularly preferably in the range of 15 to 90 ⁇ m. More preferably, it is in the range of 20 to 50 ⁇ m.
  • the plasticizer distribution is improved and the adhesion is improved on the A and B surfaces described later.
  • a retardation film having a width in the range of 1 to 4 m can be used.
  • those having a width in the range of 1.4 to 4 m are preferably used, and particularly preferably in the range of 1.6 to 3 m. If the width is 4 m or less, stable film conveyance can be performed.
  • the retardation film of the present invention has a retardation value Ro defined by the following formula (i) in the range of 30 to 130 nm, and a retardation value Rt defined by the following formula (ii) in the range of 70 to 300 nm. is there.
  • nx is the refractive index in the slow axis direction in the film plane
  • ny is the refractive index in the fast axis direction in the film plane
  • nz is in the thickness direction of the film.
  • d is the thickness (nm) of the film.
  • the retardation values Ro and Rt can be measured using an automatic birefringence meter.
  • KOBRA-21ADH manufactured by Oji Scientific Instruments Co., Ltd.
  • Oji Scientific Instruments Co., Ltd. is used as an automatic birefringence meter, and can be obtained at a wavelength of 589 nm in an environment of a temperature of 23 ° C. and a humidity of 55% RH. .
  • the retardation film has the structure defined in the present invention, and further the refractive index is controlled by operations such as control of transport tension and stretching conditions.
  • the retardation value can be changed by lowering or increasing the tension in the longitudinal direction.
  • it can control by carrying out the biaxial stretching or uniaxial stretching sequentially or simultaneously with respect to the longitudinal direction (film-forming direction) of a film and the direction orthogonal to it in a film surface, ie, a width direction.
  • the retardation film of the present invention can be provided in a polarizing plate and a liquid crystal display device using the polarizing plate.
  • the polarizing plate of the present invention is characterized by being a polarizing plate in which the retardation film of the present invention is bonded to at least one surface of a polarizer.
  • the liquid crystal display device of the present invention is characterized in that the polarizing plate of the present invention is bonded to at least one liquid crystal cell surface.
  • the polarizing plate of the present invention can be produced by a general method.
  • a method for producing a retardation film of the present invention by laminating at least one surface of a polarizer produced by subjecting the polarizer side of the retardation film to alkali saponification treatment and immersion drawing in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Is preferred.
  • the retardation film of the present invention may be used, or another film may be bonded.
  • Examples of other applicable films include commercially available cellulose ester films (for example, Konica Minoltak KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC4UA, KC8UH, KC8UH, KC8UH, KC8UH, KC8U KC8UXW-RHA-C, KC8UXW-RHA-NC, KC4UXW-RHA-NC, manufactured by Konica Minolta Co., Ltd.) can be preferably used.
  • cellulose ester films for example, Konica Minoltak KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC4UA, KC8UH, KC8UH, KC8UH, KC8UH
  • the polarizing plate used on the surface side of the liquid crystal display device can be provided with an antireflection layer, an antistatic layer, an antifouling layer, and a backcoat layer as necessary. .
  • 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 it by uniaxial stretching, or by dyeing and then uniaxially stretching and then preferably performing a durability treatment with a boron compound. .
  • the thickness of the polarizer is preferably in the range of 5 to 30 ⁇ m, particularly preferably in the range of 10 to 20 ⁇ m.
  • the ethylene unit content described in JP 2003-248123 A, JP 2003-342322 A, etc. is in the range of 1 to 4 mol%
  • the polymerization degree is in the range of 2000 to 4000
  • the saponification degree is 99.
  • Ethylene-modified polyvinyl alcohol in the range of 0.0 to 99.99 mol% is also preferably used.
  • an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature in the range of 66 to 73 ° C. is preferably used.
  • a polarizer using this ethylene-modified polyvinyl alcohol film has excellent 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 bonded with a protective film on both sides or one side.
  • the adhesive used for pasting include polyvinyl alcohol (hereinafter abbreviated as PVA) adhesives and urethane adhesives. Among them, PVA adhesives are preferably used. It is done.
  • the retardation film of the present invention can be used in a vertical alignment driving method liquid crystal display device.
  • the vertical alignment type liquid crystal display device includes a backlight, a color filter layer, a vertical alignment type liquid crystal cell formed by sandwiching liquid crystal between two transparent substrates, and a surface side of the vertical alignment type liquid crystal cell.
  • a color filter-on-array (COA) system comprising a polarizing plate including the retardation film of the present invention on the (viewing side) and the backlight side and having a color filter layer on one side of the transparent substrate is adopted. It is preferable to use a vertical alignment type liquid crystal cell.
  • the COA method includes, for example, a color filter integrated drive substrate in which a color filter is directly formed on a drive side substrate of a liquid crystal cell, and a counter electrode (conductive layer) as described in JP-A-10-206888. ) And a counter substrate with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap, and a color filter is formed on the reflective electrode, and a bonding margin is provided at high definition.
  • the yield and aperture ratio can be improved by widening.
  • FIG. 1 is a conceptual diagram showing an example of a configuration of a vertical alignment (vertical alignment) type liquid crystal display device adopting a color filter on array (COA) system according to the present invention.
  • the basic configuration of the vertical alignment type liquid crystal display device includes a liquid crystal 4 between a backlight 10, a transparent substrate 7 having a color filter 5 and a thin layer transistor (TFT) 6, and the other transparent substrate 3.
  • TFT thin layer transistor
  • polarizing plates 11 and 13 mainly composed of polarizers 1 and 9 and retardation films 2 and 8 are arranged.
  • the present invention includes (1) cellulose acylate having a total acyl group substitution degree in the range of 2.80 to 2.95, (2) disaccharide or trisaccharide, and (3) retardation.
  • I. Is a retardation film for vertical alignment having an in-plane retardation value of 30 to 130 nm at a wavelength of 589 nm and a thickness direction retardation value of 70 to 300 nm.
  • the present invention it is possible to provide a retardation film that can improve screen unevenness in a high temperature and high humidity environment.
  • Example 1 ⁇ Preparation of retardation film 1> (Preparation of cellulose acylate 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, an acetic acid-water mixed solution of magnesium acetate and calcium acetate 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. .
  • the obtained cellulose ester acylate 1 had a total acyl group substitution degree of 2.9 and a weight average molecular weight of 80000.
  • the total acyl group substitution degree was measured in accordance with ASTM D-817-91.
  • the weight average molecular weight was measured according to the above-mentioned method using gel permeation chromatography (GPC).
  • the inside of the Kolben was depressurized to 4 ⁇ 10 2 Pa or less, and after excess pyridine was distilled off at 60 ° C., the inside of the Kolben was depressurized to 1.3 ⁇ 10 Pa or less and the temperature was raised to 120 ° C. Most of the acid and benzoic acid formed were distilled off.
  • Example 1-7 a sugar ester compound 1 having a total average substitution degree of 7.0.
  • the number on the left side indicates the number of the general formula.
  • “1” in “Exemplary Compound 1-7” indicates that it is an example of General Formula (1).
  • the total average substitution degree was measured from the area ratio of the chart showing the substitution degree distribution by high performance liquid chromatography by a conventional method.
  • the relative drying time: “1” means 60 minutes, and the relative drying time: “2” means 120 minutes (hereinafter the same).
  • Fine particle additive solution 1 11 parts by mass of fine particles (Aerosil R812, dry silica manufactured by Nippon Aerosil Co., Ltd.) Primary average particle diameter: 7 ⁇ m / average particle diameter as secondary particles: 0.4 ⁇ m / apparent specific gravity: 150 g / liter) and 89 masses of ethanol The mixture was stirred and mixed with a dissolver for 50 minutes, and then dispersed with a Manton Gorin disperser to prepare a fine particle dispersion.
  • ⁇ Dope composition Methylene chloride 340 parts by mass Ethanol 64 parts by mass Cellulose acylate 1 (acetyl group substitution degree (total average substitution degree) 2.9, weight average molecular weight: about 300,000) 100 parts by mass Sugar ester compound 1 (Exemplary compound 1-7) (Total average degree of substitution is 7.0) 10 parts by weight Particulate additive solution 1 1 part by weight 2,3-diphenylquinoxaline 3 parts by weight Each of the above additives is placed in a sealed heated dissolution tank and dissolved while stirring. A dope was prepared.
  • Formation of retardation film 1 solution casting method
  • the above dope was cast uniformly on an endless stainless steel band support having a surface temperature of 22 ° C. and a width of 2 m using a die coater.
  • the solvent was evaporated until the residual amount of the solvent in the cast film reached 75% by mass, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.
  • the peeled film was stretched 20% in the width direction (TD direction) using a tenter while applying heat at 170 ° C.
  • the residual solvent amount at the start of stretching was 15% by mass.
  • drying was completed while the drying zone was conveyed by a number of rollers.
  • the drying temperature was 130 ° C. and the transport tension was 100 N / m.
  • a retardation film 1 having a dry film thickness of 40 ⁇ m was obtained.
  • ⁇ Preparation of retardation films 2 to 6> (Preparation of cellulose acylate 2-6)
  • the cellulose esterification operation was carried out in the same manner except that the amount of reactants, amount of catalyst, reaction time and reaction temperature were appropriately changed, and the degree of acetyl group substitution was 2.8, 2 respectively. .95, 2.6, 2.7, 2.98 cellulose acylate 2-6 (weight average molecular weights: about 250,000, about 300,000, about 200,000, about 220,000, about 300,000, respectively) Prepared.
  • retardation films 2 to 6 were formed in the same manner as the retardation film 1 except that cellulose acylates 2 to 6 were used in place of the cellulose acylate 1.
  • Retardation films 2 to 6 were each about 20% in the width direction (TD direction) using a tenter while applying heat of about 170 ° C. to the peeled film in the production of retardation film 1. Stretched to adjust the phase difference.
  • Hue Y. In a 55% by mass methylene chloride solution of the prepared sugar ester compounds 2-8. I. Were 5, 10, 20, 25, 35, 2, 40, respectively.
  • retardation films 7 to 13 solution casting method
  • the retardation films 7 to 13 were formed using the retardation film 1 except that the sugar ester compounds 2 to 8 (exemplary compound 1-7) were used in place of the sugar ester compound 1 (exemplary compound 1-7).
  • the method was the same as that for film formation.
  • the retardation films 7 to 13 were stretched by about 20% in the width direction (TD direction) using a tenter while applying heat at around 170 ° C. while the retardation film 1 was formed. The phase difference was adjusted.
  • the phase difference film 14 is stretched about 20% in the width direction (TD direction) by using a tenter while applying heat at around 170 ° C. while producing the phase difference film 1 while forming the phase difference film 1. Adjusted.
  • retardation films 15 to 17 were formed by using the retardation film 14 except that the sugar ester compounds 10 to 12 (exemplary compound 1-3) were used instead of the sugar ester compound 9 (exemplary compound 1-3). The method was the same as that for film formation.
  • the retardation films 15 to 17 were stretched by about 20% in the width direction (TD direction) using a tenter while applying heat at around 170 ° C. while the retardation film 14 was formed. The phase difference was adjusted.
  • ⁇ Preparation of retardation film 18> (Formation of retardation film 18: solution casting method)
  • a sugar ester compound 13 (exemplary compound 1-11, average substitution degree: 6.8, relative drying time: 1) was used instead of the sugar ester compound 1 (exemplary compound 1-7).
  • a retardation film 18 was produced in the same manner except that it was used.
  • the retardation film 18 is stretched about 20% in the width direction (TD direction) by using a tenter while applying heat at around 170 ° C. in the production of the retardation film 1 to give a retardation. Adjusted.
  • Hue Y In a 55% by mass methylene chloride solution of the prepared sugar ester compounds 14 to 16. I. Were 10, 25 and 40, respectively.
  • Retardation films 19 to 21 were each about 20% in the width direction (TD direction) using a tenter while applying heat at around 170 ° C. to the peeled film in the production of retardation film 18. Stretched to adjust the phase difference.
  • ⁇ Preparation of retardation film 22> The production of the retardation film 22 was carried out in the same manner as in the production of the retardation film 1 except that the peeled film was stretched 20% in the width direction (TD direction) using a tenter while applying heat at 175 ° C. The film was formed by the same method as the film 1 was formed.
  • ⁇ Preparation of retardation film 23> The production of the retardation film 23 was performed except that the peeled film was stretched 15% in the width direction (TD direction) using a tenter while applying heat at 170 ° C. in the production of the retardation film 1.
  • the film was formed by the same method as the film 1 was formed.
  • ⁇ Preparation of retardation film 24> The production of the retardation film 24 was performed except that the peeled film was stretched 25% in the width direction (TD direction) using a tenter while applying heat at 170 ° C. in the production of the retardation film 1.
  • the film was formed by the same method as the film 1 was formed.
  • phase difference film 25 was produced in the same manner as in the production of the phase difference film 1 except that the peeled film was stretched 20% in the width direction (TD direction) using a tenter while applying heat at 165 ° C.
  • the film was formed by the same method as the film 1 was formed.
  • Exemplified Compound 4-1 (monosaccharide) is the same as “Compound 6” in paragraph “0059” of JP-A-2009-001696.
  • the retardation films 26 to 33 were stretched by about 20% in the width direction (TD direction) by using a tenter while applying heat at around 170 ° C. while the retardation film 1 was formed. The phase difference was adjusted.
  • a 55 mass% methylene chloride solution of the sugar ester compounds 17 to 24 was prepared, and the hue Y. I. As a result, they were 7, 7, 5.5, 5.5, 5.5, 5.5, 45, and 2, respectively.
  • phase difference films 34 to 35 are formed by using Sunset Yellow FCF (manufactured by Tokyo Chemical Industry Co., Ltd., molecular formula C 16 H 10 N 2 Na 2 O 7 S 2 instead of sugar ester compound 1 (Exemplary Compound 1-7). , Molecular weight 452.38, CAS registration number: 2783-94-0, molar mass: 424.35 g / mol), Ti328 (made by Ciba Japan) having the following chemical formula
  • the retardation films 34 to 35 were stretched about 20% in the width direction (TD direction) by using a tenter while applying heat at about 170 ° C. while the retardation film 1 was formed. The phase difference was adjusted.
  • Retardation films 36 to 38 were each about 20% in the width direction (TD direction) using a tenter while applying heat at around 170 ° C. to the peeled film in the production of retardation film 1. Stretched to adjust the phase difference.
  • a 55 mass% methylene chloride solution of the sugar ester compounds 25 to 27 prepared above was prepared, and the hue Y. I. As a result of measurement, they were 8, 9, and 8.5, respectively.
  • Retardation films 39 to 43 were each about 20% in the width direction (TD direction) using a tenter while applying heat of around 170 ° C. to the peeled film in the production of retardation film 1. Stretched to adjust the phase difference.
  • Retardation film 44 9-ethylcarbazole (Tokyo Kasei / product code: E0071), Retardation film 45: 2-methylbenzoxazole (Tokyo Kasei / product code: M0557), Retardation film 46: 2- (4-tert-butylphenyl) -5- (4-biphenyl) -1,3,4-oxadiazole (Tokyo Kasei / product code: B2696), Retardation film 47: 4,5-dihydro-2-phenyloxazole (Tokyo Kasei / product code: D2155), Retardation film 48: Benzotriazole (Kanto Chemical Co., Inc./Product No .: 05084-00), Retardation film 49: 3,5-d
  • Retardation films 44 to 49 were each about 20% in the width direction (TD direction) using a tenter while applying heat at around 170 ° C. to the peeled film in the production of retardation film 1. Stretched to adjust the phase difference.
  • Retardation films 50 to 53 were produced in the same manner except that the thickness of the retardation film 1 was changed to 20 ⁇ m, 30 ⁇ m, 60 ⁇ m, and 80 ⁇ m.
  • a retardation film 55 was produced in the same manner as in the production of the retardation film 54 except that the film thickness was changed to 40 ⁇ m.
  • a retardation film 56 was produced in the same manner except that 2.5 parts by mass of TPP was further added as the additive 1 to prepare a dope.
  • a retardation film 57 was prepared in the same manner as in the preparation of the retardation film 56 except that the additive 1 was changed to BDP (bisphenol A bis-diphenyl phosphate Daihachi Chemical Industry, CAS No. 5945-33-5).
  • a retardation film 58 was produced in the same manner except that 2.5 parts by mass of the polyester compound 1 was further added as the additive 2 to prepare a dope.
  • a retardation film 59 was produced in the same manner except that 2.5 parts by mass of the polyester compound 1 was further added as the additive 2 to prepare a dope.
  • a retardation film 61 was produced in the same manner as in the production of the retardation film 60 except that the additive 1 was changed to BDP.
  • a retardation film 62 was produced in the same manner except that 2.5 parts by mass of polyester compound 1 was further added as additive 2 to prepare a dope.
  • a retardation film 63 was produced in the same manner except that the additive film 1 was changed to BDP in the production of the retardation film 62.
  • a retardation film 64 was produced in the same manner as in the production of the retardation film 58 except that the sugar ester compound of Exemplified Compound No. 1-7 was not added.
  • a retardation film 65 was produced in the same manner as in the production of the retardation film 59 except that the sugar ester compound of Exemplified Compound No. 1-7 was not added.
  • the tristimulus values X, Y, and Z of the color were obtained, and the yellow index value YI was obtained according to the following formula. .
  • Formula (I): Ro (nx ⁇ ny) ⁇ d (nm)
  • Formula (II): Rt ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d (nm)
  • d is the film thickness (nm)
  • refractive index nx reffractive index in the slow axis direction
  • ny reffractive index in the direction perpendicular to the slow axis in the film plane
  • nz in the thickness direction
  • the refractive index of the film was measured at a wavelength of 589 nm in an environment of 23 ° C. and 55% RH using an Abbe refractometer.
  • the 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 589 nm.
  • Example 2 ⁇ Preparation of polarizing plate> A 120 ⁇ m-thick polyvinyl alcohol film 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, and then washed with water. A polarizer was obtained by drying.
  • Example 2 Next, the polarizer and the retardation films 1 to 65 produced in Example 1 were bonded together according to the following steps 1 to 5, and the back side was bonded with Konica Minolta Tack KC4UY (Konica Minolta Advanced Layer Co., Ltd. cellulose ester film). A polarizing plate was produced.
  • Step 1 Each retardation film and Konica Minoltak KC4UY were immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to saponify the side to be bonded to the polarizer.
  • Step 2 The prepared 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 placed on each retardation film treated in Step 1.
  • Step 4 Each retardation film laminated in Step 3, a polarizer, and Konica Minolta Tack KC4UY on the back side were bonded at a pressure of 20 to 30 N / cm 2 and a conveyance speed of about 2 m / min.
  • Step 5 A sample obtained by bonding the polarizer prepared in Step 4 to each of the retardation films and Konica Minoltack KC4UY in a dryer at 80 ° C. is dried for 2 minutes, and polarized light corresponding to the retardation films 1 to 65, respectively. A plate was made.
  • B surface the surface in contact with the belt when forming the retardation film
  • a surface the surface opposite to the B surface
  • the polarizer and / or the retardation film cannot be peeled off and cannot be peeled off. Is good. Also, both the A side and B side of the retardation film had good adhesion.
  • Adhesiveness is a little better when part of the polarizing plate adhered on the A and B sides of the retardation film is partially peeled off between the polarizer and the transparent protective film.
  • the liquid crystal cell 2 of this liquid crystal display device has the configuration shown in FIG. 2, and the color filter 5 is arranged on the transparent substrate 3 and the thin film transistor 6 is arranged on the transparent substrate 7 with respect to the configuration shown in FIG. It is the composition which is.
  • A No color shift (color tone variation) is observed between the initial and processed liquid crystal display devices.
  • O A color shift (color tone variation) is hardly observed between the initial and processed liquid crystal display devices.
  • ⁇ Color shift (color tone fluctuation) is slightly recognized in the specific color display between the initial and processed liquid crystal display device, but there is no practical problem.
  • ⁇ Between the initial and processed liquid crystal display device, If a strong color shift (color tone fluctuation) is recognized, the quality is a problem in practical use.
  • ⁇ xy value is less than 0.05 ⁇ : ⁇ xy value is 0.05 or more and less than 0.07 ⁇ : ⁇ xy value is 0.07 or more and less than 0.09 ⁇ : ⁇ xy value Is 0.09 or more.
  • the compatibility with the sugar ester compound can be improved and the color shift can be suppressed.
  • compatibility with a sugar ester compound is bad and a color shift appears notably.
  • the color shift can be suppressed even if the yellow phosphor in the backlight disappears. I.
  • an in-plane retardation value at a wavelength of 589 nm is 30 to 130 nm and a thickness direction retardation value is 70 to 300 nm
  • the retardation of the liquid crystal is eliminated, visibility is improved, and color shift is performed. Remarkably suppressed.
  • an in-plane retardation value at a wavelength of 589 nm is 30 to 130 nm and the thickness direction retardation value is out of the range of 70 to 300 nm, the retardation of the liquid crystal cannot be eliminated. The color shift appears remarkably.
  • the disaccharide or the trisaccharide is a sugar ester compound having a total average substitution degree of more than 6.00, the compatibility with cellulose acylate is improved and the color shift is more remarkably suppressed. Further, since the yellow color is appropriate when the total mass of the disaccharide or the trisaccharide is in the range of 1 to 30% by mass with respect to 100 parts by mass of cellulose acylate, the yellow phosphor in the backlight disappears. It can be seen that the color shift can be suppressed more remarkably even if there is.
  • the present invention even if the phase difference increasing agent is decomposed by high temperature and high humidity, since the specific sugar ester compound is added, the disappearance of the yellow phosphor in the backlight is eliminated and the color shift is performed. There is also an effect that can be suppressed.
  • the thickness of the retardation film for vertical alignment is not particularly dependent on the color shift. Further, when the film thickness is in the range of the examples, the plasticizer distribution is improved, and the adhesion on the A and B surfaces is improved. Moreover, it turns out that a plasticizer distribution becomes good by combining an additive with the specific saccharide

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JP2003066230A (ja) * 2001-08-23 2003-03-05 Fuji Photo Film Co Ltd 光学補償シート、偏光板、楕円偏光板および液晶表示装置
JP2007169592A (ja) * 2005-11-22 2007-07-05 Fujifilm Corp セルロースアシレートペレットおよびその製造方法、セルロースアシレート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
JP2011126955A (ja) * 2009-12-16 2011-06-30 Konica Minolta Opto Inc 光学フィルム
WO2013094466A1 (ja) * 2011-12-22 2013-06-27 コニカミノルタ株式会社 位相差フィルム、偏光板及び液晶表示装置

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JP2003066230A (ja) * 2001-08-23 2003-03-05 Fuji Photo Film Co Ltd 光学補償シート、偏光板、楕円偏光板および液晶表示装置
JP2007169592A (ja) * 2005-11-22 2007-07-05 Fujifilm Corp セルロースアシレートペレットおよびその製造方法、セルロースアシレート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
JP2011126955A (ja) * 2009-12-16 2011-06-30 Konica Minolta Opto Inc 光学フィルム
WO2013094466A1 (ja) * 2011-12-22 2013-06-27 コニカミノルタ株式会社 位相差フィルム、偏光板及び液晶表示装置

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