WO2009101839A1 - 位相差フィルム - Google Patents
位相差フィルム Download PDFInfo
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- WO2009101839A1 WO2009101839A1 PCT/JP2009/050649 JP2009050649W WO2009101839A1 WO 2009101839 A1 WO2009101839 A1 WO 2009101839A1 JP 2009050649 W JP2009050649 W JP 2009050649W WO 2009101839 A1 WO2009101839 A1 WO 2009101839A1
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- 0 *(c1ccccc1)c1c(**2ccccc2*c2ccccc2)cccc1 Chemical compound *(c1ccccc1)c1c(**2ccccc2*c2ccccc2)cccc1 0.000 description 7
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
- G02B7/003—Alignment of optical elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/14—Mixed esters
Definitions
- the present invention relates to a retardation film used for a liquid crystal display device, and more particularly to a retardation film having excellent front contrast.
- Cellulose ester films, polycarbonate films, polycycloolefin films, and the like are often used as retardation films for liquid crystal display devices.
- the retardation film is required to have high optical transparency and low birefringence.
- the liquid crystal display device has been increased in size and brightness, and accordingly, the front contrast has been improved more strictly than ever.
- Non-Patent Document 1 proposes a single sheet technology using a polycarbonate film and a polycycloolefin film.
- an optical compensation film that also serves as a polarizing plate protective film the bonding property with polyvinyl alcohol as a polarizer is insufficient, and a polarizing plate protective film made of a cellulose ester film is Even now, it is recognized as an indispensable optical film for liquid crystal displays.
- the cellulose ester film has been used as a polarizing plate protective film because of its low birefringence, and it is not easy to impart its function.
- Patent Documents 1, 2, and 3 In order to obtain a desired retardation value, a technique (Patent Documents 1, 2, and 3) in which a compound having a retardation increasing effect is added to a cellulose ester film and the film is further stretched has been proposed. There was a problem that the transmittance
- the film transmittance deterioration is presumed to be an increase in haze (scattering factor), and a phenomenon occurs in which the front contrast of the liquid crystal display image is deteriorated.
- An object of the present invention is to provide a retardation film excellent in visibility (light leakage, uneven coloring, front contrast).
- the film slow axis is A retardation film, wherein a difference in scattered light intensity integral value between a horizontal installation on a sample stage and a vertical installation is 0.1 or less.
- the retardation film has an aromatic terminal polyester compound represented by the following general formula (I), and at least one of at least one of a pyranose structure or a furanose structure and 12 or less of all OH groups of the structure Alternatively, the retardation film as described in (1) above, which is a cellulose ester film containing at least one ester compound partially esterified.
- B is an arylcarboxylic acid residue
- G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms
- A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms
- n represents an integer of 1 or more.
- a retardation film excellent in front contrast can be provided.
- the liquid crystal display device generally has viewing angle characteristics, and there is a problem that the contrast is lowered when observed from a position having an angle from the normal line direction of the liquid crystal cell.
- the retardation is preferably such that the in-plane retardation Ro is in the range of 20 to 200 nm and the retardation Rt in the thickness direction is in the range of 70 to 400 nm.
- the cellulose ester film which is the retardation film of the invention is also preferably in this range.
- the retardation film of the present invention is characterized in that the scattered light measured by a goniophotometer is in a certain range even if it is stretched to obtain the retardation.
- the front contrast is not necessarily set to a desired value. I know that I can't.
- Anisotropic scattering refers to the difference in scattered light intensity between the slow axis direction of the film and the direction perpendicular thereto. This anisotropic scattering is measured with a goniophotometer.
- FIG. 1 shows an outline of a goniophotometer (model: GP-1-3D, manufactured by Optec Corporation). 1. 1. light source lamp; 2. Spectroscope, 3. Sample stage (also called stage) Sample, 5. It is a light receiving part.
- the light source is a 12V50W halogen bulb, and the light receiving part is a photomultiplier tube (Photomaru Hamamatsu Photonics R636-10).
- (A) shows the arrangement of a light source lamp, a spectroscope, a sample stage (stage), and an integrating sphere for measuring light intensity at the time of reference measurement for measuring reference light or transmittance measurement.
- (B) shows the arrangement of the light source lamp, spectroscope, sample stage, and integrating sphere when the measurement sample is placed on the sample stage and the reflectance is measured.
- the sample stage is usually a measurement sample vertical hanging type, and the measurement sample is fixed with a clamp, and the lower part of the stage is an angle indexing rotary table.
- the transmittance is changed by changing the angle between the sample surface and the incident surface. It is a structure that can measure the reflectance.
- the anisotropic scattering intensity according to the present invention can be measured by the arrangement (a). That is, the measurement of the scattered light intensity of a film having an incident light of 90 ° in the scattered light profile of the goniophotometer refers to the scattered light intensity when light is applied perpendicularly to the sample from the light source of the goniophotometer.
- the measurement for detecting the intensity of scattered light at a position of 95 ° to 165 ° from the light source connects the normal direction of the light source, the sample observation point, and the integrating sphere shown in FIG.
- the integrated value of the scattered light intensity measured when the angle ⁇ formed by the direction is 95 ° to 165 °.
- the difference in scattered light intensity between the case where the film slow axis is horizontally installed on the sample stage and the case where it is vertically installed is , 0.1 or less.
- ⁇ Normal level can be used for horizontal and vertical conditions.
- ⁇ 35 ° centered on 130 ° having the highest correlation with the front contrast which is the final evaluation as a liquid crystal display device
- ⁇ 1 ° The scattering intensity was measured for each, and the total value was taken as the integral value.
- the integrated value of scattered light intensity when horizontal or vertical is 0.1 to 4.0, preferably 1.0 or less, and more preferably 0.50 or less.
- the scattering intensity in the horizontal direction and the vertical direction is preferably 1.0 or less.
- the retardation film of the present invention comprises an aromatic terminal polyester compound represented by the following general formula (I): Formula (I) B- (GA) nGB (Wherein B is an arylcarboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, A Represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.)
- the cellulose ester film preferably contains at least one ester compound in which at least one of the pyranose structure or furanose structure is 1 to 12 and all or part of the OH groups of the structure are esterified.
- the cellulose ester of the present invention is not particularly limited, but the cellulose ester is a carboxylic acid ester having about 2 to 22 carbon atoms, and may be an aromatic carboxylic acid ester, particularly a lower fatty acid ester having 6 or less carbon atoms. It is preferable.
- the acyl group bonded to the hydroxyl group may be linear or branched or may form a ring. Furthermore, another substituent may be substituted. In the case of the same degree of substitution, birefringence decreases when the number of carbon atoms is large. Therefore, the number of carbon atoms is preferably selected from acyl groups having 2 to 6 carbon atoms.
- the cellulose ester preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
- the cellulose ester includes cellulose acetate propionate, cellulose acetate butyrate, or a mixed fatty acid ester of cellulose to which a propionate group or a butyrate group is bonded in addition to an acetyl group such as cellulose acetate propionate butyrate. Can be used.
- the butyryl group that forms butyrate may be linear or branched.
- cellulose ester preferably used in the present invention, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate phthalate are particularly preferably used.
- Preferred cellulose esters other than cellulose acetate phthalate for the present invention preferably satisfy the following formulas (1) and (2).
- Formula (2) 0 ⁇ Y ⁇ 1.5
- X is the degree of substitution of the acetyl group
- Y is the degree of substitution of the propionyl group or butyryl group, or a mixture thereof.
- resins having different degrees of substitution may be mixed and used.
- the mixing ratio is preferably 10:90 to 90:10 (mass ratio).
- cellulose acetate propionate is particularly preferably used.
- the method for measuring the substitution degree of the acyl group can be measured according to ASTM-D817-96.
- the number average molecular weight of the cellulose ester used in the present invention is preferably in the range of 60,000 to 300,000, and the resulting film is preferably strong in mechanical strength. Furthermore, 70,000-200000 are preferably used.
- the weight average molecular weight Mw and number average molecular weight Mn of the cellulose ester were measured using gel permeation chromatography (GPC).
- the measurement conditions are as follows.
- the cellulose used as a raw material of the cellulose ester used in the present invention is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively.
- the cellulose ester such as cellulose acetate phthalate of the present invention can be produced by a known method. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.
- Formula (I) B- (GA) nGB (Wherein B is an arylcarboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, A Represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.)
- an arylcarboxylic acid residue represented by B and an alkylene glycol residue or oxyalkylene glycol residue or arylglycol residue represented by G, an alkylenedicarboxylic acid residue or aryldicarboxylic acid represented by A And is obtained by the same reaction as a normal polyester compound.
- arylcarboxylic acid component of the aromatic-terminated polyester compound used in the present invention examples include, for example, benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal There are propylbenzoic acid, aminobenzoic acid, acetoxybenzoic acid and the like, and these can be used as one kind or a mixture of two or more kinds, respectively.
- alkylene glycol component having 2 to 12 carbon atoms of the aromatic terminal polyester compound examples 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 There are 3-pentane
- alkylene glycols having 2 to 12 carbon atoms are particularly preferable because of excellent compatibility with cellulose esters.
- Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal polyester compound include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and the like. One kind or a mixture of two or more kinds can be used.
- alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal polyester compound examples include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These are used as one kind or a mixture of two or more kinds, respectively.
- arylene dicarboxylic acid component having 6 to 12 carbon atoms examples include phthalic acid, terephthalic acid, isophthalic acid, 1,5 naphthalene dicarboxylic acid, and 1,4 naphthalene dicarboxylic acid.
- n is preferably 1 or more and 100 or less, and the number average molecular weight is preferably 300 to 1500, more preferably 400 to 1000.
- the acid value is 0.5 mgKOH / g or less, the hydroxyl value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl value is 15 mgKOH / g or less.
- the aromatic terminal polyester compound represented by the general formula (I) of the present invention is preferably contained in an amount of 0.5 to 30% by mass based on the cellulose ester.
- aromatic terminal polyester compound that can be used in the present invention are shown below, but the present invention is not limited thereto.
- the cellulose ester film of the present invention is characterized by comprising an ester compound having at least one pyranose structure or at least one furanose structure and having all or part of OH groups in the structure esterified.
- the proportion of esterification is preferably 70% or more of the OH groups present in the pyranose structure or furanose structure.
- ester compounds are collectively referred to as sugar ester compounds.
- ester compound of the present invention examples include the following, for example, but the present invention is not limited to these.
- Glucose galactose, mannose, fructose, xylose or arabinose, lactose, sucrose, nystose, 1F-fructosyl nystose, stachyose, maltitol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose or kestose .
- gentiobiose gentiotriose
- gentiotetraose gentiotetraose
- xylotriose galactosyl sucrose
- sucrose for example, sucrose, kestose, nystose, 1F-fructosyl nystose, stachyose and the like are preferable, and sucrose is more preferable.
- the monocarboxylic acid used for esterifying all or part of the OH groups in the pyranose structure or furanose structure of the present invention is not particularly limited, and known aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, An aromatic monocarboxylic acid or the like can be used.
- the carboxylic acid used may be one type or a mixture of two or more types.
- Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid , Saturated fatty acids such as tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, Examples include unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and oc
- Examples of preferable alicyclic monocarboxylic acids include acetic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.
- aromatic monocarboxylic acids examples include aromatic monocarboxylic acids having an alkyl group or alkoxy group introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, cinnamic acid, benzylic acid, biphenylcarboxylic acid, and naphthalene.
- aromatic monocarboxylic acids having two or more benzene rings such as carboxylic acid and tetralin carboxylic acid, or derivatives thereof.
- Oligosaccharide ester compounds can be applied as compounds having 1 to 12 at least one of the pyranose structure or furanose structure according to the present invention.
- Oligosaccharides are produced by allowing an enzyme such as amylase to act on starch, sucrose, etc.
- examples of oligosaccharides that can be applied to the present invention include maltooligosaccharides, isomaltoligosaccharides, fructooligosaccharides, galactooligosaccharides, and xylooligos. Sugar.
- the said ester compound is a compound which condensed 1 or more and 12 or less of at least 1 sort (s) of the pyranose structure or furanose structure represented with the following general formula (A).
- R 11 to R 15 and R 21 to R 25 each represents an acyl group having 2 to 22 carbon atoms or a hydrogen atom, m and n each represents an integer of 0 to 12, and m + n represents an integer of 1 to 12.
- R 11 to R 15 and R 21 to R 25 are preferably a benzoyl group or a hydrogen atom.
- the benzoyl group may further have a substituent R 26 (p is 0 to 5), and examples thereof include an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and further, these alkyl groups, alkenyl groups, and phenyl groups. May have a substituent.
- Oligosaccharides can also be produced by the same method as the ester compound of the present invention.
- ester compound according to the present invention will be given below, but the present invention is not limited thereto.
- the cellulose ester film of the present invention preferably contains the sugar ester compound of the present invention in an amount of 0.5 to 30% by mass of the cellulose ester film in order to suppress the fluctuation of the retardation value and stabilize the display quality.
- the content is preferably 5 to 30% by mass.
- the content of the aromatic terminal polyester compound and sugar ester compound represented by the general formula (I) of the present invention can be selected in a mass ratio ranging from 99: 1 to 1:99, and the total amount of both compounds is The content is preferably 1 to 40% by mass relative to the cellulose ester.
- the cellulose ester film of the present invention can contain a plasticizer as necessary to obtain the effects of the present invention.
- the plasticizer is not particularly limited, but is preferably a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer, a polyhydric alcohol ester plasticizer, or a polyester plasticizer. Agent, acrylic plasticizer and the like.
- At least one is preferably a polyhydric alcohol ester plasticizer.
- the polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
- a divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
- the polyhydric alcohol preferably used in the present invention is represented by the following general formula (a).
- R1- (OH) n represents an n-valent organic group
- n represents a positive integer of 2 or more
- the OH group represents an alcoholic and / or phenolic hydroxyl group.
- Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these.
- triethylene glycol triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.
- monocarboxylic acid used for polyhydric alcohol ester there is no restriction
- Preferred examples of the monocarboxylic acid include the following, but the present invention is not limited to this.
- aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used.
- the number of carbon atoms is more preferably 1-20, and particularly preferably 1-10.
- acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
- Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
- Examples of preferable alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
- aromatic monocarboxylic acids examples include those in which 1 to 3 alkoxy groups such as alkyl group, methoxy group or ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.
- the molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.
- the carboxylic acid used in the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
- the glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
- alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl
- phthalate ester plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
- citrate plasticizer examples include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.
- fatty acid ester plasticizers examples include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
- phosphate ester plasticizer examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.
- the polyvalent carboxylic acid ester compound is composed of an ester of a divalent or higher, preferably a divalent to 20valent polyvalent carboxylic acid and an alcohol.
- the aliphatic polyvalent carboxylic acid is preferably divalent to 20-valent, and in the case of an aromatic polyvalent carboxylic acid or alicyclic polyvalent carboxylic acid, it is preferably trivalent to 20-valent.
- the polyvalent carboxylic acid is represented by the following general formula (b).
- R2 (COOH) m (OH) n
- R2 is an (m + n) -valent organic group
- m is a positive integer of 2 or more
- n is an integer of 0 or more
- a COOH group is a carboxyl group
- an OH group is an alcoholic or phenolic hydroxyl group
- preferred polyvalent carboxylic acids include the following, but the present invention is not limited to these.
- Trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, tetrahydrophthal
- An aliphatic polyvalent carboxylic acid such as an acid, an oxypolyvalent carboxylic acid such as tartaric acid, tartronic acid, malic acid and citric acid can be preferably used.
- the alcohol used in the polyvalent carboxylic acid ester compound that can be used in the present invention is not particularly limited, and known alcohols and phenols can be used.
- an aliphatic saturated alcohol or aliphatic unsaturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
- alicyclic alcohols such as cyclopentanol and cyclohexanol or derivatives thereof
- aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, or derivatives thereof can be preferably used.
- the alcoholic or phenolic hydroxyl group of the oxypolycarboxylic acid may be esterified with a monocarboxylic acid.
- monocarboxylic acids include the following, but the present invention is not limited thereto.
- aliphatic monocarboxylic acid a straight-chain or side-chain fatty acid having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
- Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
- Examples of preferable alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
- aromatic monocarboxylic acids examples include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid. And aromatic monocarboxylic acids possessed by them, or derivatives thereof. Particularly preferred are acetic acid, propionic acid, and benzoic acid.
- the molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750.
- the larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.
- the alcohol used for the polyvalent carboxylic acid ester that can be used in the present invention may be one kind or a mixture of two or more kinds.
- the acid value of the polyvalent carboxylic acid ester compound that can be used in the present invention is preferably 1 mgKOH / g or less, and more preferably 0.2 mgKOH / g or less. Setting the acid value in the above range is preferable because the environmental fluctuation of retardation is also suppressed.
- the acid value refers to the number of milligrams of potassium hydroxide necessary to neutralize the acid (carboxyl group present in the sample) contained in 1 g of the sample.
- the acid value is measured according to JIS K0070.
- tributyl trimellitic acid and tetrabutyl pyromellitic acid.
- the cellulose ester film B according to the present invention can also contain an ultraviolet absorber.
- the ultraviolet absorber is intended to improve durability by absorbing ultraviolet light having a wavelength of 400 nm or less, and the transmittance at a wavelength of 370 nm is particularly preferably 10% or less, more preferably 5% or less. Preferably it is 2% or less.
- the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.
- These are commercially available products manufactured by Ciba Specialty Chemicals and can be preferably used.
- the UV absorbers preferably used in the present invention are benzotriazole UV absorbers, benzophenone UV absorbers, and triazine UV absorbers, particularly preferably benzotriazole UV absorbers and benzophenone UV absorbers. .
- a discotic compound such as a compound having a 1,3,5 triazine ring is also preferably used as an ultraviolet absorber.
- the polarizing plate protective film according to the present invention preferably contains two or more ultraviolet absorbers.
- a polymeric ultraviolet absorber can be preferably used, and in particular, a polymer type ultraviolet absorber described in JP-A-6-148430 is preferably used.
- the method for adding the UV absorber is to add the UV absorber to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane, or a mixed solvent thereof. Or you may add directly in dope composition.
- an alcohol such as methanol, ethanol or butanol
- an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane, or a mixed solvent thereof.
- inorganic powders that do not dissolve in organic solvents use a dissolver or sand mill in the organic solvent and cellulose ester to disperse them before adding them to the dope.
- the amount of the UV absorber used is not uniform depending on the type of UV absorber, the operating conditions, etc., but when the dry film thickness of the polarizing plate protective film is 30 to 200 ⁇ m, the amount used is 0.5 to the polarizing plate protective film. Is preferably 10 to 10% by mass, and more preferably 0.6 to 4% by mass.
- Antioxidant are also referred to as deterioration inhibitors.
- a liquid crystal image display device or the like is placed in a high humidity and high temperature state, the cellulose ester film may be deteriorated.
- the antioxidant has a role of delaying or preventing the cellulose ester film from being decomposed by, for example, a residual solvent amount of halogen in the cellulose ester film or phosphoric acid of a phosphoric acid plasticizer. It is preferable to make it contain in a film.
- a hindered phenol compound is preferably used.
- 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oct Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl
- 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred.
- hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
- the amount of these compounds added is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the cellulose derivative.
- the cellulose ester film according to the present invention preferably contains fine particles.
- examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, and hydrated silicic acid. Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate. Further, fine particles of an organic compound can also be preferably used.
- organic compounds include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, acrylic styrene resin, silicone resin, polycarbonate resin, benzoguanamine resin, melamine resin
- organic polymer compounds such as polyolefin powder, polyester resin, polyamide resin, polyimide resin, polyfluorinated ethylene resin, and starch.
- a polymer compound synthesized by a suspension polymerization method, a polymer compound made spherical by a spray dry method or a dispersion method, or an inorganic compound can be used.
- Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
- the average primary particle size of the fine particles is preferably 5 to 400 nm, and more preferably 10 to 300 nm.
- These may be mainly contained as secondary aggregates having a particle size of 0.05 to 0.3 ⁇ m, and may be contained as primary particles without being aggregated if the particles have an average particle size of 100 to 400 nm. preferable.
- the content of these fine particles in the polarizing plate protective film is preferably 0.01 to 1% by mass, particularly preferably 0.05 to 0.5% by mass. In the case of a polarizing plate protective film having a multilayer structure by the co-casting method, it is preferable to contain fine particles of this addition amount on the surface.
- Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). it can.
- Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.
- Examples of the polymer include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.
- Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the turbidity of the polarizing plate protective film low.
- the dynamic friction coefficient of at least one surface is 0.2 to 1.0.
- additives may be batch-added to a dope that is a cellulose ester-containing solution before film formation, or an additive solution may be separately prepared and added in-line.
- an additive solution may be separately prepared and added in-line.
- a preferable amount of the cellulose ester is 1 to 10 parts by mass, and more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the solvent.
- a static mixer manufactured by Toray Engineering
- SWJ Toray static type in-tube mixer Hi-Mixer
- the cellulose ester film according to the present invention can be preferably used regardless of whether it is a film produced by a solution casting method or a film produced by a melt casting method.
- the cellulose ester film of the present invention is prepared by dissolving a cellulose ester and an additive in a solvent to prepare a dope, casting a dope onto an endless metal support, and casting the dope. It is carried out by a step of drying as a web, a step of peeling from a metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.
- the concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become.
- the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
- the solvent used in the dope may be used alone or in combination of two or more, but it is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester in terms of production efficiency, and there are many good solvents. This is preferable from the viewpoint of the solubility of the cellulose ester.
- a preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
- the good solvent and the poor solvent change depending on the average acetylation degree (acetyl group substitution degree) of the cellulose ester.
- the good solvent and the poor solvent change depending on the average acetylation degree (acetyl group substitution degree) of the cellulose ester.
- the good solvent and the poor solvent change depending on the average acetylation degree (acetyl group substitution degree) of the cellulose ester.
- the cellulose ester acetate ester acetyl group substitution degree 2.4
- cellulose Acetate propionate is a good solvent
- cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.
- the good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetoacetate. Particularly preferred is methylene chloride or methyl acetate.
- the poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used.
- the dope preferably contains 0.01 to 2% by mass of water.
- the solvent used for dissolving the cellulose ester is used by collecting the solvent removed from the film by drying in the film-forming process and reusing it.
- the recovery solvent may contain trace amounts of additives added to the cellulose ester, such as plasticizers, UV absorbers, polymers, monomer components, etc., but even if these are included, they are preferably reused. Can be purified and reused if necessary.
- additives added to the cellulose ester such as plasticizers, UV absorbers, polymers, monomer components, etc., but even if these are included, they are preferably reused. Can be purified and reused if necessary.
- a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure.
- a method in which a cellulose ester is mixed with a poor solvent and wetted or swollen, and then a good solvent is added and dissolved is also preferably used.
- Pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside.
- a jacket type is preferable because temperature control is easy.
- the heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates.
- the preferred heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C.
- the pressure is adjusted so that the solvent does not boil at the set temperature.
- a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.
- the cellulose ester solution is filtered using an appropriate filter medium such as filter paper.
- an appropriate filter medium such as filter paper.
- the filter medium it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but there is a problem that the filter medium is likely to be clogged if the absolute filtration accuracy is too small.
- a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.
- the material of the filter medium there are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable.
- Bright spot foreign matter means that when two polarizing plates are placed in a crossed Nicol state, an optical film or the like is placed between them, light is applied from one polarizing plate side, and observation is performed from the other polarizing plate side. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm 2 or less.
- it is 100 pieces / cm 2 or less, still more preferably 50 pieces / m 2 or less, still more preferably 0 to 10 pieces / cm 2 . Further, it is preferable that the number of bright spots of 0.01 mm or less is small.
- the dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration.
- the increase in the difference (referred to as differential pressure) is small and preferable.
- the preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.
- the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
- the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
- the cast width can be 1 ⁇ 4m.
- the surface temperature of the metal support in the casting step is ⁇ 50 ° C. to less than the boiling point of the solvent, and a higher temperature is preferable because the web drying speed can be increased. May deteriorate.
- the preferred support temperature is 0 to 55 ° C, more preferably 25 to 50 ° C.
- the method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When warm air is used, wind at a temperature higher than the target temperature may be used.
- the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Particularly preferred is 20 to 30% by mass or 70 to 120% by mass.
- the amount of residual solvent is defined by the following formula.
- Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
- the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Particularly preferred is 0 to 0.01% by mass or less.
- a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method in which the web is dried while being conveyed by a tenter method are employed.
- the cellulose ester film of the present invention it is particularly preferable to perform stretching in the width direction (lateral direction) by a tenter method in which both ends of the web are held with clips or the like. Peeling is preferably performed at a peeling tension of 300 N / m or less.
- the means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but is preferably performed with hot air in terms of simplicity.
- drying temperature in the web drying process is increased stepwise from 40 to 200 ° C.
- the film thickness of the cellulose ester film is not particularly limited, but 10 to 200 ⁇ m is used.
- the film thickness is particularly preferably 10 to 100 ⁇ m. More preferably, it is 20 to 60 ⁇ m.
- the cellulose ester film of the present invention has a width of 1 to 4 m. Particularly, those having a width of 1.4 to 4 m are preferably used, and particularly preferably 1.6 to 3 m. If it exceeds 4 m, conveyance becomes difficult.
- the cellulose ester film has the structure of the present invention, and the refractive index is controlled by controlling the transport tension and stretching.
- the retardation value can be changed by lowering or increasing the tension in the longitudinal direction.
- biaxial stretching or uniaxial stretching can be performed sequentially or simultaneously with respect to the longitudinal direction (film forming direction) of the film and the direction orthogonal to the longitudinal direction of the film, that is, the width direction.
- the draw ratios in the biaxial directions perpendicular to each other are preferably in the range of 0.8 to 1.5 times in the casting direction and 1.1 to 2.5 times in the width direction, respectively. It is preferable to carry out in the range of 0.8 to 1.0 times in the direction and 1.2 to 2.0 times in the width direction.
- the stretching temperature is preferably 120 ° C. to 200 ° C., more preferably 150 ° C. to 200 ° C., more preferably more than 150 ° C. and 190 ° C. or less.
- the residual solvent in the film is preferably 20 to 0%, more preferably 15 to 0%.
- the residual solvent is stretched by 11% at 155 ° C., or the residual solvent is stretched by 2% at 155 ° C. Alternatively, it is preferable that the residual solvent is stretched at 11% at 160 ° C, or the residual solvent is stretched at less than 1% at 160 ° C.
- the method of stretching the web For example, a method in which a circumferential speed difference is applied to a plurality of rolls, and the roll circumferential speed difference is used to stretch the rolls in the longitudinal direction. And a method of stretching in the vertical direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, or a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions. Of course, these methods may be used in combination.
- a tenter it may be a pin tenter or a clip tenter.
- the slow axis or the fast axis of the cellulose ester film of the present invention exists in the film plane, and ⁇ 1 is preferably ⁇ 1 ° or more and + 1 ° or less, assuming that the angle formed with the film forming direction is ⁇ 1. More preferably, it is 5 ° or more and + 0.5 ° or less.
- This ⁇ 1 can be defined as an orientation angle, and ⁇ 1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
- ⁇ 1 satisfying the above relationship can contribute to obtaining high luminance in a display image, suppressing or preventing light leakage, and contributing to obtaining faithful color reproduction in a color liquid crystal display device.
- ⁇ Physical properties of cellulose ester film> The moisture permeability of the cellulose ester film according to the present invention is preferably 300 to 1800 g / m 2 ⁇ 24 h at 40 ° C. and 90% RH, more preferably 400 to 1500 g / m 2 ⁇ 24 h, and 40 to 1300 g / m 2 ⁇ 24 h. Is particularly preferred.
- the moisture permeability can be measured according to the method described in JIS Z 0208.
- the cellulose ester film according to the present invention has a breaking elongation of preferably 10 to 80%, more preferably 20 to 50%.
- the visible light transmittance of the cellulose ester film according to the present invention is preferably 90% or more, and more preferably 93% or more.
- the haze of the cellulose ester film according to the present invention is preferably less than 1%, particularly preferably 0 to 0.1%.
- the cellulose ester film which is the retardation film of the present invention can be used for a polarizing plate having a polarizing plate protective film and the liquid crystal display device of the present invention using the polarizing plate.
- the polarizing plate of the present invention is characterized in that it is a polarizing plate bonded to at least one surface of a polarizer using the cellulose ester film of the present invention as a polarizing plate protective film.
- the liquid crystal display device of the present invention is characterized in that the polarizing plate according to the present invention is bonded to at least one liquid crystal cell surface via an adhesive layer.
- the polarizing plate of the present invention can be produced by a general method.
- the cellulose ester film of the present invention is preferably bonded to at least one surface of a polarizer produced by subjecting the polarizer side to alkali saponification treatment and immersion drawing in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution.
- cellulose ester films for example, Konica Minoltack KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC8UX-RHA, KC8UX-RHA, KC8UX KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.
- cellulose ester films for example, Konica Minoltack KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC8UX-RHA, KC8UX-RHA, KC8UX KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.
- the polarizing plate protective film used on the surface side of the display device preferably has an antiglare layer, a clear hard coat layer, an antireflection layer, an antistatic layer, an antifouling layer, and a backcoat layer.
- a polarizer which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass.
- a typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol.
- iodine is dyed on a system film and one in which dichroic dye is dyed.
- the polarizer is formed by forming a polyvinyl alcohol aqueous solution into a film and dyeing the film by uniaxial stretching or dyeing or uniaxially stretching, and then performing a durability treatment with a boron compound.
- the film thickness of the polarizer is preferably 5 to 30 ⁇ m, particularly preferably 10 to 20 ⁇ m.
- the ethylene unit content described in JP-A-2003-248123, JP-A-2003-342322, etc. is 1 to 4 mol%
- the degree of polymerization is 2000 to 4000
- the degree of saponification is 99.0 to 99.99 mol%.
- Ethylene-modified polyvinyl alcohol is also preferably used.
- an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 66 to 73 ° C. is preferably used.
- the difference in hot water cutting temperature between two points 5 cm away in the TD direction of the film is more preferably 1 ° C. or less in order to reduce color spots, and two points separated 1 cm in the TD direction of the film. In order to reduce color spots, it is more preferable that the difference in the hot water cutting temperature is 0.5 ° C. or less.
- a polarizer using this ethylene-modified polyvinyl alcohol film is excellent in polarization performance and durability performance and has few color spots, and is particularly preferably used for a large liquid crystal display device.
- the polarizer obtained as described above is usually used as a polarizing plate with a protective film bonded to both sides or one side.
- the adhesive used for pasting include a PVA-based adhesive and a urethane-based adhesive. Among them, a PVA-based adhesive is preferably used.
- the cellulose ester film of the present invention can be used in liquid crystal display devices of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB.
- a VA (MVA, PVA) type liquid crystal display device is preferable.
- liquid crystal display device with a 30-inch screen or more can obtain a liquid crystal display device with excellent visibility such as uneven coloring and front contrast with little environmental fluctuation, reduced light leakage.
- Example 1 ⁇ Production of Cellulose Ester Film 101> ⁇ Fine particle dispersion 1> Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by weight Ethanol 89 parts by weight The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.
- Fine particle addition liquid 1 The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.
- a main dope solution having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose esters A and B were added to a pressurized dissolution tank containing a solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope solution was prepared by filtration using 244.
- the dope solution was uniformly cast on a stainless steel belt support at a temperature of 33 ° C. and a width of 1500 mm. The temperature of the stainless steel belt was controlled at 30 ° C.
- the solvent was evaporated until the amount of residual solvent in the cast (cast) film reached 75%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.
- the peeled cellulose ester film was stretched 36% in the width direction using a tenter while applying heat at 150 ° C.
- the residual solvent at the start of stretching was 15%.
- drying was terminated while the drying zone was conveyed by a number of rolls.
- the drying temperature was 130 ° C. and the transport tension was 100 N / m.
- a cellulose ester film 101 having a dry film thickness of 40 ⁇ m was obtained.
- cellulose ester films 102 to 115 were prepared in substantially the same manner except that 109 and 111 were further added with a plasticizer and the solvent type, film thickness, and draw ratio were changed as shown in Table 2.
- Plasticizer A Triphenyl phosphate Plasticizer B: Ethylphthalylethyl glycolate Plasticizer C: Trimethylolpropane benzoate Further, 201 to 207 were prepared as comparative samples.
- ⁇ Haze ⁇ Measurement was performed according to JIS K-6714 using a haze meter 1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.
- the samples were measured by fixing the slow axis of the film horizontally and vertically on the sample stage.
- Example 2 Preparation of polarizing plate> A polyvinyl alcohol film having a thickness of 120 ⁇ m was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times).
- a polarizer, the cellulose ester films 101 to 207, and Konica Minolta Tack KC4UY (cellulose ester film manufactured by Konica Minolta Opto Co., Ltd.) were bonded to the back side to prepare a polarizing plate.
- Step 1 Soaked in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to obtain a saponified cellulose ester film bonded to the polarizer.
- Step 2 The polarizer was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
- Step 3 Excess adhesive adhered to the polarizer in Step 2 was gently wiped off and placed on the cellulose ester film treated in Step 1.
- Step 4 The cellulose ester films 101 to 207 laminated in Step 3 were bonded together with a polarizer and a back side cellulose ester film at a pressure of 20 to 30 N / cm 2 and a conveying speed of about 2 m / min.
- Step 5 A sample obtained by bonding the polarizer prepared in Step 4 with the cellulose ester films 101 to 207 and Konica Minoltack KC4UY in a drier at 80 ° C. is dried for 2 minutes, and the polarizing plates 101 to 116 and 201 to 207 are bonded.
- ⁇ Production of liquid crystal display device> A liquid crystal panel for viewing angle measurement was produced as follows, and the characteristics as a liquid crystal display device were evaluated.
- the polarizing plates on both sides of the 40-inch display KLV-40J3000 made by SONY were peeled off in advance, and the prepared polarizing plates 101 to 116 were respectively bonded to both surfaces of the glass surface of the liquid crystal cell.
- the direction of bonding of the polarizing plate is such that the surface of the cellulose ester film of the present invention is on the liquid crystal cell side, and the absorption axis is in the same direction as the polarizing plate previously bonded.
- liquid crystal display devices 101 to 116 and 201 to 207 were produced.
- This liquid crystal display device was evaluated for color variation and front contrast. The results are shown in Table 3.
- Front contrast (brightness of white display measured from normal direction of display device) / (brightness of black display measured from normal direction of display device)
- liquid crystal display devices 101 to 116 of the present invention are liquid crystal display devices excellent in color variation and front contrast.
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Abstract
Description
(式中、Bはアリールカルボン酸残基、Gは炭素数2~12のアルキレングリコール残基または炭素数6~12のアリールグリコール残基または炭素数が4~12のオキシアルキレングリコール残基、Aは炭素数4~12のアルキレンジカルボン酸残基または炭素数6~12のアリールジカルボン酸残基を表し、またnは1以上の整数を表す。)
2 分光器
3 試料台(ステージ)
4 試料
5 受光部分
θ 光源の法線方向と、サンプルの観察点と積分球とを結ぶ方向とがなす角
Rt=((nx+ny)/2-nz)×d
(式中、nxは位相差フィルムの面内の遅相軸方向の屈折率を、nyは面内で遅相軸に直交する方向の屈折率を、nzは厚み方向の屈折率を、dは位相差フィルムの厚み(nm)をそれぞれ表す。屈折率の測定波長は590nmである。)
上記屈折率は、例えばKOBRA-21ADH(王子計測機器(株))を用いて、23℃、55%RHの環境下で、波長が590nmで求めることができる。
<ゴニオフォトメーターにより測定される散乱光>
本発明の位相差フィルムは、前記レターデーションを得るために延伸処理をしても、ゴニオフォトメーターによって測定された散乱光が、一定の範囲にあることを特徴とする。
図1にゴニオフォトメーター(型式:GP-1-3D、オプテック(株)製)の概略を示す。1.光源ランプ、2.分光器、3.試料台(ステージともいう)、4.試料、5.受光部分である。
一般式(I) B-(G-A)n-G-B
(式中、Bはアリールカルボン酸残基、Gは炭素数2~12のアルキレングリコール残基または炭素数6~12のアリールグリコール残基または炭素数が4~12のオキシアルキレングリコール残基、Aは炭素数4~12のアルキレンジカルボン酸残基または炭素数6~12のアリールジカルボン酸残基を表し、またnは1以上の整数を表す。)
およびピラノース構造またはフラノース構造の少なくとも1種を1個以上12個以下有しその構造のOH基のすべてもしくは一部をエステル化したエステル化合物を、少なくとも一種含有するセルロースエステルフィルムであることが好ましい。
本発明のセルロースエステルとしては特に限定はないが、セルロースエステルとして炭素数2~22程度のカルボン酸エステルであり、芳香族カルボン酸のエステルでもよく、特に炭素数が6以下の低級脂肪酸エステルであることが好ましい。
式(2) 0≦Y≦1.5
式中、Xはアセチル基の置換度、Yはプロピオニル基またはブチリル基、もしくはその混合物の置換度である。
カラム: Shodex K806、K805、K803G(昭和電工(株)製を3本接続して使用した)
カラム温度:25℃
試料濃度: 0.1質量%
検出器: RI Model 504(GLサイエンス社製)
ポンプ: L6000(日立製作所(株)製)
流量: 1.0ml/min
校正曲線: 標準ポリスチレンSTK standard ポリスチレン(東ソー(株)製)Mw=1000000~500の13サンプルによる校正曲線を使用した。13サンプルは、ほぼ等間隔に用いる。
本発明では、下記一般式(I)で表せる芳香族末端ポリエステル系化合物を使用する。
(式中、Bはアリールカルボン酸残基、Gは炭素数2~12のアルキレングリコール残基または炭素数6~12のアリールグリコール残基または炭素数が4~12のオキシアルキレングリコール残基、Aは炭素数4~12のアルキレンジカルボン酸残基または炭素数6~12のアリールジカルボン酸残基を表し、またnは1以上の整数を表す。)
一般式(I)中、Bで示されるアリールカルボン酸残基とGで示されるアルキレングリコール残基またはオキシアルキレングリコール残基またはアリールグリコール残基、Aで示されるアルキレンジカルボン酸残基またはアリールジカルボン酸残基とから構成されるものであり、通常のポリエステル系化合物と同様の反応により得られる。
本発明のセルロースエステルフィルムは、ピラノース構造またはフラノース構造の少なくとも1種を1個以上12個以下有しその構造のOH基のすべてもしくは一部をエステル化したエステル化合物を含むことを特徴とする。
〈その他の添加剤〉
(可塑剤)
本発明のセルロースエステルフィルムは、本発明の効果を得る上で必要に応じて可塑剤を含有することができる。
但し、R1はn価の有機基、nは2以上の正の整数、OH基はアルコール性、及び/またはフェノール性水酸基を表す。
(但し、R2は(m+n)価の有機基、mは2以上の正の整数、nは0以上の整数、COOH基はカルボキシル基、OH基はアルコール性またはフェノール性水酸基を表す)
好ましい多価カルボン酸の例としては、例えば以下のようなものを挙げることができるが、本発明はこれらに限定されるものではない。
本発明に係るセルロースエステルフィルムBは、紫外線吸収剤を含有することもできる。紫外線吸収剤は400nm以下の紫外線を吸収することで、耐久性を向上させることを目的としており、特に波長370nmでの透過率が10%以下であることが好ましく、より好ましくは5%以下、更に好ましくは2%以下である。
酸化防止剤は劣化防止剤ともいわれる。高湿高温の状態に液晶画像表示装置などがおかれた場合には、セルロースエステルフィルムの劣化が起こる場合がある。
本発明に係るセルロースエステルフィルムは、微粒子を含有することが好ましい。
〈セルロースエステルフィルムの製造方法〉
次に、本発明のセルロースエステルフィルムの製造方法について説明する。
尚、Mはウェブまたはフィルムを製造中または製造後の任意の時点で採取した試料の質量で、NはMを115℃で1時間の加熱後の質量である。
〈セルロースエステルフィルムの物性〉
本発明に係るセルロースエステルフィルムの透湿度は、40℃、90%RHで300~1800g/m2・24hが好ましく、更に400~1500g/m2・24hが好ましく、40~1300g/m2・24hが特に好ましい。透湿度はJIS Z 0208に記載の方法に従い測定することができる。
本発明の位相差フィルムであるセルロースエステルフィルムを、偏光板保護フィルムとした偏光板、それを用いた本発明の液晶表示装置に使用することができる。
本発明の偏光板を液晶表示装置に用いることによって、種々の視認性に優れた本発明の液晶表示装置を作製することができる。
<セルロースエステルフィルム101の作製>
〈微粒子分散液1〉
微粒子(アエロジル R972V 日本アエロジル(株)製) 11質量部
エタノール 89質量部
以上をディゾルバーで50分間攪拌混合した後、マントンゴーリンで分散を行った。
メチレンクロライドを入れた溶解タンクに十分攪拌しながら、微粒子分散液1をゆっくりと添加した。更に、二次粒子の粒径が所定の大きさとなるようにアトライターにて分散を行った。これを日本精線(株)製のファインメットNFで濾過し、微粒子添加液1を調製した。
微粒子分散液1 5質量部
下記組成の主ドープ液を調製した。まず加圧溶解タンクにメチレンクロライドとエタノールを添加した。溶剤の入った加圧溶解タンクにセルロースエステルA,Bを攪拌しながら投入した。これを加熱し、攪拌しながら、完全に溶解し。これを安積濾紙(株)製の安積濾紙No.244を使用して濾過し、主ドープ液を調製した。
メチレンクロライド 340質量部
エタノール 64質量部
本発明のセルロースエステルA 100質量部
本発明のポリエステル系化合物14 6.5質量部
本発明の糖エステル化合物3 6.0質量部
微粒子添加液1 1質量部
以上を密閉容器に投入し、攪拌しながら溶解してドープ液を調製した。次いで、無端ベルト流延装置を用い、ドープ液を温度33℃、1500mm幅でステンレスベルト支持体上に均一に流延した。ステンレスベルトの温度は30℃に制御した。
可塑剤B:エチルフタリルエチルグリコレート
可塑剤C:トリメチロールプロパン安息香酸エステル
また、比較試料として201~207を作製した。
得られたフィルムから試料35mm×35mmを切り出し、25℃,55%RHで2時間調湿し、自動複屈折計(KOBRA21DH、王子計測(株))で、590nmにおける垂直方向から測定した値とフィルム面を傾けながら同様に測定したレターデーション値の外挿値より算出した。
ヘイズメーター1001DP型、日本電色工業(株)製を使用してJIS K-6714に準じて測定した。
ゴニオフォトメーター型式:GP-1-3D、オプテック(株)製(光源は、12V50Wハロゲン球、受光部は、光電子増倍管(フォトマル 浜松フォトニクス R636-10))を用いて測定した。
実施例2
<偏光板の作製>
厚さ、120μmのポリビニルアルコールフィルムを、一軸延伸(温度110℃、延伸倍率5倍)した。
<液晶表示装置の作製>
視野角測定を行う液晶パネルを以下のようにして作製し、液晶表示装置としての特性を評価した。
上記作製した各液晶表示装置について、測定機(EZ-Contrast160D、ELDIM社製)を用いて色味変動について測定した。CIE1976、UCS座標において、上下方向(表示法線から上80°~下80°)での最大色味変動幅Δu‘v’を比較した。
23℃55%RHの環境で、各々の液晶表示装置のバックライトを1週間連続点灯した後、測定を行った。測定にはELDIM社製EZ-Contrast160Dを用いて、液晶表示装置で白表示と黒表示の表示画面の法線方向からの輝度を測定し、その比を正面コントラストとした。
Claims (2)
- ゴニオフォトメーターの散乱光プロファイルの入射光90°のフィルムの散乱光強度測定であって、光源から95°~165°の位置における散乱光強度を検出する測定において、フィルム遅相軸を水平に試料台へ設置した場合と垂直に設置した場合の散乱光強度積分値の差が、0.1以下であることを特徴とする位相差フィルム。
- 前記位相差フィルムが、下記一般式(I)に示す芳香族末端ポリエステル系化合物、およびピラノース構造またはフラノース構造の少なくとも1種を1個以上12個以下有しその構造のOH基のすべてもしくは一部をエステル化したエステル化合物を、少なくとも一種含有するセルロースエステルフィルムであることを特徴とする請求の範囲第1項に記載の位相差フィルム。
一般式(I) B-(G-A)n-G-B
(式中、Bはアリールカルボン酸残基、Gは炭素数2~12のアルキレングリコール残基または炭素数6~12のアリールグリコール残基または炭素数が4~12のオキシアルキレングリコール残基、Aは炭素数4~12のアルキレンジカルボン酸残基または炭素数6~12のアリールジカルボン酸残基を表し、またnは1以上の整数を表す。)
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KR1020167012124A KR101739712B1 (ko) | 2008-02-12 | 2009-01-19 | 위상차 필름 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US20110141429A1 (en) * | 2009-12-14 | 2011-06-16 | Fujifilm Corporation | Cellulose acylate film, method for producing cellulose acylate film, polarizer and liquid crystal display device |
CN102295787A (zh) * | 2010-06-21 | 2011-12-28 | 富士胶片株式会社 | 纤维素酰化物膜的制备方法、纤维素酰化物膜、偏振片液晶显示装置和光学补偿膜 |
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US20110019138A1 (en) * | 2008-02-12 | 2011-01-27 | Konica Minolta Opto, Inc. | Retardation film |
WO2012096118A1 (ja) * | 2011-01-11 | 2012-07-19 | コニカミノルタオプト株式会社 | 光学フィルム、該光学フィルムを用いた偏光板、該偏光板の製造方法、並びに液晶表示装置 |
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WO2007043358A1 (ja) * | 2005-10-07 | 2007-04-19 | Konica Minolta Opto, Inc. | セルロースエステルフィルムの製造方法、セルロースエステルフィルム、偏光板及び液晶表示装置 |
WO2008136266A1 (ja) * | 2007-04-26 | 2008-11-13 | Konica Minolta Opto, Inc. | 光学補償フィルムとそれを用いた偏光板及び液晶表示装置 |
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JP2003306577A (ja) * | 2002-04-15 | 2003-10-31 | Daicel Chem Ind Ltd | セルロース系樹脂組成物 |
TWI275835B (en) * | 2002-10-08 | 2007-03-11 | Nitto Denko Corp | Polarizer, optical film, and image display |
JP2005266696A (ja) * | 2004-03-22 | 2005-09-29 | Nitto Denko Corp | 円偏光板、光学フィルムおよび画像表示装置 |
KR101352677B1 (ko) * | 2006-04-25 | 2014-01-16 | 코니카 미놀타 어드밴스드 레이어즈 인코포레이티드 | 위상차 필름, 편광판 및 액정 표시 장치 |
JP5299270B2 (ja) * | 2007-03-20 | 2013-09-25 | コニカミノルタ株式会社 | 位相差フィルム、偏光板、液晶表示装置および位相差フィルムの製造方法 |
US20110019138A1 (en) * | 2008-02-12 | 2011-01-27 | Konica Minolta Opto, Inc. | Retardation film |
-
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- 2009-01-19 CN CN2009801046654A patent/CN101939673B/zh active Active
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WO2007043358A1 (ja) * | 2005-10-07 | 2007-04-19 | Konica Minolta Opto, Inc. | セルロースエステルフィルムの製造方法、セルロースエステルフィルム、偏光板及び液晶表示装置 |
WO2008136266A1 (ja) * | 2007-04-26 | 2008-11-13 | Konica Minolta Opto, Inc. | 光学補償フィルムとそれを用いた偏光板及び液晶表示装置 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110141429A1 (en) * | 2009-12-14 | 2011-06-16 | Fujifilm Corporation | Cellulose acylate film, method for producing cellulose acylate film, polarizer and liquid crystal display device |
JP2011121327A (ja) * | 2009-12-14 | 2011-06-23 | Fujifilm Corp | セルロースアシレートフィルム、その製造方法、偏光板および液晶表示装置 |
CN102295787A (zh) * | 2010-06-21 | 2011-12-28 | 富士胶片株式会社 | 纤维素酰化物膜的制备方法、纤维素酰化物膜、偏振片液晶显示装置和光学补偿膜 |
JP2012067272A (ja) * | 2010-06-21 | 2012-04-05 | Fujifilm Corp | セルロースアシレートフィルムの製造方法、セルロースアシレートフィルム、偏光板、液晶表示装置及び光学補償フィルム |
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US20100309552A1 (en) | 2010-12-09 |
CN101939673B (zh) | 2012-08-08 |
KR20160060144A (ko) | 2016-05-27 |
KR101739712B1 (ko) | 2017-05-24 |
KR20100131425A (ko) | 2010-12-15 |
CN101939673A (zh) | 2011-01-05 |
JPWO2009101839A1 (ja) | 2011-06-09 |
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