CN102890301A - Polarizing film and liquid crystal display device - Google Patents
Polarizing film and liquid crystal display device Download PDFInfo
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- CN102890301A CN102890301A CN2012102539629A CN201210253962A CN102890301A CN 102890301 A CN102890301 A CN 102890301A CN 2012102539629 A CN2012102539629 A CN 2012102539629A CN 201210253962 A CN201210253962 A CN 201210253962A CN 102890301 A CN102890301 A CN 102890301A
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Abstract
The invention provides a polarizing film which improves the problem of unfilled corners in stamping a rectangle compared with a polarizing film for a TN mode liquid crystal, and a liquid crystal display device using the polarizing film. The rectangle-shaped polarizing film suitable for the liquid crystal display device consists of a polarizer, a protective film adhered to one face of the polarizer, and a phase difference film adhered to the other face of the polarizer. The long side or short side of the rectangle-shaped polarizing film forms a 45-degree angle with an absorption axis of the polarizer, a slow axis of the phase difference film is parallel with or orthogonal to the absorption axis of the polarizer, the phase difference film has cellulose acylates as main components, and in the cellulose acylates, the total substituted degree of acyl for hydroxyl which constitutes glucose units of the cellulose acylates is 2.2 to 2.6, the value of Vs/Vf of the phase difference film is above 1.15, the polarizer is constituted by polyvinyl alcohol, and E/d is above 2.0.
Description
Technical field
The present invention relates to TN mode liquid crystal unit with polaroid, used the liquid crystal indicator of this polaroid.
Background technology
In the past, proposed in the viewing angle compensation of TN mode LCD, to utilize the optical anisotropic layer of the hybrid orientation that has used discotic mesogenic, and also made it practical.By utilizing above-mentioned optical anisotropic layer, the viewing angle characteristic of TN mode LCD significantly improves.
On the other hand, proposed in the situation of not using above-mentioned like that special optical anisotropic layer, to have adopted the TN mode LCD of the phase retardation film of optics twin shaft.For example, in TOHKEMY 2009-037231 communique, proposed do not adopting the phase retardation film of optics twin shaft and the visual angle that light-diffusing films improves the TN mode LCD in the situation with above-mentioned like that special optical anisotropic layer.
Except TOHKEMY 2009-037231 communique, many technology are disclosed about the phase retardation film of optics twin shaft, can say roughly the technology of orientation of the polymkeric substance of control display birefringence.For example, the phase retardation film of cellulose system can be under the state that has cooperated various adjuvants and exist under the state of suitable temperature, suitable solvent and make by uniaxial tension.
Polymer orientation state for phase retardation film has various analysis means, but as easy method, can utilize the mensuration of the velocity of sound.For example, in TOHKEMY 2007-264287 communique, have about the relation of the velocity of sound of length direction in the blooming made from the spool form and the velocity of sound of Width to disclose.
Control the phase retardation film of cellulose system of orientation by stretching take thinning as purpose, in order to realize identical phase differential, the state of orientation of having to further improve with less thickness.
But, if state of orientation improves, then impact is also appearred in physical strength.The polaroid that is used for VA pattern or IPS pattern carries out punching press according to the rectangular-shaped long limit or the minor face mode parallel with the length direction of the polaroid of spool form that are fitted on the panel, but as shown in Figure 1, come the punching press rectangle 45 ° of TN pattern purposes medium dips.
Because phase retardation film has the feature of splitting along draw direction easily, so at Fig. 2 (a) and the place (b), the fault so-called angle that lacks easily rectangle, that can not see occurs in the polaroid that VA pattern or IPS pattern are used.
Summary of the invention
Invent problem to be solved
Problem of the present invention is, the polaroid of the unfilled corner of having improved the punching press rectangle for the polaroid of using for the TN mode liquid crystal and the liquid crystal indicator that has used this polaroid are provided.Particularly, problem is, provide can reduce by the spool form tilt 45 ° rectangular-shaped polaroid the unfilled corner fault and can improve the polaroid of yield rate of polaroid and the liquid crystal indicator that has used this polaroid.
For the means of dealing with problems
As described below for the means that address the above problem.
[1] a kind of polaroid; it is characterized in that; it is the rectangular-shaped polaroid that is applicable to liquid crystal indicator; described polaroid is by the polarizer; be bonded in the diaphragm on the one face; and the phase retardation film that is bonded on another face consists of; the long limit of described rectangular-shaped polaroid or the absorption axes angulation of minor face and the described polarizer are 45 °; the slow axis of described phase retardation film or quadrature parallel with the absorption axes of the described polarizer; described phase retardation film contains cellulose acylate as principal ingredient; in the described cellulose acylate; acyl group is 2.2～2.6 to total degree of substitution of the hydroxyl of the glucose unit of formation cellulose acylate; be made as Vs in the velocity of sound with the slow-axis direction of described phase retardation film; when the velocity of sound of quick shaft direction is made as Vf; the value of Vs/Vf is more than 1.15; the described polarizer is made of polyvinyl alcohol (PVA); the axial elastic modulus of the absorption of the described polarizer is being made as E; when the thickness of the described polarizer was made as d, its ratio E/d was more than 0.2.
[2] according to the polaroid of [1], wherein, above-mentioned cellulose acylate is cellulose acetate or the cellulose acetate propionate that satisfies following formula (1) and (2).
（1）2.2≤A+B≤2.6
（2）0≤B≤1.2
Wherein, A represents the degree of substitution of the acetyl group in the cellulose acylate, and B represents the degree of substitution of the propiono in the cellulose acylate.
[3] according to the polaroid of [1] or [2], wherein, postpone Re(550 in the face of above-mentioned phase retardation film under wavelength 550nm) be 20～80nm, the thickness direction retardation Rth(550 under this wavelength) be 100～180nm.
[4] each polaroid in basis [1]～[3], wherein, above-mentioned E/d is 0.22～0.50.
[5] each polaroid in basis [1]～[4], wherein, above-mentioned Vs/Vf is more than 1.15.
[6] according to each described polaroid in [1]～[5], wherein, the average film thickness of said protection film is 20～30 μ m.
[7] according to each described polaroid in [1]～[6], wherein, the tensile modulus of elasticity of said protection film is 4.0～7.0GPa in MD direction, TD direction.
[8] a kind of liquid crystal indicator is characterized in that, it has each polaroid in [1]～[7].
The invention effect
According to the present invention, can provide the polaroid of the unfilled corner of having improved the punching press rectangle for the polaroid of using for the TN mode liquid crystal and the liquid crystal indicator that has used this polaroid.Particularly, can reduce from the unfilled corner fault of the rectangular-shaped polaroid of 45 ° of spool form inclinations, can improve the yield rate of polaroid.
Description of drawings
Fig. 1 is the skeleton diagram of the direction of expression when rectangular polaroid of the present invention carried out punching press.
Fig. 2 is the draw direction of the phase retardation film of expression when in the past rectangular polaroid is carried out punching press and the skeleton diagram at unfilled corner place.Among the figure, the draw direction when arrow represents to make phase retardation film.
Fig. 3 is the diagrammatic cross-section of an example of TN mode LCD of the present invention.
Among the above-mentioned figure, 10 expression liquid crystal layers, 12,14 expression substrates, 16, the 18 expression polarizers, 20 expression phase retardation films, 24,25 expression diaphragms, 30, BL represents backlightly, PL1, PL2 represent polaroid, LC represents liquid crystal cells.
Embodiment
Below listing embodiments of the present invention is elaborated.In addition, the numerical range with "～" expression refers to comprise the numerical value of its front and back record as the scope of lower limit and higher limit in this instructions.
At first, the term that adopts in this instructions is described.
Re(λ), Rth(λ) represent respectively to postpone in the face under the wavelength X and the delay of thickness direction.Re(λ) be in KOBRA 21ADH or prince's WR(instrumentation machine Co., Ltd. system) in, be that the light of λ nm is measured along the normal direction incident wavelength of film.When Selective determination wavelength X nm, can manually change wavelength selective filters or measure by conversion measured values such as programs.When the film of measuring represents with the indicatrix of single shaft or twin shaft, can calculate Rth(λ by following method).
With respect to (not having in the situation of slow axis as sloping shaft (turning axle) with the slow axis in the face (judging by KOBRA21ADH or WR), with the arbitrarily direction in the face as turning axle) embrane method line direction, from normal direction play one-sided 50 ° take 10 degree as the interval light from the direction incident wavelength of this inclination as λ nm respectively, measure whole above-mentioned Re(λ at 6), based on length of delay and the default of mean refractive index and the film thickness value of inputting of this mensuration, calculate Rth(λ by KOBRA21ADH or WR).In above-mentioned, from normal direction with the slow axis in the face as turning axle and have at certain angle of inclination in the situation of film of direction of value vanishing of delay, for greater than the length of delay under the angle of inclination at this angle of inclination, its variation of sign for after negative, is calculated by KOBRA21ADH or WR.In addition, can (not have in the situation of slow axis as sloping shaft (turning axle) with slow axis yet, with the arbitrarily direction in the face as turning axle), from 2 direction detection length of delays that tilt arbitrarily, based on the default of this value and mean refractive index and the film thickness value of inputting, calculate Rth by following formula (A) and formula (B).
In addition, above-mentioned Re(θ) expression is from the length of delay of the direction of normal direction tilt angle theta.In addition, the refractive index of the slow-axis direction in the nx presentation surface in the formula (A), ny is illustrated in the face refractive index with the direction of nx quadrature, and nz represents the refractive index with the direction of nx and ny quadrature.D represents to measure the thickness of film.
Rth=((nx+ny)/2-nz) * d formula (B)
For in can not the situation with the indicatrix of single shaft or twin shaft film performance, that do not have so-called optic axis (optic axis), calculate Rth(λ by following method at the film of measuring).With the slow axis in the face (judging by KOBRA 21ADH or WR) as sloping shaft (turning axle), with respect to embrane method line direction from-50 ° begin till+50 ° take 10 ° as the interval light from the direction incident wavelength of this inclination as λ nm respectively, measure 11 above-mentioned Re(λ), based on length of delay and the default of mean refractive index and the film thickness value of inputting of this mensuration, calculate Rth(λ by KOBRA 21ADH or WR).In addition, in above-mentioned mensuration, the default of mean refractive index can use polymer handbook (JOHN WILEY﹠amp; SONS, INC), the value of the goods catalogue of various bloomings.For the film of the value of still not knowing mean refractive index, can measure with Abbe refractometer.The value illustration of the mean refractive index of main blooming is as follows: cellulose acylate (1.48), cyclic olefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), polystyrene (1.59).By default and the thickness of inputting these mean refractive indexs, calculate nx, ny, nz by KOBRA21ADH or WR.By this nx that calculates, ny, nz, further calculate Nz=(nx-nz)/(nx-ny).
In this instructions, " parallel ", " quadrature " refer to be lower than in the scope of strict angle ± 10 °.The error of this scope and strict angle be preferably be lower than ± 5 °, more preferably be lower than ± 2 °.In addition, " slow axis " refers to that refractive index reaches maximum direction.
In addition, as long as no specifying, the mensuration wavelength of refractive index is exactly the value under the λ=550nm of visible region, about the mensuration wavelength of Re and Rth, as long as no specifying, then is set as 550nm.
The present invention relates to be made as Vs in the velocity of sound with the slow-axis direction of phase retardation film, when the velocity of sound of quick shaft direction is made as Vf, the value of Vs/Vf is the phase retardation film more than 1.15.In addition, in this instructions, with the velocity of propagation of the sound in the film medium referred to as " velocity of sound of film ".
By thinning, the height-oriented phase retardation film of polymer chain also shows anisotropy significantly on the mechanics physical property.In 45 ° the unfilled corner fault of rectangular-shaped polaroid of tilting, lack 1～2mm angle of phase retardation film, and occur along the direction of the stretching of phase retardation film.The stress that phase retardation film is applied by the punching press cutter is direct reason, but thinks that the easy generation of unfilled corner depends on the Vs/Vf of phase retardation film, and is relevant with the orientation of polymer chain.
As the physical property of the orientation that embodies polymer chain, adopt above-mentioned velocity of sound ratio among the present invention.
Scope as the value of the Vs/Vf that can obtain remarkable result is preferably 1.15～1.50, is particularly preferably 1.20～1.40.In addition, the scope of the velocity of sound of film of the present invention is 1.4～3.0km/ second.
Here, the velocity of sound refers to acoustic wave propagation velocity, for the film of under 25 ℃, 60%RH, fully adjusting humidity, under equivalent environment, use sound wave meter (for example wild village's business SST-110 processed), can obtain the velocity of propagation that the compressional wave of the ultrasonic pulse of MD direction (length direction during manufacturing) along film or TD direction (Width during manufacturing) vibrates.
The velocity of sound height of TD direction and the high homology of the degree of orientation of the TD direction of film.Usually, in the high direction of the degree of orientation, the density polymer in the film also uprises, and it is large that the value of the velocity of sound becomes.
The invention is characterized in that it is the rectangular-shaped polaroid that comprises the polarizer, is bonded in the diaphragm on the one face and is bonded in the phase retardation film on another face,
The long limit of described rectangular-shaped polaroid or the absorption axes angulation of minor face and the described polarizer are 45 °,
The slow axis of described phase retardation film or quadrature parallel with the absorption axes of the described polarizer,
Described phase retardation film contains cellulose acylate as principal ingredient, and in the described cellulose acylate, acyl group is 2.2～2.6 to total degree of substitution of the hydroxyl of the glucose unit of formation cellulose acylate,
Be made as Vs in the velocity of sound with the slow-axis direction of described phase retardation film, when the velocity of sound of quick shaft direction is made as Vf, the value of Vs/Vf is more than 1.15,
The described polarizer is made of polyvinyl alcohol (PVA), the axial elastic modulus of the absorption of the described polarizer is made as E, when the thickness of the described polarizer is made as d, its ratio E/d is more than 0.2.
Below, the various members that use among the present invention are described.
1. phase retardation film
Among the present invention; contain cellulose acylate as principal ingredient; in the described cellulose acylate; acyl group is 2.2～2.6 to total degree of substitution of the hydroxyl of the glucose unit of formation cellulose acylate; and then; be made as Vs in the velocity of sound with the slow-axis direction of above-mentioned phase retardation film, when the velocity of sound of quick shaft direction is made as Vf, the value of Vs/Vf is more than 1.15.
About cellulose acylate, be preferably the cellulose acetate or the cellulose acetate propionate that satisfy following formula (1) and (2).
（1）2.2≤A+B≤2.6
（2）0≤B≤1.2
Wherein, A refers to the degree of substitution of the acetyl group in the cellulose acylate, and B refers to the degree of substitution of the propiono in the cellulose acylate.
In this instructions; so-called " containing ... as principal ingredient ", when the cellulose acylate as the materials'use of film is a kind, refer to this cellulose acylate; when being multiple, refer to the cellulose acylate to contain the most at high proportion at the cellulose acylate as the materials'use of film.In the cellulose, the glucose unit of each β-Isosorbide-5-Nitrae bonding has free hydroxyl at 2,3 and 6.The cellulose acylate that uses among the present invention is that the hydrogen atom of average 2.2～2.6 hydroxyls in these 3 hydroxyls is replaced by acetyl group or propiono and the cellulose acetate or the cellulose acetate propionate that are replaced by propiono of the hydrogen atom of 0～1.2 hydroxyl wherein.
In addition, in this instructions, the acetyl group in the cellulose acylate and propiono degree of substitution separately can be calculated by the bonding fatty acid amount of measuring cellulosic Component units unit mass.Assay method is implemented according to " ASTM D817-91 ".
As the cellulose of cellulose acylated raw material, cotton linter or wood pulp (broad leaf tree paper pulp, conifer paper pulp) etc. are arranged, can use the cellulose acylate that is obtained by any raw cellulose, also can according to circumstances mix use.The detailed record of relevant these raw celluloses, (cellulose of record is not particularly limited in the public skill designation of distribution) Huo Development Ming Association Hui Gong Open skill Reported in 1970 2001-1745 number (7 pages～8 pages) for example can to use ball pool, space field work " プ ラ ス チ Star Network Cai Liao Talk seat (17) Xian Victoria prime system Trees fat " the new Wen society of daily magazine industry.
Above-mentioned cellulose acylate preferably has 350～800 the equal degree of polymerization of matter, further preferably has 370～600 the equal degree of polymerization of matter.The cellulose acylate that uses among the present invention in addition preferably has 70000～230000 number-average molecular weight, further preferably has 75000～230000 number-average molecular weight, further preferably has 78000～120000 number-average molecular weight.
Above-mentioned cellulose acylate can synthesize as acylating agent with acid anhydrides or acyl chlorides.As the most general industrial synthetic method, as described below.To carry out esterification with the mixed organic acid composition that contains the organic acid corresponding with acetyl group and propiono (acetic acid, propionic acid) or their acid anhydrides (acetic anhydride, propionic andydride) by the cellulose that cotton linter or wood pulp etc. obtains, can synthesize target fibers element acylate.
The phase retardation film that uses among the present invention can in the cellulose acylate that contains as principal ingredient, contain at least a kind of adjuvant according to various purposes.When making this phase retardation film by the solution film-forming method, these adjuvants can add in the cellulose acylate rubber cement.For being not particularly limited the opportunity of adding.Adjuvant is selected from the adjuvant of compatible with cellulose acylate (dissolving in the solution film-forming method in the cellulose acylate rubber cement).Adjuvant is that the characteristic etc. of adjusting the optical characteristics of cellulose acylate and adjusting other is added for purpose.
Above-mentioned phase retardation film contains plastifier, can improve masking etc., so preferred.Wherein, using the polycondensation ester is that plastifier considers it is preferred from the aspect of birefringent embodiment.The polycondensation ester is that plastifier can be selected from the condensed polymer of dicarboxylic acid and glycol.The polycondensation ester is that plastifier is not particularly limited, but the preferred polycondensation ester that has aromatic rings in molecule is plastifier, and the polycondensation ester that more preferably has phenyl ring is plastifier.Wherein, preferably from the condensed polymer of aromatic dicarboxylic acid and aliphatic diol, select.Aromatic dicarboxylic acid and aliphatic diol can be respectively a kind, also can be more than 2 kinds.
In the example of above-mentioned aromatic dicarboxylic acid, comprise phthalic acid, terephthalic acid (TPA), m-phthalic acid, 1, the carbon numbers such as 5-naphthalene dicarboxylic acids, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids are 6～12 arlydene dicarboxylic acid.Wherein, be plastifier as terephthalic acid (TPA) etc. at the polycondensation ester that contraposition has the benzene derivative of 2 carboxylic acids if use the dicarboxylic acid composition, then birefringent embodiment uprises, so preferred.
In the example of above-mentioned aliphatic dihydroxy alcohol, comprise that carbon number is 2～12 aklylene glycol, particularly, comprise ethylene glycol, 1,2-PD, 1,3-PD, 1, the 2-butylene glycol, 1,3-BDO, 1,2-PD, the 2-methyl isophthalic acid, ammediol, BDO, 1,5-PD, 2,2-dimethyl-1,3-propylene glycol (neopentyl glycol), 2,2-diethyl-1, ammediol (3,3-dihydroxymethyl pentane), 2-normal-butyl-2-ethyl-1,3-PD (3,3-dihydroxymethyl heptane), the 3-methyl isophthalic acid, the 5-pentanediol, 1, the 6-hexanediol, 2,2,4-trimethyl-1, the 3-pentanediol, 2-ethyl-1, the 3-hexanediol, the 2-methyl isophthalic acid, the 8-ethohexadiol, 1,9-nonanediol, 1, the 10-decanediol, 1,12-octacosanol etc.These glycol can use a kind or use as the potpourri more than 2 kinds.
Utilizable polycondensation ester is that the preferred terminal hydroxyl of plastifier is by end-blocking among the present invention.End-blocking can use the aromatic series monocarboxylic acid, and wherein, preferred use can have substituent benzene monocarboxylic acid.As concrete example, can list benzoic acid, p-tert-butyl benzoic acid, o-toluic acid, m-methyl benzoic acid, p-methylbenzoic acid, mesitylenic acid, ethyl benzoate, n-propylbenzene formic acid, aminobenzoic acid, acetoxy-benzoic acid etc.They can use respectively a kind or use as the potpourri more than 2 kinds.
Below, illustrate that utilizable polycondensation ester is the object lesson of plastifier among the present invention, but be not limited to following object lesson.
Table 1
The polycondensation ester that can use is that the number-average molecular weight of plastifier is preferably 300～2000, more preferably 400～1500 scope.In addition, its acid number is that 0.5mgKOH/g is following, hydroxyl value is below the 25mgKOH/g, and more preferably acid number is that 0.3mgKOH/g is following, hydroxyl value is below the 15mgKOH/g.
The addition that above-mentioned polycondensation ester is plastifier is preferably 1～25 quality % with respect to cellulose acylate, more preferably 2～15 quality %.But, be not limited to this scope.
As utilizable preferred plastifier among the present invention except above-mentioned, can list the plastifier of carbohydrates system, be monose or the derivant that comprises the carbohydrates of 2～10 monosaccharide units, the group that can replace in the preferred molecule of these monose or polysaccharide (such as hydroxyl, carboxyl, amino, sulfydryl etc.) is substituted.
As substituent example, can list ether, ester group, amide group, imide etc.
As monose or comprise the example of the carbohydrates of 2～10 monosaccharide units, for example can list erythrose, threose, ribose, arabinose, wood sugar, lyxose, allose, altrose, glucose, fructose, mannose, gulose, idose, galactose, talose, trehalose, isotrehalose, neotrehalose, mycosamine, kojibiose, black mould sugar, maltose, maltitol, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, lactose amine, lactitol, the lettuce disaccharides, melibiose, primeverose, rutinose, scillabiose, sucrose, Sucralose, turanose, vicianose, cellotriose, chacotriose, gentianose, Isomaltotriose, isopanose, maltotriose, manninotriose, melezitose, glucityl maltose, plantain seed sugar, gossypose, solatriose, umbelliferose, lycotetraose, maltotetraose, stachyose, maltopentaose, verbascose, MALTOHAXAOASE, alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, δ-cyclodextrin, xylitol, D-sorbite etc.
Be preferably ribose, arabinose, wood sugar, lyxose, glucose, fructose, mannose, galactose, trehalose, maltose, cellobiose, lactose, sucrose, Sucralose, alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, δ-cyclodextrin, xylitol, D-sorbite, arabinose more preferably, wood sugar, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, beta-schardinger dextrin-, gamma-cyclodextrin is particularly preferably wood sugar, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, xylitol, D-sorbite.
In addition; be the substituent example of plastifier as carbohydrates; (preferred carbon number is 1～22 can to list ether; more preferably carbon number is 1～12; particularly preferably carbon number is 1～8 alkylether radicals; methyl ether for example; the ethyl ether; the propyl group ether; the hydroxyethyl ether; the hydroxypropyl ether; 2-cyano ethyl ether; the phenyl ether; benzyl ether etc.); (preferred carbon number is 1～22 to ester group; more preferably carbon number is 2～12; particularly preferably carbon number is 2～8 acyl ester group; acetyl group for example; propiono; bytyry; valeryl; caproyl; caprylyl; benzoyl; toluyl groups; phthalyl etc.); (preferred carbon number is 1～22 to amide group; more preferably carbon number is 2～12; particularly preferably carbon number is 2～8 acid amides; formamido for example; acetamido etc.); (preferred carbon number is 4～22 to imide; more preferably carbon number is 4～12; particularly preferably carbon number is 4～8 imide, for example succinimido; phthalimide-based etc.).
In these substituting groups, more preferably ether or ester group are particularly preferably ester group.
Be the preference of plastifier as carbohydrates, can list following example.But operable carbohydrates is that plastifier is not limited to these among the present invention.
Namely, be preferably the wood sugar tetracetate, alpha-glucose pentaacetate, the fructose pentaacetate, the mannose pentaacetate, the galactose pentaacetate, the maltose octaacetate, the cellobiose octaacetate, sucrose octaacetate, the xylitol pentaacetate, sorbitol hexaacetate, wood sugar four propionic esters, glucose pentapropiopanoate, fructose five propionic esters, mannose five propionic esters, galactose five propionic esters, maltose eight propionic esters, cellobiose eight propionic esters, sucrose eight propionic esters, xylitol five propionic esters, D-sorbite six propionic esters, wood sugar four butyric esters, Glucose Pentabutyrate, fructose five butyric esters, mannose five butyric esters, galactose five butyric esters, maltose eight butyric esters, cellobiose eight butyric esters, sucrose eight butyric esters, xylitol five butyric esters, D-sorbite six butyric esters, wood sugar four benzoic ethers, glucose pentaphene formic ether, fructose pentaphene formic ether, mannose pentaphene formic ether, galactose pentaphene formic ether, maltose eight benzoic ethers, cellobiose eight benzoic ethers, sucrose eight benzoic ethers, xylitol pentaphene formic ether, D-sorbite six benzoic ethers etc., wood sugar tetracetate more preferably, alpha-glucose pentaacetate, the fructose pentaacetate, the mannose pentaacetate, the galactose pentaacetate, the maltose octaacetate, the cellobiose octaacetate, sucrose octaacetate, the xylitol pentaacetate, sorbitol hexaacetate, wood sugar four propionic esters, glucose pentapropiopanoate, fructose five propionic esters, mannose five propionic esters, galactose five propionic esters, maltose eight propionic esters, cellobiose eight propionic esters, sucrose eight propionic esters, xylitol five propionic esters, D-sorbite six propionic esters, wood sugar four benzoic ethers, glucose pentaphene formic ether, fructose pentaphene formic ether, mannose pentaphene formic ether, galactose pentaphene formic ether, maltose eight benzoic ethers, cellobiose eight benzoic ethers, sucrose eight benzoic ethers, xylitol pentaphene formic ether, D-sorbite six benzoic ethers etc. are particularly preferably the maltose octaacetate, the cellobiose octaacetate, sucrose octaacetate, wood sugar four propionic esters, glucose pentapropiopanoate, fructose five propionic esters, mannose five propionic esters, galactose five propionic esters, maltose eight propionic esters, cellobiose eight propionic esters, sucrose eight propionic esters, wood sugar four benzoic ethers, glucose pentaphene formic ether, fructose pentaphene formic ether, mannose pentaphene formic ether, galactose pentaphene formic ether, maltose eight benzoic ethers, cellobiose eight benzoic ethers, sucrose eight benzoic ethers, xylitol pentaphene formic ether, D-sorbite six benzoic ethers etc.
Above-mentioned phase retardation film also can contain other plastifier, for example, can contain at least a kind from polyol ester be plastifier, carbohydrate be plastifier, and phosphate be other plastifier of selection the plastifier etc.About object lesson, on the books in the communiques such as TOHKEMY 2010-079241 number and TOHKEMY 2007-169592 number.
In addition, above-mentioned phase retardation film also can contain other adjuvant, also can contain more than 1 kinds of various adjuvants such as particulate, anti-deterioration agent, remover, optical characteristics correctives.The example of these adjuvants is on the books in TOHKEMY 2010-079241 communique, can reference.
In addition, the content of total that comprises whole adjuvants of plastifier is preferably below the 25 quality % with respect to cellulose acylate.
Film-forming method for above-mentioned phase retardation film is not particularly limited.In solution film-forming method and the melting masking method any one all can be utilized.Be preferably the film that obtains by solution film-forming method (solvent cast method) masking.In the solvent cast method; the cellulose acylate of regulation is dissolved in the organic solvent and the modulation rubber cement; with the surface of rubber cement curtain coating to the supporter that is formed by metal etc.; drying and masking; then; film is stripped from supporting body surface, carry out stretch processing (for example biaxial stretch-formed processing) according to expectation, make thus.About the solvent cast method, on the books in various documents, can reference.For example, can be with reference to the record in [0064]～[0079] of TOHKEMY 2010-079241 communique.
Except the curtain coating of general individual layer sol slurry, also can use the multilayer common the tape casting that is filmed of curtain coating simultaneously by multiple cellulose acylate solution.
Especially preferably have the superficial layer that when making by solution film-forming, contacts with supporter (below be also referred to as epidermis A layer), and the supporter superficial layer of contact side (below be also referred to as epidermis B layer) and between two superficial layers and account for the stepped construction more than 3 layers or 3 layers of the central stratum more than 50% (below be also referred to as sandwich layer) of total film thickness not, be particularly preferably the 3-tier architecture of epidermis A layer/sandwich layer/epidermis B layer.
In the situation of above-mentioned 3-tier architecture; each layer as the cellulose acylate of principal ingredient so long as the formation of so-called high substituted degree layer/low degree of substitution layer/high substituted degree layer, and total acyl substituted degree of sandwich layer is that 2.20～2.60 cellulose acylated resin of scope of the present invention gets final product.
In addition; epidermal area A is the high substituted degree layer; preferred from the viewpoint of the fissility of supporter and the viewpoint of dimensional stability when improving solution film-forming; and then; contained cellulose acylate uses the cellulose acylate of identical acyl substituted degree among epidermal area A, the epidermal area B, follows the damp and hot variation of environment and the viewpoint of the amount of curl that produces is preferred from manufacturing cost, dimensional stability and reduction.
Above-mentioned phase retardation film also can be the film of having adjusted its delay by stretch processing.Stretch processing can be carried out in film-forming process, also can carry out after masking.Being stretching under normal temperature or the heating condition of film implemented.Heating-up temperature is preferably before and after the glass transition temperature of film ± and 20 ℃.This is because if stretch with the temperature more much lower than glass transition temperature, then easily fracture can't embody desired optical characteristics.In addition, if stretch with the temperature more much higher than glass transition temperature, the film that molecular orientation then occurs by stretching is before by heat fixation, and the heat when stretching relaxes, and can't be orientated immobilization, the manifesting property variation of optical characteristics.
The stretching of film can be uniaxial tension, also can be biaxial stretch-formed, for the value of the above-mentioned velocity of sound than Vs/Vf is adjusted to more than 1.15, preferably carries out uniaxial tension along the TD direction.The stretching ratio of TD direction is preferably 1.1 times～2 times, preferably carries out stretch processing with 1.1～1.6 times stretching ratio.
Also can implement surface treatment to the phase retardation film of such making.In the surface-treated example, can list Corona discharge Treatment, glow discharge processing, flame treatment, acid treatment, alkali treatment or ultraviolet treatment with irradiation.In addition, also preferably as putting down in writing in the Japanese kokai publication hei 7-333433 communique, undercoat is set.When use as diaphragm on the surface that is fitted in the polarizer, from the viewpoint of the cementability of the polarizer, particularly preferably implementing acid treatment or alkali treatment is that saponification is processed.The surface energy of above-mentioned phase retardation film is preferably more than the 55mN/m, and more preferably 60mN/m is above and be below the 75mN/m.
Phase differential for utilizable phase retardation film among the present invention, preferably postpone Re(550 in the face under wavelength 550nm) be 20～80nm, and the thickness direction retardation Rth(550 under this wavelength) be 100～180nm, more preferably Re(550) be 30～60nm, and Rth(550) be preferably 110～160nm.
2. polaroid
Above-mentioned phase retardation film after integrated with the polarizer (polarizing coating), namely make the polaroid of stepped construction after, can attach on the liquid crystal cells.An example of above-mentioned polaroid is made of two polaroid protective films (hyaline membrane) on the polarizer and its two sides of protection, has above-mentioned phase retardation film as a polaroid protective film.The slow axis of above-mentioned phase retardation film is the relation of or quadrature parallel with the absorption axes of the above-mentioned polarizer.
For the polarizer that uses among the present invention, will absorb axial elastic modulus be made as E, when its thickness is made as d, its ratio E/d is more than 0.2.Can think that the elastic modulus of the polarizer is higher, thickness is less, and then quadrature and stable is got on the surface of punching press cutter and phase retardation film surface, so the unfilled corner when more being difficult for causing the punching press polaroid.The ratio of E/d is preferably 0.20～1.50, is particularly preferably 0.20～1.00, most preferably is 0.22～0.50.When the ratio of E/d is lower than 0.20, be the elastic modulus the thickness excessively low or polarizer of polarizer when blocked up, the punching press cutter is pressed into whole polaroid, make its distortion and with the Surface Contact of phase retardation film, so the surface of punching press cutter and phase retardation film surface are non-orthogonal, its angle is unfixing yet.If the punching press cutter is the punching press polaroid under this state, unfilled corner then occurs.
Absorb axial elastic modulus and be preferably 3.0～7.0GPa, be particularly preferably 4.0～7.0GPa.
In addition, being made as Vs in the velocity of sound with the slow-axis direction of phase retardation film, when the velocity of sound of quick shaft direction is made as Vf, is that phase retardation film effect more than 1.15 is remarkable for the value of Vs/Vf, more preferably 1.15～1.40 scope.
The thickness of the polarizer is preferably 5～30 μ m, is particularly preferably 10～25 μ m.
As the above-mentioned polarizer, be not particularly limited.For example, can use polyvinyl alcohol film is impregnated into the polarizer that forms etc. that stretches in the iodine solution.The bonding agent that uses when above-mentioned phase retardation film and the polarizer are fitted can use the aqueous solution of polyvinyl alcohol (PVA) or Pioloform, polyvinyl acetal (for example polyvinyl butyral), the latex of vinyl based polymer (for example butyl polyacrylate).Particularly preferred bonding agent is the aqueous solution of fully saponified polyvinyl alcohol (PVA).
Diaphragm about another surface (becoming the surface in the outside of the polarizer when namely being assembled in the liquid crystal indicator) of being fitted in the polarizer; can utilize various polymer films, the styrenics such as the acrylic acid series polymeric compounds such as polyester based polymer, polymethylmethacrylate, polystyrene or acrylonitritrile-styrene resins such as cellulose acylate, polycarbonate based polymer, polyethylene terephthalate or PEN (AS resin) etc.In addition; can be from tygon; the polyolefin such as polypropylene; the cyclopolyolefins such as norborene; polyolefin polymkeric substance as ethylene-propylene copolymer; vinyl chloride-based polymer; the acid amides such as nylon or aromatic polyamide based polymer; the imide series polymkeric substance; the sulfone based polymer; the polyethersulfone based polymer; the polyetheretherketone based polymer; the polyphenylene sulfide based polymer; the vinylidene chloride based polymer; the vinyl alcohol based polymer; the vinyl butyral based polymer; the arylide based polymer; the polyoxymethylene based polymer; the epoxy based polymer; or mixed in the polymkeric substance etc. of above-mentioned polymkeric substance and selected one kind or two or more polymkeric substance; make to make polymer film as principal ingredient, as diaphragm.Also can use in addition the polymer film of general commercially available product.
The thickness of diaphragm of outer surface that is fitted in the polarizer is thinner, easier generation unfilled corner fault then, but effect of the present invention becomes remarkable.As the average film thickness of diaphragm, be preferably 10～60 μ m, more preferably 15～45 μ m are particularly preferably 20～30 μ m.
Mean breadth as diaphragm is preferably 1000～2500mm, more preferably 1500～2500mm.
In addition, the tensile modulus of elasticity of diaphragm all is preferably the scope of 3.5～8.0GPa on MD direction, TD direction, 4.0～7.0GPa more preferably, and more preferably 5.0～7.0GPa most preferably is 6.0～7.0GPa.
In addition, about the method for the cellulose-based diaphragm of the tensile modulus of elasticity that make to show above-mentioned preferred scope, can be with reference to No. 4759317 communique of Jap.P..
When using cellulose-based diaphragm as diaphragm, preferably take the cellulose acetate of degree of substitution with acetyl group as 2.70～2.90 as principal ingredient.
An example of the manufacture method of polaroid of the present invention comprises following operation at least: with the polarizer, phase retardation film and the diaphragm of making respectively strip according to separately the consistent mode of length direction is fitted and obtain the operation of duplexer; And with above-mentioned duplexer be cut into take with respect to length direction as 45 ° the direction operation as rectangular-shaped form on one side.The polarizer that is made into strip has absorption axes along its length usually, and in addition, the phase retardation film that carries out stretch processing along MD direction or TD direction has slow axis in the face of or quadrature parallel with length direction usually.By will make length direction as one man the stacked above-mentioned duplexer that obtains be cut in the direction that with respect to length direction is 45 ° and have on one side rectangular-shaped, can easily make following polaroid: the absorption axes angulation of its long limit or minor face and the polarizer is 45 °, and the slow axis of phase retardation film is parallel with the absorption axes of the above-mentioned polarizer or quadrature.And then, above-mentioned phase retardation film since Vs/Vf within the limits prescribed, and the E/d of the above-mentioned polarizer within the limits prescribed, so the generation of the unfilled corner in the time of can suppressing the cutting of 45 ° of directions.
3. liquid crystal indicator
Polaroid of the present invention can be used for liquid crystal indicator, is preferred in the liquid crystal indicator of TN pattern.Fig. 3 represents the diagrammatic cross-section of an example of TN mode LCD of the present invention.In addition, among the figure, the relativeness of the thickness of each layer not necessarily relativeness with each layer thickness of the liquid crystal indicator of reality is consistent.
It is backlight 30 of a pair of viewable side polaroid PL1 and backlight side polaroid PL2, the TN mode liquid crystal unit LC that disposes therebetween and the more lateral that is positioned at the backlight side polarizer 18 that TN mode LCD shown in Figure 3 possesses polaroid of the present invention.
The polarizer 16 and 18 axis of homology separately is orthogonal, and at 45 ° or 135 ° of ground configurations with respect to display surface horizontal direction (sometimes being also referred to as 0 ° of direction).In an example, the axis of homology of the polarizer 16 is parallel with the friction mandrel of substrate 12, and the axis of homology of the polarizer 18 is parallel with the friction mandrel of substrate 14, in another example, the friction mandrel quadrature of the axis of homology of the polarizer 16 and substrate 12, and the friction mandrel quadrature of the axis of homology of the polarizer 18 and substrate 14.
Liquid crystal cells LC have a pair of substrate 12 and 14 and therebetween the configuration the liquid crystal layer that contains nematic liquid crystal material 10.Internal surface configurations in substrate 12 and 14 has friction orientation film (not shown), and the orientation of nematic liquid crystal is controlled by frictional direction separately, and orientation twists.In addition, the inside surface in substrate 12 and 14 is formed with electrode layer (not shown), and when applying voltage, the twist alignment of nematic liquid crystal is eliminated, and consists of according to the mode vertical orientated with respect to real estate.Liquid crystal cells LC also can comprise other the parts such as color filter.
About TN pattern liquid crystal cells LC, be not particularly limited, the liquid crystal cells of the formation that proposes as the TN pattern can use.The Δ nd of the liquid crystal cells of TN pattern is generally 350～450nm.
The light source that uses in BL backlight etc. is not particularly limited.BL backlight can regulate such as prismatic lens, diffusion barrier etc. by the member that configuration has an effect of the directive property of regulating light.
Embodiment
(embodiment A)
Below listing embodiment and comparative example more specifically describes feature of the present invention.Material shown in the following embodiment, use amount, ratio, contents processing, treatment step etc. only otherwise exceed purport of the present invention can suitably change.Therefore, scope of the present invention should not be subjected to the limited explanation of concrete example shown below.
1. the making of phase retardation film A
Use cellulose acylate and the adjuvant of the degree of substitution of putting down in writing in the following table, and then under the stretching condition shown in the following table, carry out stretch processing, make phase retardation film A.
The modulation of particle dispersion liquid
Following composition is mixed the modulation particle dispersion liquid.
Particulate (R972V(Japan Aerosil Co., Ltd. system)) 11 mass parts
Ethanol 89 mass parts
The modulation of particulate annex solution
In the dissolving tank that methylene chloride is housed, add cellulose acylate with following ratio, after heating is dissolved it fully, use the long-pending filter paper No.244 of peace of the long-pending filter paper Co., Ltd. of peace system that it is filtered.Cellulose acylate solution after will filtering on one side fully stirs, one side the ratio put down in writing in the following table to the particle dispersion liquid that wherein adds lentamente above-mentioned modulation.And then, utilize masher to disperse.Its FINEMET NF with Japan Jingxian Co., Ltd's system is filtered modulation particulate annex solution.
Methylene chloride 99 mass parts
Cellulose acylate (with reference to following table) 4 mass parts
Particle dispersion liquid 11 mass parts
The modulation of main rubber cement liquid
Modulate the main rubber cement liquid of following composition.At first, in the dissolved under pressure tank, add methylene chloride and ethanol.In the dissolved under pressure tank that solvent is housed, drop into cellulose acylate while stirring.It is heated, while stir it is dissolved fully, further add and dissolve the plastifier of putting down in writing in the following table.Use the long-pending filter paper No.244 of peace of the long-pending filter paper Co., Ltd. of peace system that it is filtered, modulate main rubber cement liquid.
The composition of＜main rubber cement liquid 〉
Main rubber cement liquid 100 mass parts and particulate annex solution 2 mass parts are fully mixed with line mixer (mixer Hi-Mixer, SVII in the Toray company silent oscillation pipe processed) and modulate rubber cement, use the belt casting device, with its equably curtain coating to wide be on the stainless steel band supporter of 2m.On the stainless steel band supporter, make solvent be evaporated to the residual solvent amount and reach till 40%, peel off from the stainless steel band supporter.With stenter the tablet both ends are controlled, the residual solvent amount when stretching beginning is that 15 quality %, temperature are to stretch 30% along width (TD) direction in 130 ℃～140 ℃ the scope.And then, in being set as 125 ℃ the 3rd arid region, carry and carried out drying in 30 minutes, making respectively wide is the cellulose acylate film of thickness shown in the following table of annular knurl of 8 μ m for 1cm, height for 1.5m and end have wide.Use respectively them as phase retardation film A.
Resulting phase retardation film is fully adjusted humidity with film under 25 ℃, the mensuration environment of 60%RH, with the wild village of sound wave meter SST-110(business system) measure the velocity of sound of MD direction and the velocity of sound (sound wave conduction of velocity) of TD direction.Above-mentioned phase retardation film is Vs owing to have slow axis in the TD direction so establish the velocity of sound of TD direction, and the velocity of sound of establishing the MD direction is Vf.
2. the making of the polarizer
(polarizer of embodiment 1)
Use that the degree of polymerization is 2400, saponification degree is 99.9% polyvinyl alcohol film, in iodine/potassium iodide mixed liquor, film is stretched after 6.3 times along length (MD) direction, and is lax to 5.9 times, obtains the polarizer.The crosslinked of film during polarizer masking carries out simultaneously with stretching in 4% boric acid aqueous solution.
(polarizer of embodiment 2)
Use that the degree of polymerization is 2400, saponification degree is 99.9% polyvinyl alcohol film, in iodine/potassium iodide mixed liquor, implement dyeing after, with film take boric acid as matrix and mixed glyoxal stretch 6.2 times along length (MD) direction in the aqueous solution, obtain the polarizer.Boric acid/glyoxal in the aqueous solution mixing ratio carry out with weight ratio 7:3, and keep the pH=4(in the aqueous solution acid).
(polarizer of embodiment 3)
Use that the degree of polymerization is 2400, saponification degree is 99.9% polyvinyl alcohol film, in iodine/potassium iodide mixed liquor, film is stretched after 7.0 times along length (MD) direction, and is lax to 6.5 times, obtains the polarizer.The crosslinked of film during polarizer masking carries out simultaneously with stretching in 4% boric acid aqueous solution.
(polarizer of comparative example 1)
Use that the degree of polymerization is 2400, saponification degree is 99.9% polyvinyl alcohol film, in iodine/potassium iodide mixed liquor, film is stretched 5.5 times along length (MD) direction, then, in 4% BAS, carry out crosslinked/stretching, so that total stretching ratio reaches 6.2 times, obtain the polarizer.
(polarizer of comparative example 2)
Use that the degree of polymerization is 2400, saponification degree is 99.9% polyvinyl alcohol film, in iodine/potassium iodide mixed liquor, film is stretched after 6.5 times along length (MD) direction, and is lax to 6.0 times, obtains the polarizer.The crosslinked of film during polarizer masking carries out simultaneously with stretching in 4% boric acid aqueous solution.
(mensuration of the MD direction elastic modulus of the polarizer)
For the resulting polarizer, measure MD direction elastic modulus.To the results are shown in the table.When measuring, sample 10mm * 200mm is adjusted humidity 2 hours under 25 ℃, 60%RH, with cupping machine (the smart mechanism of Storograph R2(Japan)), specimen length is that 100mm, draw speed are under 10mm/ minute in the early stage, is calculated by stress and the length growth rate at the initial stage of stretching.In addition, the resulting polarizer all is that the monomer transmissivity is more than 43.5%, and degree of polarization is more than 99.5%.
3. the making of polaroid
Both sides at the PVA of resulting strip polarizer film; to carry out the diaphragm that saponification processes with the sodium hydroxide aqueous solution is fitted on the face; to carry out each phase retardation film that saponification processes with identical sodium hydroxide aqueous solution is fitted on the opposite face; be bonding agent with commercially available PVA; make 3 to gather to fit at length direction, make respectively simultaneously the polaroid of spool form.In addition, as diaphragm, used thickness is the tri cellulose acetate membrane (FUJITAC TD40) of 40 μ m.
In addition, the tensile modulus of elasticity of TD40 is the measured value of the scope of 4.0～4.6GPa in MD direction, TD direction.
(coating of adhesive phase)
The making of＜acrylic acid series polymeric compounds solution 〉
N-butyl acrylate (n-BA) 75 mass parts, methyl acrylate (MA) 20 mass parts, acrylic acid 2-hydroxy ester (2-HEA) 5 mass parts, ethyl acetate 100 mass parts and azobis isobutyronitrile (AIBN) 0.2 mass parts are added in the reaction vessel, with the air in this reaction vessel with nitrogen replacement after, under agitation in blanket of nitrogen, make this reaction vessel be warming up to 60 ℃, reacted 4 hours.After 4 hours, add toluene 100 mass parts, α-methylstyrenedimer 5 mass parts and AIBN2 mass parts, be warming up to 90 ℃, further reacted 4 hours.After the reaction, with the ethyl acetate dilution, obtain the acrylic acid polymer solution that solid constituent is 20 quality %.In solid constituent 100 mass parts of polymer solution, add isocyanate-based crosslinking chemical (trade name: CORONATE L, Japanese polyurethane Co., Ltd. system) 1.0 mass parts, fully stir, obtain adhesive composition.
(with the making of the polaroid of bonding agent)
Applying adhesive on each polaroid of above-mentioned making.
To contain the adhesive composition of aforesaid propylene acid polymer solution at the adhesive phase that forms 25 μ m through the film of lift-off processing, it is transferred on the polaroid (on the phase retardation film of cell side), slaking is 7 days under the condition of 23 ℃ of temperature, humidity 65%, has made the polaroid with bonding agent.Further attach stripping film at this adhesive phase.Attach diaphragm at the diaphragm with the unit opposition side.
4. estimate
(1) evaluation of polaroid
The polaroid with bonding agent by the spool form carries out punch test by the Thomson cutting die to rectangular-shaped polaroid.Each polaroid spool is the absorption axes of the polarizer, rectangular-shaped long limit and minor face with respect to this absorption axes according to length direction is that the mode of 45 ° direction cuts polaroid.By 1 volume with 100 of each punching presses of same size, the sheet number of any the rectangular-shaped polaroid jaggy in 4 jiaos of the number rectangles that go out to cut.
In the table, with jaggy number/100 expression.
Table 2
By the result shown in the upper table; can be understood as; long limit by making rectangular-shaped polaroid or the absorption axes angulation of minor face and the polarizer are 45 °; the slow axis of phase retardation film or quadrature parallel with the absorption axes of the polarizer; it is that 2.2～2.6 cellulose acylate is as principal ingredient to total degree of substitution of the hydroxyl of the glucose unit that consists of cellulose acylate that phase retardation film contains acyl group; the value of the Vs/Vf of phase retardation film is more than 1.15; the polarizer is formed by polyvinyl alcohol (PVA); E/d is more than 0.2, thereby has reduced the frequency of unfilled corner fault.
(Embodiment B)
(making of phase retardation film B)
The modulation of＜cellulose acylate solution B c 〉
Cellulose acylate and following composition are dropped in the mixing channel, stir, with each composition dissolving, modulated cellulose acylate solution B c.
* CE-1: degree of substitution with acetyl group is 2.42, total degree of substitution is 2.42
* polyester oligomer B-1: record in the table 3
Table 3
* polyester oligomer B-1
The modulation of＜cellulose acylate solution B s 〉
Cellulose acylate and following composition are dropped in the mixing channel, stir, with each composition dissolving, modulated cellulose acylate solution B s.
* CE-2: degree of substitution with acetyl group is 2.81, total degree of substitution is 2.81
The modulation of＜matting agent solution B m 〉
Following composition is dropped in the dispersion machine, stir, with each composition dissolving, modulated matting agent solution B m.
As casting method, rubber cement is carried out three layer altogether curtain coating with rubber cement/skin (air layer) with the order of rubber cement with rubber cement/sandwich layer according to outer (belt) with metal belt casting machine, after the drying, by stripping drum film is stripped from being with.
The sandwich layer rubber cement is cellulose acylate solution B c, and outer is to have mixed the above-mentioned matting agent solution B m of 1.35 mass parts and the solution that obtains with respect to 100 mass parts of cellulose acylate solution B s with rubber cement.
Carry out take the stiff end uniaxial tension after stretching ratio stretches as 1.05 times MD at the above-mentioned film that under 185 ℃ the atmosphere temperature residual solvent levels is lower than 1%, residual solvent levels being lower than 1% above-mentioned film under 185 ℃ atmosphere temperature, carry out stretching ratio in the stenter zone be that 1.30 times TD stretches.Then, unload clip and carry out drying, made the wide film 6 of 2000mm that is.The residual solvent amount of the phase retardation film 2 of made is 0.1%, and its average film thickness is 50 μ m.
By the method identical with embodiment A, measure face interior phase differential Re, the thickness direction phase differential Rth of resulting film, the velocity of sound that reaches the MD direction and the velocity of sound (sound wave conduction of velocity) of TD direction.
To the results are shown in the following table 4.
The making of＜diaphragm B 〉
The composition of following middle record is dropped in the mixing channel, heat while stirring, with each composition dissolving, modulated rubber cement.
(rubber cement composition)
Use the belt casting device, with the rubber cement of above-mentioned modulation from the curtain coating mould equably curtain coating to the endless belt (curtain coating supporter) of stainless steel.
Residual solvent amount in rubber cement reaches the moment of 40 quality %, peels off with the form of polymeric membrane from the curtain coating supporter, 120 ℃ of lower dryings, slices off limit section in the arid region, obtains the wide cellulose acetate membrane of 2000mm that is.
As diaphragm B, its average film thickness is 27 μ m with the film of made.
5 places in the 2000mm width of diaphragm B are measured tensile modulus of elasticity, and the result is the measured value of the scope of 4.0～4.5GPa in MD direction, TD direction.
With respect to embodiment 1,2,3, comparative example 1, each polaroid of 2; phase retardation film 1 is changed to phase retardation film B; and then will change to as the TD40 of diaphragm diaphragm B, and made respectively polaroid, similarly estimate the frequency of the unfilled corner fault of polaroid with embodiment A.
To the results are shown in the table 4.
Embodiment B 2, B3 are good especially results.
Table 4
Embodiment C
The making of＜diaphragm C 〉
The composition of following record is dropped in the mixing channel, heat while stirring, with each composition dissolving, modulated rubber cement.
(rubber cement composition)
With above-mentioned rubber cement belt casting machine curtain coating.For take the residual solvent amount as 25～35 quality % from the film that strips; draft temperature be than the glass transition temperature of cellulose acylate film low about 5 ℃ temperature under the condition of the scope of high about 5 ℃ temperature; use stenter to carry out the stretching of multiplying power 120% along stretching and broad ways that operating direction carries out multiplying power 120%, make cellulose acylate film.
Before reeling end, cut away both ends, obtain the wide cellulose acetate membrane of 2000mm that is.
As diaphragm C, its average film thickness is 25 μ m with the film of made.
10 places in the 2000mm width of diaphragm C are measured tensile modulus of elasticity, and MD direction, TD direction are the measured value of the scope of 6.2～6.8GPa as a result.
With respect to the polaroid of Embodiment B 1, diaphragm B is changed to diaphragm C, made polaroid (Embodiment C 1), estimate the frequency of the unfilled corner fault of polaroid.
In several 100 of test pieces, the unfilled corner fault obtain 0 time good result.
Claims (18)
1. a polaroid is characterized in that, it is the rectangular-shaped polaroid that is applicable to liquid crystal indicator,
Described polaroid by the polarizer, be bonded in the diaphragm on the one face and the phase retardation film that is bonded on another face consists of,
The long limit of described rectangular-shaped polaroid or the absorption axes angulation of minor face and the described polarizer are 45 °,
The slow axis of described phase retardation film or quadrature parallel with the absorption axes of the described polarizer,
Described phase retardation film contains cellulose acylate as principal ingredient, and in the described cellulose acylate, acyl group is 2.2～2.6 to total degree of substitution of the hydroxyl of the glucose unit of formation cellulose acylate,
Be made as Vs in the velocity of sound with the slow-axis direction of described phase retardation film, when the velocity of sound of quick shaft direction is made as Vf, the value of Vs/Vf is more than 1.15,
The described polarizer is made of polyvinyl alcohol (PVA), the axial elastic modulus of the absorption of the described polarizer is made as E, when the thickness of the described polarizer is made as d, its ratio E/d is more than 0.2.
2. polaroid according to claim 1, wherein, described cellulose acylate is cellulose acetate or the cellulose acetate propionate that satisfies following formula (1) and (2),
（1）2.2≤A+B≤2.6
（2）0≤B≤1.2
Wherein, A represents the degree of substitution of the acetyl group in the cellulose acylate, and B represents the degree of substitution of the propiono in the cellulose acylate.
3. polaroid according to claim 1 wherein, postpones Re(550 in the face of described phase retardation film under wavelength 550nm) be 20～80nm, the thickness direction retardation Rth(550 under this wavelength) be 100～180nm.
4. polaroid according to claim 2 wherein, postpones Re(550 in the face of described phase retardation film under wavelength 550nm) be 20～80nm, the thickness direction retardation Rth(550 under this wavelength) be 100～180nm.
5. polaroid according to claim 1, wherein, described E/d is 0.22～0.50.
6. polaroid according to claim 2, wherein, described E/d is 0.22～0.50.
7. polaroid according to claim 3, wherein, described E/d is 0.22～0.50.
8. polaroid according to claim 1, wherein, described Vs/Vf is more than 1.15.
9. polaroid according to claim 2, wherein, described Vs/Vf is more than 1.15.
10. polaroid according to claim 3, wherein, described Vs/Vf is more than 1.15.
11. polaroid according to claim 5, wherein, described Vs/Vf is more than 1.15.
12. polaroid according to claim 1, wherein, the average film thickness of described diaphragm is 20～30 μ m.
13. polaroid according to claim 1, wherein, the tensile modulus of elasticity of described diaphragm is 4.0～7.0GPa in MD direction, TD direction.
14. polaroid according to claim 2, wherein, the tensile modulus of elasticity of described diaphragm is 4.0～7.0GPa in MD direction, TD direction.
15. polaroid according to claim 3, wherein, the tensile modulus of elasticity of described diaphragm is 4.0～7.0GPa in MD direction, TD direction.
16. polaroid according to claim 5, wherein, the tensile modulus of elasticity of described diaphragm is 4.0～7.0GPa in MD direction, TD direction.
17. polaroid according to claim 8, wherein, the tensile modulus of elasticity of described diaphragm is 4.0～7.0GPa in MD direction, TD direction.
18. a liquid crystal indicator is characterized in that, it has each described polaroid in the claim 1～17.
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| CN105319640A (en) * | 2014-08-05 | 2016-02-10 | 东友精细化工有限公司 | Phase difference film and polarizing plate comprising the same |
| CN105717571A (en) * | 2014-12-22 | 2016-06-29 | 住友化学株式会社 | Polarizing film, manufacturing method thereof, polarizing film set, liquid crystal display panel and liquid crystal display device |
| JP2016118761A (en) * | 2014-12-22 | 2016-06-30 | 住友化学株式会社 | Polarizing plate and manufacturing method of the same, and set of polarizing plates, liquid crystal panel, and liquid crystal display device |
| CN106980148A (en) * | 2016-01-19 | 2017-07-25 | 住友化学株式会社 | Polarization plates and image display device |
| CN107111035A (en) * | 2014-12-12 | 2017-08-29 | 住友化学株式会社 | The manufacture method and polarizing coating of polarizing coating |
| CN107850720A (en) * | 2015-07-22 | 2018-03-27 | 柯尼卡美能达株式会社 | Polarizer and the liquid crystal display device using polarizer |
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| JP2016118761A (en) * | 2014-12-22 | 2016-06-30 | 住友化学株式会社 | Polarizing plate and manufacturing method of the same, and set of polarizing plates, liquid crystal panel, and liquid crystal display device |
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| CN107850720B (en) * | 2015-07-22 | 2020-09-01 | 柯尼卡美能达株式会社 | Polarizing plate and liquid crystal display device using the same |
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