CN101153935A - Optical compensation film, its manufacturing method, polarization optical panel and liquid crystal display - Google Patents

Abstract

The invention provides an optical compensating film which can provide a correct optical compensation to the liquid crystal unit and a high contrast and improve the colourbias of the angle of field depended on the black display, and its producing method, a polarized light board, and provides a liquid crystal display device to obtain a good contrast and prevent the light leakage. Thereof, the optical compensating film is characterized by meeting the requirement of following mathematics formula (1)-(4): 50<=Re(550)<=200...(1); 0.4<=Rth(550)/Re(550)<=0.6...(2); 0.1<Re(450)/Re(550)<0.95...(3); 1.03<Re(650)/Re(550)<1.93...(4).

Description

Optical compensating film and manufacture method thereof, polarization plate and liquid crystal indicator

Technical field

The present invention relates to optical compensating film and manufacture method thereof, polarization plate and liquid crystal indicator.

Background technology

Liquid crystal indicator has liquid crystal cells and polarization plate.Above-mentioned polarization plate generally has protective film and the polarization film of being made up of cellulose acetate, for example, with iodine the polarization film of being made up of polyvinyl alcohol film is dyeed, and stretches, and with protective film its two sides lamination is obtained.

In transmission type liquid crystal display device, also some is that polarization plate is installed in the liquid crystal cells both sides, disposes the optical compensating film more than again.

In reflection-type liquid-crystal display device, press the arranged in order of reflecting plate, liquid crystal cells, the optical compensating film more than, polarization plate usually.Liquid crystal cells by the liquid crystal liquid crystal property molecule, the electrode layer that is used to enclose its two substrates and is used for applying voltage on the liquid crystal liquid crystal property molecule forms.

For liquid crystal cells, proposed to carry out ON, OFF and shown, seen through and the display mode of TN (Twisted Nematic) that reflection-type can both be suitable for, IPS (In-Plane Switching), OCB (Optically Compensatory Bend), VA (Vertically Aligned), ECB (Electrically Controlled Birefringence) by means of the difference of the state of orientation of liquid crystal liquid crystal property molecule.

In such LCD, for the high purposes that shows grade of needs, adopt to have the nematic liquid crystal molecules of positive dielectric constant anisotropy the main 90 degree twisted nematic liquid crystals display device (hereinafter referred to as the TN mode) that drive by thin film transistor (TFT) that adopt.

Yet, the TN mode has in the occasion of seeing from the front and has outstanding display characteristic, but the occasion contrast of seeing from tilted direction reduces, and gray shade scale shows generations such as the gray shade scale counter-rotating that brightness down reverses and make the such angle of visibility characteristic of display characteristic variation that very hope is improved.

On the other hand, the liquid crystal mode of the wide view angle that IPS mode, OCB mode and VA mode are such, along with the increase in demand of in recent years LCD TV, its share enlarges.Each mode all improves the demonstration grade every year, and but, the problem of the colo(u)r bias that produces when tiltedly seeing does not solve.

In addition, knew in the past, polarizer as the macromolecular orientation film, 1/4 wavelength plate particularly, satisfy 0.6＜Δ nd (450)/Δ nd (550)＜0.97,1.01＜Δ nd (650)/Δ nd (550)＜1.35 (Δ nd (λ) is the phase differential of the macromolecular orientation film at wavelength X nm place) (opening the 2000-137116 communique) with reference to the spy.

Yet the method for patent documentation 1 record does not obtain the effect that sufficient colo(u)r bias is improved for the TV purposes that requires very high demonstration grade.

Summary of the invention

Problem of the present invention is the problems referred to above before solving, and reaches following purpose.That is, the object of the present invention is to provide and a kind ofly can correctly carry out optical compensation, to high contrast with the colo(u)r bias of the angle of visibility direction when depending on black demonstration optical compensating film and the polarization plate that improve liquid crystal cells.

Also have, the object of the present invention is to provide a kind of contrast of having improved, improved particularly VA, the IPS of the colo(u)r bias that depends on the angle of visibility direction when deceiving demonstration and the liquid crystal indicator of OCB mode.

In order to solve above-mentioned problem, present inventors obtain following opinion through further investigation.That is, according to given stretching condition, the Rth/Re that makes optical compensating film is near 0.5, thereby colour cast is from just compensating such opinion to heavens.

The above-mentioned opinion that the present invention is based on present inventors proposes, and the scheme that is used to solve above-mentioned problem is as follows.That is,

The feature of optical compensating film of the present invention is to satisfy following mathematical expression (1)～(4).

50≤Re (550)≤200 mathematical expression (1)

0.4≤Rth (550)/Re (550)≤0.6 mathematical expression (2)

0.1＜Re (450)/Re (550)＜0.95 mathematical expression (3)

1.03＜Re (650)/Re (550)＜1.93 mathematical expression (4)

In above-mentioned mathematical expression (1)～(4), Re (450), Re (550), Re (650) are that (unit: nm), Rth (550) is the lagged value (unit: nm) of the thickness direction that arrives of the photo measure with wavelength 550nm to lagged value in the face that arrives with the photo measure of wavelength 450nm, 550nm, 650nm respectively.

The feature of the manufacture method of optical compensating film of the present invention is length direction and the stretching process of any one direction in the Width and the contraction process that another direction is shunk that comprises oriented film.

The feature of the manufacture method of polarization plate of the present invention is that the optical compensating film and the polarizer that comprise the microscler shape that satisfies above-mentioned mathematical expression (1)～(4) that the manufacture method that adopts optical compensating film is made carry out bonding operation by volume to volume, and the manufacture method of above-mentioned optical compensating film comprises length direction and the stretching process of any one direction in the Width and the contraction process that another direction is shunk of oriented film.

The feature of polarization plate of the present invention is to adopt the manufacture method of polarization plate to make, the manufacture method of above-mentioned polarization plate comprises that the optical compensating film and the polarizer of the microscler shape that satisfies above-mentioned mathematical expression (1)～(4) that the manufacture method that adopts optical compensating film is made carry out bonding operation by volume to volume, and the manufacture method of above-mentioned optical compensating film comprises length direction and the stretching process of any one direction in the Width and the contraction process that another direction is shunk of oriented film.

The feature of liquid crystal indicator of the present invention is the polarization plate with manufacture method making of adopting polarization plate, liquid crystal cells, with the polarization plate that possesses the optical anisotropic layer that satisfies following mathematical expression (7-1) and mathematical expression (7-2), the manufacture method of above-mentioned polarization plate comprises that the optical compensating film and the polarizer of the microscler shape that satisfies above-mentioned mathematical expression (1)～(4) that the manufacture method that adopts optical compensating film is made carry out bonding operation by volume to volume, and the manufacture method of above-mentioned optical compensating film comprises length direction and the stretching process of any one direction in the Width and the contraction process that another direction is shunk of oriented film.

-10＜Re (550)＜10 mathematical expression (7-1)

100＜| Rth (550) |＜300 mathematical expressions (7-2)

Embodiment

Below describe the present invention in detail.In addition, use the numerical range of "～" expression to be meant to comprise the scope of the numerical value of record before and after "～" in this manual as lower limit and higher limit.

In addition, in this manual, " 45 ° ", " parallel " or " quadrature " are meant in the scope of angle ± 5 ° less than strictness.The error of following strict angle is preferably less than 4 °, even more preferably less than 3 °.Also have, about angle, "+" is meant clockwise direction, and "-" is meant counterclockwise.Also have, " slow axis " is meant that refractive index becomes maximum direction.Also have, " visible region " is meant 380～780nm.Have, the measurement wavelength of refractive index not having under the special situation about recording and narrating, is the value at the λ=550nm place of visible region again.

Also have, in this manual, " polarization plate ", under situation about not particularly pointing out, to comprise long polarization plate and to cut out both meanings of polarization plate that (in this manual, reaching " cutting out " etc. for " cutting out " also comprises " die-cut ") form by the size in the liquid-crystal apparatus of packing into and use.Also have, in this manual, difference uses " polarization film " to reach " polarization plate ", and but, " polarization plate " is meant the laminate of the transparent protective film that has this polarization film of protection on the single face at least of " polarization film ".

In this manual, Re (λ), Rth (λ) represent the hysteresis in the face of af at wavelength lambda and the hysteresis of thickness direction respectively.Re (λ) is in KOBRA 21ADH or WR (prince measures machine (strain) system), allows the light of wavelength X nm measure to the incident of film normal direction.

In the occasion that measured film is represented with 1 or 2 indicatrix, calculate Rth (λ) according to following method.

Rth (λ) is for above-mentioned Re (λ), slow axis (judging according to KOBRA 21ADH or WR) in the face is tilted respectively with 10 degree step-lengths to one-sided 50 degree from normal direction with respect to the film normal direction as sloping shaft (revolving shaft) (is slow axis with any direction in the pellicular front in the occasion that does not have revolving shaft), allow the light of wavelength X nm from this direction incident of having tilted, measure whole 6 points, based on the assumed value of this lagged value that measures and mean refractive index and the film thickness value imported, calculate KOBRA21ADH or WR.

In above-mentioned, have from normal direction, be revolving shaft with the slow axis in the face, at certain angle of inclination, the value of hysteresis becomes the occasion of the film of zero direction, the lagged value at the angle of inclination bigger than this angle of inclination, its variation of sign for after negative, calculate KOBRA21ADH or WR.

In addition, also can be sloping shaft (revolving shaft) (is revolving shaft with any direction in the pellicular front in the occasion that does not have slow axis) with the slow axis, 2 orientation measurement lagged values from any inclination, based on the assumed value of this value and mean refractive index and the film thickness value imported, calculate Rth according to following mathematical expression (I) and formula (II).

$\mathrm{Re}\left(\mathrm{\&theta;}\right)=[\mathrm{nx}-\frac{\mathrm{ny}\&times;\mathrm{nz}}{\sqrt{{\{\mathrm{ny}\sin \left({\sin }^{-1}\left(\frac{\sin (-\mathrm{\&theta;})}{\mathrm{nx}}\right)\right)\}}^2+{\{\mathrm{nz}\cos \left({\sin }^{-1}\left(\frac{\sin (-\mathrm{\&theta;})}{\mathrm{nx}}\right)\right)\}}^2}}]\&times;\frac{d}{\cos \{{\sin }^{-1}\left(\frac{\sin (-\mathrm{\&theta;})}{\mathrm{nx}}\right)\}}$

Mathematical expression (I)

Herein, the lagged value of the direction that tilted with angle θ from normal direction of above-mentioned Re (θ) expression.

Also have, the refractive index of the slow axis direction in the nx presentation surface in the mathematical expression (I), 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.

Rth=((nx+ny)/2-nz) * d mathematical expression (II)

At measured film is the occasion that the what is called that can not show with 1,2 indicatrix does not have the film of optic axis (optic axis), calculates Rth (λ) according to following method.

Rth (λ) is for above-mentioned Re (λ), with the slow axis in the face (judging) according to KOBRA 21ADH or WR be sloping shaft (revolving shaft) and with respect to the film normal direction from-50 spend+50 degree tilt respectively with 10 degree step-lengths, allow the light of wavelength X nm from this direction incident of having tilted, measure whole 11 points, based on the assumed value of this lagged value that measures and mean refractive index and the film thickness value imported, calculate KOBRA21ADH or WR.

In above-mentioned measurement, the assumed value of mean refractive index can be used polymer handbook (JOHNWILEY﹠amp; SONS, INC), the value of the catalogue of various optical compensating films.

Also having, is not known situation for the value of mean refractive index, measures with the ABBE refractometer.The value of the mean refractive index of the optical compensating film that following illustration is main: acylated cellulose (1.48), cycloolefine polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), polystyrene (1.59).Import the assumed value and the thickness of these mean refractive indexs, calculate nx, ny, nz by KOBRA21ADH or WR.Calculate Nz=(nx-nz)/(nx-ny) according to this nx, ny, nz that has calculated again.

(optical compensating film)

The feature of optical compensating film of the present invention is; acidylate cellophane and have incident light in normal direction with to its tilted direction that has tilted; when for example polar angle 60 was spent directions, the optical characteristics that the wavelength dispersion of hysteresis is different was used it for optical compensation energetically.

The optical characteristics of＜optical compensating film 〉

Optical compensating film of the present invention, for the colour cast that angle of visibility caused of improving liquid crystal indicator from, have the optical characteristics that satisfies following mathematical expression (1)～(5).

50≤Re (550)≤200 mathematical expression (1)

0.4≤Rth (550)/Re (550)≤0.6 mathematical expression (2)

0.1＜Re (450)/Re (550)＜0.95 mathematical expression (3)

1.03＜Re (650)/Re (550)＜1.93 mathematical expression (4)

In addition, in above-mentioned mathematical expression (1)～(4), Re (450), Re (550) and Re (650) are that (unit: nm), Rth (450), Rth (550) and Rth (650) are the lagged value (units: nm) of the thickness direction that arrives with the photo measure of wavelength 450nm, 550nm, 650nm respectively to lagged value in the face that arrives with the photo measure of wavelength 450nm, 550nm, 650nm respectively.

Also have, the Re (550) of above-mentioned mathematical expression (1) even more preferably satisfies 80≤Re (550)≤180, more preferably satisfies 100≤Re (550)≤150.

Also have, the Rth (550) of above-mentioned mathematical expression (2)/Re (550) even more preferably satisfies 0.43≤Rth (550)/Re (550)≤0.57, more preferably satisfies 0.45≤Rth (550)/Re (550)≤0.55.

Also have, the Re (450) of above-mentioned mathematical expression (3)/Re (550) even more preferably satisfies 0.3＜Re (450)/Re (550)＜0.9, more preferably satisfies 0.5＜Re (450)/Re (550)＜0.85.

Also have, the Re (650) of above-mentioned mathematical expression (4)/Re (550) even more preferably satisfies 1.08＜Re (650)/Re (550)＜1.80, more preferably satisfies 1.11＜Re (650)/Re (550)＜1.70.

Also have, be applicable to the occasion of liquid crystal indicator, the axle that sees through that preferably makes slow axis be parallel to the polarizer disposes above-mentioned optical compensating film.

Have again, preferably use the optical anisotropic layer that satisfies following mathematical expression (7-1) and mathematical expression (7-2) in the lump.

-10＜Re (550)＜10 mathematical expression (7-1)

100＜| Rth (550) |＜300 mathematical expressions (7-2)

Here, be the occasion (being the occasion of VA mode liquid crystal indicator) of VA mode at above-mentioned liquid crystal cells, even more preferably satisfy following mathematical expression (7-3) and mathematical expression (7-4), more preferably satisfy following mathematical expression (7-5) and mathematical expression (7-6).

-8＜Re (550)＜8 mathematical expression (7-3)

140＜| Rth (550) |＜240 mathematical expressions (7-4)

-5＜Re (550)＜5 mathematical expression (7-5)

160＜| Rth (550) |＜200 mathematical expressions (7-6)

＜water percentage is the polymkeric substance below 1.0% 〉

It is polymkeric substance below 1.0% that optical compensating film of the present invention preferably uses water percentage.Because liquid crystal indicator is to use under diversified environment, this is in order to alleviate the influence that humiture (particularly humidity) is caused.

As the polymkeric substance that optical compensating film of the present invention was suitable for, for example can enumerate polycarbonate-copolymerized compound, have the fluoropolymer resin that ring-type alkene is constructed.

Example as polycarbonate-copolymerized compound, can enumerate by the represented recurring unit of following general formula (1) and the represented recurring unit of following general formula (2) and form, the represented recurring unit of above-mentioned general formula (1) accounts for the polycarbonate-copolymerized compound of 80 all～30mol%.

[Chemical formula 1]

-general formula (1)

In above-mentioned general formula (1), R ₁～R ₈Be independently selected from the alkyl of hydrogen atom, halogen atom and carbon number 1～6 respectively.As the alkyl of this carbon number 1～6, can enumerate aryl such as alkyl such as methyl, ethyl, isopropyl, cyclohexyl, phenyl.Wherein, preferably hydrogen atom, methyl.

In above-mentioned general formula (1), X is following general formula (3), R ₉And R ₁₀Independent separately, be the alkyl of hydrogen atom, halogen atom or carbon number 1～3.As the alkyl of halogen atom, carbon number 1～3, can enumerate the thing identical with above-mentioned thing.

[Chemical formula 2]

General formula (2)

[chemical formula 3]

General formula (3)

In above-mentioned general formula (2), R ₁₁～R ₁₈Be independently selected from the alkyl of hydrogen atom, halogen atom and carbon number 1～22 respectively.As the alkyl of this carbon number 1～22, can enumerate the aryl such as alkyl, phenyl, xenyl, terphenyl of carbon numbers such as methyl, ethyl, isopropyl, cyclohexyl 1～9.Wherein, preferably hydrogen atom, methyl.

In above-mentioned general formula (2), Y is following formula group, R ₁₉～R ₂₁, R ₂₃And R ₂₄It is at least a kind of base that is independently selected from the alkyl of hydrogen atom, halogen atom and carbon number 1～22 respectively.About this alkyl, can enumerate the thing identical with above-mentioned thing.Also has R ₂₂And R ₂₅Be independently selected from the alkyl of carbon number 1～20 respectively,, can enumerate methine, ethylidine, propenyl, butenyl group, ring second subunit, phenylene, naphthylene, terphenyl as this alkyl.As Ar ₁～Ar ₃Phenyl can be enumerated the aryl of carbon numbers 6～10 such as naphthyl.

[chemical formula 4]

[polycarbonate-copolymerized compound]

As above-mentioned polycarbonate-copolymerized compound, the polycarbonate-copolymerized compound of forming by represented 30～60mol% of recurring unit of following general formula (4) and the represented 70～40mol% of recurring unit of following general formula (5) preferably, the even more preferably polycarbonate-copolymerized compound of forming by represented 45～55mol% of recurring unit of following general formula (4) and the represented 55～45mol% of recurring unit of following general formula (5).

[chemical formula 5]

General formula (4)

[chemical formula 6]

General formula (5)

In above-mentioned general formula (4), R ₂₆～R ₂₇Independent separately, be hydrogen atom or methyl, from operability methyl preferably.

In above-mentioned general formula (5), R ₂₈～R ₂₉Independent separately, be hydrogen atom or methyl, wait preferably hydrogen atom from economy, film characteristics.

Optical compensating film among the present invention has preferably adopted the thing of the polycarbonate-copolymerized compound with above-mentioned fluorene skeleton.As polycarbonate-copolymerized compound with this fluorene skeleton, the mixture of the polycarbonate-copolymerized compound of the different ratio of componentss of for example forming by represented recurring unit of above-mentioned general formula (1) and the represented recurring unit of above-mentioned general formula (2) preferably, 30 all～80mol% of the preferably polycarbonate-copolymerized compound of the containing ratio of above-mentioned general formula (1), even more preferably 35～75mol%, more preferably 40～70mol%.

Above-mentioned co-polymer can be the thing that above-mentioned general formula (1) and the represented recurring unit of general formula (2) is made up gained more than 2 kinds respectively.

Here, above-mentioned mol ratio can be all for the amount of the polycarbonate that constitutes optical compensating film, for example tried to achieve by nuclear magnetic resonance (NMR) device.

Above-mentioned polycarbonate-copolymerized compound can be made according to known method.Polycarbonate be fit to adopt the heavily condensation of dihydroxy compounds and phosgene method, dissolve heavy condensation method etc.

The limiting viscosity of above-mentioned polycarbonate-copolymerized compound is 0.3～2.0dL/g preferably.Can become fragile less than 0.3, the irretentive problem of physical strength is arranged, surpass 2.0, because solution viscosity rises too much, so the problem of the problems such as generation of die line, the refining difficulty that becomes when polymerization finishes is arranged in solution film-forming.

Also have, optical compensating film of the present invention can be the composition (mixture) of above-mentioned polycarbonate-copolymerized compound and other macromolecular compounds.In this occasion, as this macromolecular compound, must be transparent on the optics, so the thing that can mix with above-mentioned polycarbonate-copolymerized compound preferably, perhaps each high molecular refractive index is about equally.

As other high molecular object lessons, can enumerate many (phenylethylene-maleic anhydrides) etc., the ratio of components of polycarbonate-copolymerized compound and macromolecular compound, preferably, polycarbonate-copolymerized compound 30～80 quality %, macromolecular compound body 20～70 quality %, even more preferably, polycarbonate-copolymerized compound 40～80 quality %, macromolecular compound body 20～60 quality %.

Occasion at mixture also is to make up the recurring unit of the above-mentioned polycarbonate-copolymerized compound more than 2 kinds respectively.

Also have, in the occasion of mixture, preferably intermiscibility mixes, and but, even not exclusively mix, if the refractive index match between composition also can suppress the light scattering between composition, improves the transparency.In addition, mixture also can be the material of combination more than 3 kinds, can make up multiple polycarbonate-copolymerized compound and other macromolecular compounds.

The quality mean molecular weight of polycarbonate-copolymerized compound preferably 1,000～1,000,000, even more preferably 5,000～500,000.Also has the quality mean molecular weight of other macromolecular compounds preferably 500～100,000, even more preferably 1,000～50,000.

[polymkeric substance] with ring-type alkene structure

Hydride etc. with polymkeric substance, (4) ethene ester ring type hydrocarbon polymer and above-mentioned (1)～(4) of polymkeric substance that the ring-type alkene of (1) norbornene-based polymer, (2) monocycle is arranged in the example of fluoropolymer resin (below be also referred to as " the ring-type polyenoid is a resin " or " ring-type polyenoid ") of ring-type alkene structure, (3) cyclic conjugated diene.

The preferred polymkeric substance of the present invention is additional (being total to) polymkeric substance ring-type polyenoid that comprises the represented recurring unit of following general formula (II) more than at least a kind, and as required, comprise additional (being total to) polymkeric substance ring-type polyenoid that forms more than at least a kind of the represented recurring unit of general formula (I) again.

Also have, also can preferably use additional (being total to) polymkeric substance (also comprising open loop (being total to) polymkeric substance) that comprises the represented ring-type recurring unit of a kind of general formula (III) at least.

Also have, also can preferably use at least a kind of the represented recurring unit of general formula (III), as required, comprise additional (being total to) polymkeric substance ring-type polyenoid that forms more than at least a kind of the represented recurring unit of general formula (I) again.

[chemical formula 7]

General formula (I)

[chemical formula 8]

General formula (II)

[chemical formula 9]

General formula (III)

In the above-mentioned general formula (II)～(III), m represents 0～4 integer.R ¹～R ⁶The alkyl of expression hydrogen atom or carbon number 1～10, X ¹～X ³And Y ¹～Y ³The alkyl of expression hydrogen atom, carbon number 1～10, halogen atom, with the alkyl of the carbon number 1～10 of halogen atom displacement gained ,-(CH ₂) _nCOOR ¹¹,-(CH ₂) _nOCOR ¹²,-(CH ₂) _nNCO ,-(CH ₂) _nNO ₂,-(CH ₂) _nCN ,-(CH ₂) _nCONR ¹³R ¹⁴,-(CH ₂) _nNR ¹³R ¹⁴,-(CH ₂) _nOZ ,-(CH ₂) _nW or by X ¹And Y ¹, X ²And Y ²Perhaps X ³And Y ³Constitute (CO) ₂O, (CO) ₂NR ¹⁵

In addition, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵The alkyl of expression hydrogen atom, carbon number 1～20, Z represent alkyl or with the alkyl of halogen displacement gained, W represents SiR ¹⁶ _pD _3-p(R ¹⁶The expression carbon number 1～10 alkyl, D represent halogen atom ,-OCOR ¹⁶Or-OR ¹⁶, p represents 0～3 integer), n represents 0～10 integer.

In X ¹～X ³, Y ¹～Y ³Sub stituent import the big functional group of polarizability, thereby the thickness direction that can strengthen optical compensating film lags behind (Rth), the manifesting property of lag behind in the increasing face (Re).The optical compensating film that manifesting property of Re is big strengthens the Re value by stretching in film-forming process.

Additional (be total to) polymkeric substance of norborene system is disclosed in the spy and opens flat 10-7732 communique, the special 2002-504184 of showing communique, US2004229157A1 number or WO2004/070463A1 number etc.By the additional polymerization norborene is that the polycyclic unsaturated compound obtains.

Also having, as required, also can the additional polymerization norborene be polycyclic unsaturated compound and ethene, propylene, butylene, butadiene, the such conjugated diolefine of isoprene; The non-conjugated diene that ethylidene norbornene is such; Vinyl cyanide, acrylic acid, acrylic acid, anhydrous maleic acid, acrylate, methacrylate, maleic anhydride wire diolefin compounds such as imines, vinyl acetate, vinyl chloride that contract partially.

This additional (being total to) polymkeric substance of norborene system is sold with the trade name of A Peier (ア ペ Le) by Mitsui Chemicals (strain), and the different for example APL8008T of glass temperature (Tg) (Tg70 ℃), APL6013T (Tg125 ℃) or APL6015T ranks such as (Tg145 ℃) are arranged.Also have, by poly-ly mould TOPAS8007 that (Port リ プ ラ ス チ Star Network) (strain) sell, with 6013, with particles such as 6015.Have again, sell Appear3000 by Ferrania company.

Norbornene-based polymer hydride, as the spy open flat 1-240517 number, spy open flat 7-196736 number, spy open clear 60-26024 number, spy open clear 62-19801 number, the spy opens 2003-159767 number or special open 2004-309979 number etc. disclose, additional polymerization or transposition ring-opening polymerization polycyclic unsaturated compound add hydrogen later on to be made.

In the used norbornene-based polymer of the present invention, R ⁵～R ⁶Preferably hydrogen atom or-CH ₃, X ³And Y ³Preferably hydrogen atom, Cl ,-COOCH ₃, other bases can suitably be selected.

This norbornene resin is by JSR (strain) Yi Atong (Arton) G or Ah sells with the trade name of F, also have, then Europe (Zeon) (strain) is with that (Zeonor) ZF14, ZF16 of Europe then, Ou Nakesi (Zeonex) the 250 or then trade name of Ou Nakesi 280 is sent out the dealer then by Japan, and these can both use.

[have positive intrinsic birefringent resin and have negative intrinsic birefringent resin]

On the other hand, from the viewpoint (satisfying above-mentioned mathematical expression (3)～(4)) of optical characteristics, preferably mixing or lamination have the polymkeric substance of positive intrinsic birefringence and the polymkeric substance with negative intrinsic birefringence.As such example, can enumerate the spy and open flat 2004-309979 communique, spy and open flat 2005-126576 communique, spy and open that flat 2003-292639 communique, spy are opened flat 2006-058540 communique, the spy opens flat 2004-325971 communique, but not limited by this.

The manufacture method of＜optical compensating film 〉

Present inventors find that through further investigation adopting the stretching process to comprise oriented film is the manufacture method of feature with making the contraction process of its contraction, can obtain to have the acylated cellulose film of above-mentioned preferred optical physics characteristic.

Here, when the size that is meant film during the beginning of contraction process substantially began to reduce, the minimizing of this film dimensions comprised the situation that for example film is applied the external force of physical property, or thermal shrinkage does not apply the situation of the external force of physical property like that to film.When the minimizing that is meant the size of film during the end of contraction process substantially finishes.

Equally, the size that is meant film during the beginning of stretching process substantially begins to increase, and the increase of the size of this film is for example afterburning and physically implement stretch processing and cause on film.Be meant during the end of stretching process stop film afterburning and when physically finishing stretch processing.

In the present invention, particularly preferably be and adopt stretching process that the carriage direction be included in film stretches and control film and make the manufacture method of the contraction process of its contraction, or be included in stretching process that the Width of film stretches and the manufacture method that makes the contraction process of its contraction at the carriage direction of film at the Width of film.

At first, stretching process that the carriage direction that is included in film stretches and control film at the Width of film and make the manufacture method of the contraction process of its contraction is described.

In this occasion, be at the carriage direction oriented film of film, and as the method that the carriage direction at film stretches, adopt preferably that to make a plurality of volumes (ロ one Le) have a peripheral speed poor, the method for utilizing volume peripheral speed difference to stretch betwixt at longitudinal direction.Also have, in the related system film of solution casting method, preferably adopt on stainless band or drum and carry out curtain coating, when peeling off the film that becomes the partial desiccation state, regulate the speed of transporting roller (ロ one ラ one) of film, make the method for the coiling speed of film faster than the speed that strips of film.

At the Width of film, can slowly narrow the broadening of tentering device, thereby film and draw direction are roughly shunk orthogonally with controlling the two ends of film by anchor clamps, the fixing device that is called the tentering device of pin and transporting.

Stretching process and contraction process can by stretch to shrink one by one and contraction stretching in any one order carry out one by one.

Also have, also can be on one side control at the tentering device of the two direction of principal axis action of the carriage direction of film and Width by chain type, screw, pantograph type, tubular linear motor driven etc., slowly enlarge the interval of anchor clamps at carriage direction, thereby one side oriented film, slowly narrow the broadening of tentering device on one side, thereby it is shunk at orthogonal directions.

On the other hand, make in the manufacture method of contraction process of its contraction at stretching process that the Width of film stretches with at the carriage direction of film, can control at the tentering device of the two direction of principal axis action of the carriage direction of film and Width by chain type, screw, pantograph type, tubular linear motor driven etc., stretch on one side and slowly narrow the interval of anchor clamps at carriage direction on one side, thereby film is shunk at the Width of film.

The above-mentioned employing that has illustrated can carry out at least a portion of stretching process and contraction process simultaneously in the method for the tentering device of the two direction of principal axis action of the carriage direction of film and Width.Present inventors handle the timing, multiplying power, the speed that have by adjustment stretching contraction through discovering in the time of such, alleviate inhomogeneous such advantage that the stretching in the pellicular front that is called Boeing (ボ one イ Application ゲ) is shunk easily.

In addition, as the length direction of the film as described above that stretches particularly and any one party in the Width, the opposing party is shunk, make the stretching device of the stretching process that the thickness of film increases simultaneously, can preferably adopt city's metal working industry corporate system FITZ machine etc.Relevant this device is opened in the 2001-38802 communique on the books the spy.

Here, about extensibility in the stretching process and the shrinkage factor in the contraction process, present inventors find through further investigation, in order to make scope that Re enters hope (for example, 50～200nm), and satisfy the relation of above-mentioned mathematical expression (2), it is effective that extensibility X% in the stretching process and the relation of the shrinkage factor Y% in the contraction process satisfy following mathematical expression (Z).

[formula 3]

$90-1000/\sqrt{100+X}\&le;Y\&le;110-1000/\sqrt{100+X}\&CenterDot;\&CenterDot;\&CenterDot;\&CenterDot;\&CenterDot;\&CenterDot;$ Mathematical expression (Z)

Be lower than the occasion of the lower limit of mathematical expression (Z) in the relation of extensibility and shrinkage factor, for the satisfied Re that wishes and the relation of mathematical expression (2), the technology correspondences such as mixing of use, dissimilar polymer in the lump that just need special additive, they can cause that the look of adjuvant oozes other problems such as raising of (the tears I goes out レ), manufacturing cost.On the other hand, surpass the occasion of the upper limit of mathematical expression (Z) in the relation of extensibility and shrinkage factor, wrinkle can appear in the film after extensibility and the contraction process, can not use as optical compensating film.

In addition, the said extensibility of the present invention, be meant the stretch ratio of the length of the film after the stretching of draw direction to the length of the film before stretching, shrinkage factor is meant the ratio of the contracted length of the film after the contraction of shrinkage direction to the length of perisystolic film.

In the scope that satisfies above-mentioned mathematical expression (Z), as extensibility, preferably 5～45%, even more preferably 10～30%.Also have, as shrinkage factor, preferably 3～25%, even more preferably 5～15%.

Also have, on the basis of the optical physics characteristic that reaches hope, preferably ℃ stretch and contraction process in glass temperature+(5～50) of the film of handling time point.

Optical compensating film as manufacturing method according to the invention is made preferably satisfies following mathematical expression (A).

In addition, in following mathematical expression (A), Rth (550) 10%RH, (550) 60%RH are respectively the Rth (550) at 25 ℃ 10% and 60%RH.

10 〉=| Rth (550) 10%RH-Rth (550) 60%RH| mathematical expression (A)

Here, above-mentioned mathematical expression (A) is represented value that thickness direction hysteresis Rth (λ) preferably measures at 25 ℃, 60%RH and the absolute value of the difference of the value that measures at 25 ℃ of 10%RH is below the 10nm.

The absolute value of the difference of value that measures at 25 ℃ of 60%RH as above-mentioned thickness direction hysteresis Rth and the value that measures at 25 ℃ of 10%RH is more preferably below the 5nm.

In addition, the measurement of the glass temperature among the present invention is to film test portion (not stretching) 5mm * 30mm, adopt dynamic viscoelastic measurement mechanism (grand (バ イ Block ロ Application): the DVA-225 of white portion, peace is put forward control (ア イ テ イ Yi Meter Measuring system is driven) (strain) system of measuring), between clamping apart from 20mm, 2 ℃/minute of programming rates, measure 30～200 ℃ of temperature ranges, measure under the frequency 1Hz, the longitudinal axis is got the storage spring rate with logarithmic axis, transverse axis with linear axle get temperature (℃) time, the temperature that the expression storage spring rate that the storage spring rate is seen when solid area is transferred to the vitrifacation zone sharply reduces is as glass temperature Tg.

Particularly, on the figure that obtains, draw straight line 1 in solid area, the straight line 1 when straight line 2 is drawn in the vitrifacation zone and the intersection point of straight line 2 be exactly when heating up the storage spring rate reduce sharp and temperature that film begins to soften, be the temperature that begins to transfer to the vitrifacation zone, thus with it as glass temperature Tg (dynamically viscosity elasticity).

Also have, the temperature of above-mentioned transverse axis is meant the temperature of the film surface that measures with the noncontact infra-red thermometer.

The present invention can stretch by the wet type that stretches in the dry way according to the film of solution casting legal system film gained and implement.

Also have, after according to the drying that dissolves the film of extruding legal system film gained or solution film-forming film, carry out stretch processing continuously, also have,, all be fine in case after batching, implement stretch processing in addition.

Also have, also go for according to the not solvent-laden in fact stretching that dissolves the film of legal system film gained.

The stretching of film or shrink and can carry out with 1 section also can be carried out with multistage.In the occasion of carrying out with multistage as long as each stretching ratio long-pending enters above-mentioned preferable range.

Draw speed preferably 5～1,000%/minute, even more preferably 10～500%/minute.Stretch preferably by means of warm-up mill or/and radiant heat source (IR electric heater etc.), warm wind carry out.

On the other hand, in order to satisfy the relation of above-mentioned mathematical expression (1)～(2), the optical compensating film before stretching preferably satisfies following mathematical expression (5)～(6).

-20≤Reb (550)≤20 mathematical expression (5)

-20≤Rthb (550)≤20 mathematical expression (6)

(in above-mentioned mathematical expression (5)～(6), Reb (550) is that (unit: nm), Rthb (550) is the thickness direction lagged value (unit: nm) of the preceding optical compensating film of the stretching of arriving of the photo measure with 550nm to lagged value in the face of the optical compensating film before the stretching of arriving of the photo measure with wavelength 550nm.)

In order to realize the optical characteristics of above-mentioned mathematical expression (5)～(6), preferably be arranged on the preceding preheating procedure that film is prepared heating of stretching process.Serviceability temperature in this preheating procedure is glass temperature+(25～100) ℃ preferably.Heat treatment time preferably 1 second to 3 minute kind.

Also have, also can behind stretching process, heat-treat.Heat treatment temperature is preferably with from carrying out to high 10 ℃ temperature than the value of low 20 ℃ of the glass temperature of acetyl cellulose film, heat treatment time preferably 1 second to 3 minute kind.

Also have, heating means can be the section heating, also can be the part heating of adopting infrared heater.Also can in the way of operation or at last, cut the film two ends.These minutes smear metal is preferably reclaimed and is utilized as raw material again.

Have again, about the tentering device, in the Te Kaiping 11-077718 communique disclosure is arranged, it has disclosed when using the tentering device to keep width to make net (ウ エ Block) dry, by appropriateness control dry gas blow out method, blow out angle, wind speed profile, wind speed, air quantity, temperature difference, air quantity are poor, blow out air quantity up and down than the use of, high specific heat dry gas etc., the technology that guarantee to prevent the related raising speed of solution casting method, quality such as planarity reduces when enlarging the net width.

Also have, the spy opens and has put down in writing in the flat 11-077822 communique to preventing irregular generation, to the thermoplastic resin membrane who has stretched, behind stretching process, temperature gradient is set and the invention of heat-treating at the Width of film in heat mitigation operation.

Have, in order to prevent irregular generation, the spy opens and put down in writing the solvent containing ratio that makes film in the flat 4-204503 communique is 2～10% inventions that stretch by solid-state amount benchmark again.

Also have, in order to suppress the nip related crimping of regulation of width of anchor clamps, the spy opens to have put down in writing in the 2002-248680 communique by tentering device anchor clamps width D≤(33/ (the log extensibility * log volatile quantity)) of nipping and stretches, thereby the inhibition crimping makes film behind the stretching process transport to become and is easy to invention.

Have, transport and stretch in order to take into account the high speed mantle, the spy opens that to have put down in writing by first half in the 2002-337224 communique be pin, and latter half is that anchor clamps switch the invention that the tentering device transports.

Also have, the spy opens to have put down in writing in the 2002-187960 communique and can improve the angle of visibility characteristic easily, and to improve angle of visibility is purpose, cellulose esters dope liquid curtain coating in the curtain coating supporter, then, the net of having peeled off with supporter from curtain coating (film), residual solvent amount in net is below the 100 quality %, particularly be under the situation between the scope of 10～100 quality %, stretch 1.0～4.0 times in 1 direction at least, thereby have the invention of biaxiality on the optics that obtains.Have, as optimal way, the residual solvent amount of having put down in writing in net is below the 100 quality % again, particularly is under the situation between the scope of 10～100 quality %, at least in stretch 1.0～4.0 times situation of 1 direction.

Have again, ooze out few in order to make adjuvant, and the phenomenon of peeling off of interlayer does not have yet, and sliding is good, the phase-contrast film that the transparency is outstanding, as the spy open put down in writing in the 2003-014933 communique, put down in writing modulation and comprised resin, the dope A of adjuvant and organic solvent, do not comprise adjuvant, perhaps the amount of adjuvant comprises resin than what dope A lacked, the dope B of adjuvant and organic solvent, it is total to curtain coating on supporter, makes dope A become core layer, dope B becomes superficial layer, make organic solvent evaporation to the strippable degree, net is peeled off from supporter, and the residual solvent in the resin film when stretching is under the situation of scope of 3～50 quality % again, with it at least in stretch 1.1～1.3 times the invention of 1 direction of principal axis.

Have again, as optimal way, put down in writing the situation of some below the utilization: net is peeled off from supporter, again under draft temperature is 140～200 ℃ the situation of scope, with it at least in stretch 1.1～3.0 times situation of 1 direction of principal axis, modulation comprises the dope A of resin and organic solvent, with comprise resin, the dope B of particulate and organic solvent, it is total to curtain coating on supporter, make dope A become core layer, dope B becomes superficial layer, make organic solvent evaporation to the strippable degree, net is peeled off from supporter, residual solvent in the resin film when stretching is under the situation of scope of 3～50 quality % again, with it at least in stretch 1.1～3.0 times situation of 1 direction of principal axis, again under draft temperature is 140～200 ℃ the situation of scope, with it at least in stretch 1.1～3.0 times situation of 1 direction of principal axis, modulation comprises resin, the dope A of organic solvent and adjuvant, do not comprise adjuvant, perhaps the amount of adjuvant comprises resin than what dope A lacked, the dope B of adjuvant and organic solvent, comprise resin, the dope C of particulate and organic solvent, it is total to curtain coating on supporter, make dope A become core layer, dope B becomes superficial layer, dope C becomes the superficial layer of the opposition side of dope B, make organic solvent evaporation to the strippable degree, net is peeled off from supporter, residual solvent in the resin film when stretching is under the situation of scope of 3～50 quality % again, with it at least in stretch 1.1～3.0 times situation of 1 direction of principal axis, be under 140～200 ℃ the situation of scope at draft temperature, with it at least in stretch 1.1～3.0 times situation of 1 direction of principal axis, additive capacity among the dope A is 1～30 quality % with respect to resin, additive capacity among the dope B is 0～5 quality % with respect to resin, adjuvant is a plasticizer, or ultraviolet light absorber, or lag behind to adjust the situation of agent, among the dope A and the organic solvent among the dope B by with respect to the situation that contains methylene chloride or methyl acetate more than the full organic solvent 50 quality %.

Have again,, improve from taking off property for the foaming of the net that prevents tentering device drying, prevent to send out dirt, the spy opens in the 2003-004374 communique and has put down in writing in drying device, makes the width of exsiccator be shorter than the width of net, thereby makes the hot blast of exsiccator not run into the invention of net two edge portions.

Also have, the foaming for the net that prevents tentering device drying improves from taking off property, prevents to send out dirt, and the spy opens to have put down in writing in the 2003-019757 communique in net both side ends inboard deep bead is set, thereby makes dry wind not run into the invention of the maintaining part of tentering device.

Have again, for stably transport, drying, the dried thickness that the spy opens the both ends of having put down in writing the film that is gripped by pin tentering device in the 2003-053749 communique is X μ m, the dried average thickness of the goods portion of film is the words of T μ m, the relation of X and T satisfies when formula (1) T≤60, and 40≤X≤200 are when formula (2) 60＜T≤120,40+ (T-60) * 0.2≤X≤300 or when formula (3) 120＜T, the invention of the relation of 52+ (T-120) * 0.2≤X≤400.

Also have, do not produce wrinkle in order to make multisection type tentering device, the spy opens in the flat 2-182654 communique and has put down in writing in the tentering apparatus, and heating chamber and cooling chamber are set in the exsiccator of multisection type tentering device, respectively the invention of the anchor clamps chain about the cooling.

Have, for breaking of preventing to net, wrinkle, transport badly, the spy opens the pin of having put down in writing in the flat 9-077315 communique for pin tentering device, strengthens inboard pin density, reduces the invention of the pin density in the outside again.

Also have, in order to prevent that foaming, net in tentering device Intranet itself from adhering in maintaining body, put down in writing in the Te Kaiping 9-085846 communique in tentering device drying device, keep net both side edges portion pin to be cooled to blowing temperature with blowing out the type refrigeratory, and wedging net pin before is cooled to the invention below gelatinization temperature+15 ℃ of dope with the conduit type refrigeratory less than net.

Have again, throw off for anti-shotpin tentering device, improve foreign matter, the spy opens and has put down in writing in the 2003-103542 communique in pin tentering device, tectosome is inserted in cooling, and the surface temperature of the feasible net that contacts with the insertion tectosome is no more than the invention that relates to solution film-forming method of the gelatinization temperature of net.

Also have, in order to prevent to come raising speed by solution casting method, quality such as planarity when enlarging the width of netting with the tentering device reduce, put down in writing in the Te Kaiping 11-077718 communique when tentering device inner drying net, making wind speed is 0.5～20 (40) m/s, the transverse direction Temperature Distribution is below 10%, and descending the air quantity ratio on the net is 0.2～1, and dry gas is than being the invention of 30～250J/Kmol.

Have again, disclosed in the drying in the tentering device, the preferred drying condition corresponding with the amount of residual solvent.

Specifically put down in writing following situation, after supporter has been peeled off net, residual solvent amount in net to become till the 4 quality % during, from the angle that blows out of blow-off outlet with respect to the scope of thin film planar at 30～150 °, for the wind speed profile on the film surface that blows out extending direction that is positioned at dry gas, when the higher limit with wind speed is benchmark, the difference of higher limit and lower limit be made as higher limit 20% in, blow out dry gas, make the net dry situation, residual solvent amount in net is when 70 quality % are above below the 130 quality %, be made as situation below the above 20m/sec of 0.5m/sec from blowing out dry gas that the type dryer blows out at the wind speed on the net surface, in the residual solvent amount is less than 70 quality %, when 4 quality % are above, make its drying by the dry gas wind that blows out below the above 40m/sec of wind speed 0.5m/sec with dry gas, the Temperature Distribution of the dry gas of the Width of net, when the higher limit with gas temperature is benchmark, the difference of higher limit and lower limit be made as higher limit 10% with interior situation, residual solvent amount in net is when 200 quality % are following more than the 4 quality %, and the air quantity of the dry gas that blows out from the blow-off outlet of the type that the blows out dryer up and down that is positioned at the net that is transported is made as the situation of 0.2≤q≤1 than q.

Have again, as optimal way, disclosed and used a kind of gas at least as dry gas, its mean specific heat is more than the 31.0J/Kmol, the situation that 250J/Kmol is following is that the dry gas of the saturated vapor pressure below 50% carries out dry situation etc. with the concentration of the organic compound of liquid under the normal temperature that comprises in the dry gas in the drying.

Also have, in order to prevent owing to the generation of polluter planarity, coating to be worsened, the spy opens in the flat 11-077719 communique and has put down in writing in the manufacturing installation of TAC (Triafol T), the invention of the built-in heating part of anchor clamps of tentering device.

As preferred mode, disclosed and be provided with after the anchor clamps of tentering device unclamp net, to gripping once more between the net, remove the situation of the device of the foreign matter that produces in the contact portion of anchor clamps and net, the situation of removing foreign matter with the gas that sprays or liquid and brush, residual quantity during the contacting of anchor clamps or pin and net is the following situations of the above 50 quality % of 12 quality %, and the surface temperature of the contact site of anchor clamps or pin and net is the situation of (even more preferably more than 80 ℃ below 120 ℃) etc. more than 60 ℃ below 200 ℃.

In order to improve planarity, the quality of improving in the tentering device that cracking caused reduces, improve productivity, put down in writing in tentering device anchor clamps the transporting length L t (m) arbitrarily and keep the ratio Lr=Ltt/Lt of summation Ltt (m) of length of carriage direction of the part of net to be made as the invention of 1.0≤Lr≤1.99 of tentering device in the Te Kaiping 11-090943 communique with the anchor clamps of the tentering device of Lt equal length.And as optimal way, disclosed that the part that keeps net looks from the net Width is situation about disposing very close to each otherly.

Also have, when importing net in order to improve on the tentering device, because of the lax planarity deterioration that causes and the importing instability of net, the spy opens in the flat 11-090944 communique and has put down in writing in the manufacturing installation of plastic sheeting, has the invention of the lax restraining device of net Width before tentering device inlet.

In addition, as preferred mode, disclosed lax restraining device and be in the angle of the Width expansion situation at 2～60 ° the rotating revolution roller of direction scope, had the situation of getter device on the top of net, having can be from the situation of the pressure fan of air-supply off the net etc.

Purpose is not cause the deterioration of quality and hinders productive laxly that the spy opens in the flat 11-090945 communique and put down in writing in the method for making of TAC, makes the net of having peeled off from supporter have angle with respect to level and is directed in the invention of tentering device.

Also have, in order to make the film of stable physical characteristics, the spy open put down in writing in the 2000-289903 communique be stripped from, the time point of solvent containing ratio 50～12 quality %, give tension force and in the conveyer that transports in the broadening direction of net, have the width detection mechanism of net and the maintaining body of net, the changeable bending point more than 2, by the width detection of net, come computing net width according to the signal that detects, the invention of the position of change bending point.

Have again, in order to improve clamping, what prevent between long-term to net breaks, obtain the outstanding film of quality, the spy opens the left and right sides of having put down in writing near the part inlet of tentering device in the 2003-033933 communique, above the left and right sides edge portion of net and below at least below configuration net side edge part crimping prevent from use guide plate, the net subtend face of guide plate by the net in the carriage direction configuration of net contact with resin portion with net the situation about constituting that contacts with metal part.

Have again, as preferred mode, disclosed following situation: the net contact of the net subtend face of guide plate is configured in the upstream side of net carriage direction with resin portion, net contact is configured in situation with the downstream with metal part, the net contact of guide plate is that 500 μ m are with interior situation with resin portion and net contact with the step between the metal part (comprising inclination), the net contact of guide plate is respectively the situation of 2～150mm with the distance of the Width that contacts with net of metal part with resin portion and net contact, the net contact of guide plate is respectively the situation of 5～120mm with the distance of the net carriage direction that contacts with net of metal part with resin portion and net contact, the net contact of guide plate is to cover with paint, lacquer, colour wash, etc. situation about being provided with by surface resin processing or resin on metallic guiding substrate with resin portion, the situation that the net contact of guide plate is made up of resin monomer with resin portion, distance below the left and right sides edge portion of net reaches up between the net subtend face of the guide plate of configuration is the situation of 3～30mm, left and right sides edge portion at net, distance between the net subtend face of two guide plates up and down, at the Width of net and towards interior side, every width 100mm is in the above ratio condition of enlarged of 2mm, left and right sides edge portion at net, two guide plates have the length of 10～300mm respectively up and down, and two guide plates dispose before and after the carriage direction of net with departing from up and down, up and down the distance that departs between two guide plates be-200～+ situation of 200mm, the situation that the net subtend face of top guide plate only is made of resin or metal, the net contact of guide plate is special teflon (registered trademark) system with resin portion, netting contact is the situation of stainless steel with metal part, and the net subtend face of guide plate or the net contact that is provided with on it are the following situation of 3 μ m etc. with the surfaceness that resin portion and/or net contact with metal part.

Also have, also put down in writing net side edge part crimping prevent to use lower guide plate optimum seeking site is set be from supporter peel off side end to the tentering device introduction part, particularly preferably be near situation about being arranged at the tentering device inlet partly.

Have again, for the fracture of the net that prevents from tentering device inner drying, to produce, irregular, put down in writing after peeling off in the Te Kaiping 11-048271 communique, the time point of the solvent containing ratio 50～12wt% of net, stretch with the width tension device, carry out drying, and the time point below the solvent containing ratio 10wt% of net is given the invention of the pressure of 0.2～10KPa from the two sides of net by pressue device.

Have again, as optimal way, the time point that has disclosed more than solvent containing ratio 4 quality % finishes the situation that tension force gives, as the method for exerting pressure from net (film) two sides, in the occasion that adopts the pincers withdrawing roll to exert pressure, the pincers withdrawing roll is to 1 to 8 group degree preferably, and the temperature of pressurized applications is 100～200 ℃ situation preferably.

Also have, open the 2002-036266 communique,, disclosed tentering device front and back are made as 8N/mm to net in the difference of the tension force that works along its carriage direction as optimal way spy as the invention of the thin TAC of high-quality that is used for obtaining thickness 20～85 μ m ²Following situation possesses after stripping process the preheating procedure of preheated web, after this preheating procedure, with the stretching process of tentering device stretching nets, after this stretching process, make situation of the mitigation operation that net relaxes with the amount of lacking than the amount of tension of this stretching process etc.

Disclosed the temperature T in preheating procedure and the above-mentioned stretching process ₁Be made as more than (the glass temperature Tg-60 of film) ℃, and the temperature T that relaxes in the operation ₂Be made as (T ₁-10) situation ℃ by being made as 0～30% with respect to the ratio that enters the net width before this stretching process, is made as the extensibility of the net under the mitigation operation-10～10% situation etc. to the extensibility of the net under the stretching process.

Have again, purpose be to make dry film thickness be the outstanding spy of little permanance of the slimming of 10～60 μ m and lightweight moisture-penetrability open the 2002-225054 communique disclosed peeling off after, between becoming till the 10 quality % to the residual solvent amount of netting, control the two ends of net with anchor clamps, the drying of carrying out under the width maintenance is shunk inhibition, and/or stretch at Width, form following formula, the represented planar orientation degree (S) of S={ (Nx+Ny)/2}-Nz is that the situation of 0.0008～0.0020 film is (in the formula, Nx is the refractive index of the direction of the interior refractive index maximum of the face of film, Ny is the refractive index with respect to Nx vertical direction in face, Nz is the refractive index of the film thickness direction of film), the situation that is made as 30～90 seconds from curtain coating to the time of peeling off, situation that the net after peeling off is stretched at Width and/or length direction etc.

Also have, the spy opens to have put down in writing in the 2002-341144 communique to have for suppressing optics irregularly, and the mass concentration of control (rising) agent that lags behind has more the solution film-forming method near the stretching process of the high more optical profile of thin-film width direction central authorities.

Have again; open stretching ratio that the 2003-071863 communique put down in writing the broadening direction preferably 0～100% spy as the invention of the film that is used for obtaining not producing cloud point; as the occasion of polarization plate protective film, even more preferably 5～20%, 8～15% situation more preferably.

Have again, on the other hand, disclosed as the stretching ratio of the broadening direction of the occasion of phase-contrast film even more preferably 10～40%, more preferably 20～30%, can control Ro by stretching ratio, stretching ratio is high more, the planarity of the film of finishing runs off look, thereby is preferred situation.

Have again, the residual solvent amount that has provided the film of the occasion of carrying out tentering preferably is 20～100 quality % when tentering begins, and preferably till becoming below the 10 quality %, the residual solvent amount of film carries out drying, even more preferably the following situation of 5 quality % while carrying out tentering.

Also have, preferably 30～150 ℃ of the baking temperatures of the occasion of carrying out tentering have also been disclosed, even more preferably 50～120 ℃, more preferably 70～100 ℃, baking temperature is low more, and the evaporation of ultraviolet light absorber, plasticizer etc. is few more, can reduce operation pollutes, on the other hand, baking temperature is high more, and the planarity of film runs off the situation of look.

Also have, when under as high-temperature, high humidity, preserving, the spy who reduces the invention of longitudinal and transverse dimensional variations opens and has put down in writing curtain coating cellulose ester solution on supporter in the 2002-248639 communique, it is peeled off continuously, make in the manufacture method of its dry film, make drying shrinkage satisfy following formula, the residual solvent amount (%) of 0≤drying shrinkage (%)≤0.1 * when peeling off and make the invention of its drying.

Have again, as optimal way, when the residual solvent amount that has disclosed the cellulose ester film after peeling off is in the scope of 40～100 quality %, transport at the tentering device on one side and control the both ends of cellulose ester film down, at least make the residual solvent amount reduce the above situation of 30 quality % on one side, the residual solvent amount that the tentering device of the cellulose ester film after peeling off transports the porch is 40～100 quality %, the residual solvent amount in exit is the situation of 4～20 quality %, make and transport the situation that inlet that the tension force that transports down cellulose ester film transports from the tentering device increases towards outlet, transport the tension force situation about equally etc. of the Width of the tension force that transports cellulose ester film down and cellulose ester film at the tentering device at the tentering device.

In addition, thin in order to obtain thickness, the isotropy of optics, the film that planarity is outstanding, the relation that the spy opens the residual solvent rate X that disclosed in the 2000-239403 communique when peeling off and residual solvent rate Y when the tentering device imports are made as the scope of 0.3X≤Y≤0.9X and make the situation of film.

Open the method that has disclosed in the 2002-286933 communique as the film by curtain coating system film that stretches the spy, can enumerate the method that under heating condition, stretches and contain the method for having ready conditions and stretching down at solvent, the occasion that under heating condition, stretches, preferably stretch with the nearby following temperature of the vitrifying point of resin, on the other hand, the occasion that the film of casting film gained stretches under to solvent impregnated condition, the film that once can make dry contacts and immersion solvent with solvent once more, to its situation about stretching.

[dissolving the system film]

The method for making of optical compensating film of the present invention also can be to dissolve the system film.Can dissolve the heating of raw materials such as the polymkeric substance that becomes raw material, adjuvant, it is extruded, carry out filming, also can be sandwiched in warmed-up 2 plates to raw material, carry out filming by punching press by ejection formation.

The temperature that heating dissolves is not particularly limited so long as the temperature that raw polymer is together evenly dissolved gets final product, and can suitably select according to purpose, for example, is heated to the above temperature of fusing point or softening point.In order to obtain uniform film, preferably be heated to the temperature higher than the fusing point of raw polymer, even more preferably high 5～40 ℃ temperature than fusing point, more preferably high 8～30 ℃ than fusing point temperature dissolves it.

＜optical anisotropic layer 〉

As doing one's utmost to reduce Re, the method for control Rth preferably adopts by the method that is coated with the optical anisotropic layer that liquid crystal layer etc. makes.

Object lesson as liquid crystal layer, can enumerate and make discoid liquid crystal become 5 degree with the method (spy opens flat 10-312166 communique) that interior mode is orientated, make rod shaped liquid crystal become the method (spy opens the 2000-304932 communique) that 5 degree are orientated in interior mode by the angle of its major axis and above-mentioned optical compensating film face by the angle of its disc face and above-mentioned optical compensating film face.

This optical anisotropic layer is for liquid crystal indicator, and particularly the expansion of the angle of visibility ratio of the liquid crystal indicator of OCB mode, VA mode and the alleviating of colo(u)r bias that depend on angle of visibility have contribution.

Optical compensating film can be configured between the polarization plate of observer's side and the liquid crystal cells or be configured between the polarization plate and liquid crystal cells of rear side, also can be disposed at both.

For example, can be used as independently the parts liquid crystal indicator inside of packing into, also have, also can give optical characteristics, it is worked as transparent membrane, as parts of the polarization plate liquid crystal indicator inside of packing into the diaphragm of protection polarization film.

[ultraviolet light absorber]

Preferably adopt ultraviolet light absorber in the optical compensating film of the present invention.

As ultraviolet light absorber, be not particularly limited, can suitably select according to purpose, for example, can adopt absorbing agents such as salicylate system, benzophenone series, benzotriazole system, benzoic ether system, cyanoacrylate system, nickel complex salt system, preferably benzophenone series, benzotriazole system, salicylate system.

Example as the benzophenone series ultraviolet light absorber, can enumerate 2,4-dihydroxy benaophenonel, 2-hydroxyl-4-acetate benzophenone, 2-hydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxy-4-methoxy benzophenone, 2,2 '-dihydroxy-4,4 '-methoxy benzophenone, Octabenzone, 2-hydroxyl-4-dodecyl hydroxyethyl benzophenone, 2-hydroxyl-4-(2-hydroxy-3-methyl acryloxy) propoxyl group benzophenone etc.

As benzotriazole is ultraviolet light absorber, can enumerate 2 (2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole, 2 (2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2 (2 '-hydroxyl-3 ', 5 '-the diamyl phenyl) benzotriazole, 2 (2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorinated benzotriazole, 2 (2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole etc.

As salicylate system, can enumerate phenyl salicytate, p-octylphenyl salicylate, p-t-butylphenyl salicylate etc.

In these illustrative ultraviolet light absorbers, particularly preferably be 2-hydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxy-4,4 '-methoxy benzophenone, 2 (2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole, 2 (2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2 (2 '-hydroxyl-3 ', 5 '-the diamyl phenyl) benzotriazole, 2 (2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorinated benzotriazole.

A plurality of absorbing agents that the compound employing absorbing wavelength of ultraviolet light absorber is inequality preferably can obtain high partition effect in big wavelength coverage.

Liquid crystal with ultraviolet light absorber preferably, from preventing the viewpoint of liquid crystal deterioration, the following ultraviolet receptivity of wavelength 370nm is outstanding, and, from the viewpoint of liquid crystal expressivity, the few thing of absorption of the visible light that wavelength 400nm is above.Particularly, the benzotriazole based compound that had before provided, benzophenone based compound, salicylate based compound are preferred as ultraviolet light absorber, and wherein, the benzotriazole based compound is because useless painted few, thereby preferred especially.

Also have, about ultraviolet light absorber, also can adopt the spy open clear 60-235852 number, spy open flat 3-199201 number, with 5-1907073 number, with 5-194789 number, with 5-271471 number, with 6-107854 number, with 6-118233 number, with 6-148430 number, with 7-11056 number, with 7-11055 number, with 7-11056 number, with 8-29619 number, open the compound of putting down in writing in each communique of 2000-204173 number with 8-239509 number, spy.

The addition of ultraviolet light absorber is 0.001～5 quality % with respect to polymkeric substance preferably, even more preferably 0.01～1 quality %.Additive effect can be given full play to if addition is more than the 0.001 quality %, thereby is preferred, if addition is 5 quality % with next the oozing out of ultraviolet light absorber that can suppress on the film surface, thereby is preferred.

Also have, ultraviolet light absorber can add when polymer dissolution simultaneously, also can make an addition to the dope (occasion of solution film-forming) after the dissolving.Particularly adopt static mixer etc., before curtain coating, can easily adjust spectral absorption characteristics, thereby be preferred to the mode of dope interpolation UVA agent solution.

[preventing degradation]

Also have,, suitably use to prevent that degradation from also being preferred to prevent the optical compensating film deterioration, to be decomposed into purpose.

As preventing degradation, can enumerate butylamine, hindered amine compound (spy opens flat 8-325537 communique), guanidine compound (spy opens flat 5-271471 communique), benzotriazole is UV absorbing agent (spy opens flat 6-235819 communique), benzophenone series UV absorbing agent compounds such as (spy open flat 6-118233 communique).

[dyestuff]

Also have, in the present invention, can add the dyestuff that is used for the form and aspect adjustment.The amount of dyestuff is 10～1 with respect to the mass ratio of polymkeric substance preferably, 000ppm, even more preferably 50～500ppm.Contain dyestuff like this, the right rolling of optical compensating film just can reduce, and can improve yellow hue.These compounds preferably add in polymer solution, or mixing when polymkeric substance dissolves.

[matting agent particulate]

In the optical compensating film that the present invention preferably adopts, preferably add particulate as matting agent.As the particulate that uses among the present invention, can enumerate silicon dioxide, titania, aluminium oxide, zirconia, lime carbonate, talcum, clay, burn till porcelain earth, burn till calcium silicate, hydrated calcium silicate, alumina silicate, magnesium silicate and calcium phosphate.Particulate aspect the turbidity step-down, preferably contains the thing of silicon, particularly preferably is silicon dioxide.

The particulate of silicon dioxide preferably 1 averaged particles directly is below the 20nm, and outward appearance proportion is the above thing of 70g/L.The mean diameter of 1 particle is little, be 5～16nm thing can reduce the mist degree of film, be more preferably.Outward appearance proportion is preferably more than 90～200g/L, even more preferably more than 100～200g/L.Outward appearance proportion is big more, can make the dispersion liquid of high concentration more, and mist degree, condensation product can improve, thereby be preferred more.

In the occasion that adopts silicon dioxide particles as matting agent, its use amount is 0.01～0.3 mass parts with respect to component of polymer 100 mass parts that comprise acylated cellulose preferably.

These particulates form 2 particles that averaged particles directly is 0.1～3.0 μ m usually, and the condensed matter as 1 particle exists in film, forms the concavo-convex of 0.1～3.0 μ m on film surface.

The averaged particles footpath of 2 particles is preferably below the above 1.5 μ m of 0.2 μ m, even more preferably below the above 1.2 μ m of 0.4 μ m, more preferably below the above 1.1 μ m of 0.6 μ m.If this averaged particles directly is below the 1.5 μ m, mist degree just can not be strong excessively, also has, if be more than the 0.2 μ m, just can give full play to the effect that prevents rough sense.

Atomic 1 time, 2 times particles directly are with the particle in the scanning electron microscope viewing film, with the external diameter of a circle of particle be particle diameter.Also having, change the place and observe 200 particles, is the averaged particles footpath with its mean value.

The particulate of silicon dioxide for example, can use " Ah Ei Lou Ji Shandong (ア エ ロ ジ Le) " R972, R972V, R974, R812,200,200V, 300, R202, OX50, TT600 commercially available products such as (above for making Japanese Ah Ei Lou Ji Shandong (strain)).Zirconic particulate for example, is sold with the trade name of " Ah Ei Lou Ji Shandong " R976 and R811 (above is Japanese Ah Ei Lou Ji Shandong (strain) system), can use.

Wherein " Ah Ei Lou Ji Shandong 200V ", " Ah Ei Lou Ji Shandong R972V " are that 1 averaged particles is directly for below the 20nm, and outward appearance proportion is the particulate of the above silicon dioxide of 70g/L, because very the lowland keeps the turbidity of optical compensating film, and the effect that reduces friction factor is big, thereby is particularly preferred.

In the present invention, in order to obtain to contain the optical compensating film of the little particle in 2 averaged particles footpaths, when the atomic dispersion liquid of modulation, can consider several gimmicks.

For example, have in advance and to make the micro-dispersed liquid that mixes solvent and particulate gained, the small amount of polymer solution that this micro-dispersed liquid is added on other preparation is carried out stirring and dissolving, again the method for mixing with main polymkeric substance dope liquid.

This method is because the good dispersion of silicon dioxide particles, so be preferred method for making at silicon dioxide particles aspect being difficult to condense again.

In addition, also have in solvent, to add a spot of polymkeric substance, carry out after the stirring and dissolving, add particulate therein, disperse with dispersion machine, with it as the particulate annex solution, the method that this particulate annex solution is mixed fully with stirring machine on the line and dope liquid.

In the present invention, not limited by these methods, but, the concentration of silicon dioxide when silicon dioxide particles being mixed with solvent etc. and disperse is 5～30 quality %, even more preferably 10～25 quality %, more preferably 15～20 quality % preferably.

Gao Ze is low more with respect to the liquid turbidity of addition more to disperse concentration, and mist degree, condensation product can improve, thereby be preferred more.The preferably every 1m of the addition of the matting agent in the dope solution of final polymkeric substance ²Be 0.01～1.0g, even more preferably 0.03～0.3g, more preferably 0.08～0.16g.

Employed solvent as lower alcohols, can be enumerated preferred methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols etc.Solvent as beyond the lower alcohol is not particularly limited, and but, preferably adopts solvent used when the system film of cellulose esters.

＜water percentage 〉

Have again, the preferred optical compensating film that uses among the present invention, 25 ℃, the equilibrium moisture content at 80%RH place are to be preferred aspect the tonal variation that timeliness caused of minimizing liquid crystal indicator below 1.0%.

The mensuration of water percentage is to adopt optical compensating film test portion 7mm * 35mm drimeter (CA-03, Mitsubishi Chemical's (strain) system), test portion drying device (VA-05, Mitsubishi Chemical's (strain) system) to measure with Ka Er Brigit Fischer (Schmidt) method.Amount of moisture (g) is calculated divided by test portion quality (g).

＜spring rate 〉

The measurement of spring rate is that optical compensating film test portion 10mm * 150mm is carried out under 25 ℃, 60%RH more than 2 hours after the damping, with cupping machine (Si Telugu pressgang (ス ト ロ ゲ ラ Off)-R2, the smart mechanism of (strain) Japan is done made), carrying out under dividing apart from 100mm, 25 ℃ of temperature, draw speed 10mm/ between chuck.

The measurement of moisture expantion coefficient is the size of placing the film more than 2 hours down according to 25 ℃, 80%RH, the value L that measures with pin gauge _80%With the size that 25 ℃, 10%RH are placed the film more than 2 hours down, the value L that measures with pin gauge _10%, (B) tries to achieve by following mathematical expression.

(L _80%-L _10%)/(80%RH-10%RH) * 10 ⁶Mathematical expression (B)

＜mist degree 〉

Also have, the preferred optical compensating film that uses among the present invention, its mist degree is 0.01～2% scope preferably.

In the present invention, the measurement of mist degree is that optical compensating film test portion 40mm * 80mm is measured by JIS K-6714 with haze meter (HGM-2DP, SUGA testing machine (strain) system) under 25 ℃, 60%RH.

＜change in size 〉

Also have, among the present invention the preferred optical compensating film that uses preferably under 60 ℃, the condition of 95%RH, leave standstill 24 hours occasion change in size and under 90 ℃, the condition of 5%RH, leave standstill 24 hours the change in size of occasion all in 0～5% scope.

＜photoelastic coefficient 〉

Have, the photoelastic coefficient of optical compensating film of the present invention is 50 * 10 again ^-13Cm ²Below/the dyne, be preferred aspect the homogeneity when making it improve with the liquid crystal indicator stickup.

As concrete measuring method, be that long axis direction to optical compensating film test portion 10mm * 100mm adds drawing stress, with ellipsometer (エ リ プ ソ メ one one) (M150, Japan's beam split (strain) system) measures the hysteresis of this moment, calculate photoelastic coefficient according to variable quantity with respect to the hysteresis of stress.

(polarization plate)

In the present invention, provide the polarization plate of being made up of a pair of diaphragm of polarization film and this polarization film of clamping, promptly at least one of said protection film (is to watch side in occasion of the present invention) is the polarization plate of acylated cellulose film.

For example, can adopt polarization film to dye, stretch, lamination is carried out with protective film and the polarization plate that obtains in its two sides with iodine to forming by polyvinyl alcohol film etc.

This polarization plate is configured in the outside of liquid crystal cells.Preferably the mode of a pair of polarization plate of being made up of a pair of diaphragm of polarization film and this polarization film of clamping with the holding liquid crystal unit disposed.

In addition, be configured in the diaphragm optical compensating film preferably of the present invention of liquid crystal cell side.

＜bonding agent 〉

The bonding agent of polarization film and diaphragm is not particularly limited, and can enumerate PVA is resin (comprising sex change PVA such as acetoacetyl, sulfonic group, carboxyl, oxyalkylene group), boron compound aqueous solution etc., and wherein preferably PVA is a resin.0.01～10 micron of the preferably dry back of bond layer thickness, even more preferably 0.05～5 micron.

The coherent manufacturing process of＜polarization film and diaphragm 〉

Among the present invention spendable polarization plate be have polarization film with film stretching after; make its contraction and reduce the drying process of volatility and make acquisition; but, preferably after drying or in the drying at least the one side bonding diaphragm after, have back heating process.

As concrete method of attaching; have in the drying process of film; under the state that keeps two ends, use bonding agent to paste diaphragm to polarization film; after this limit is cut at its two ends; perhaps after drying; remove the polarized light membrane films from the two ends maintaining part, the limit is cut at the film two ends after, the method for pasting diaphragm etc.As the method for cutting the limit, can be the method that adopts cutter etc. to shear, adopt the general technology such as method of laser.

After bonding,,, preferably heat in order to improve the polarized light performance in order to make the bonding agent drying.As the condition of heating, different with bonding agent, but, and in the occasion of water system, preferably more than 30 ℃, even more preferably 40～100 ℃, more preferably 50～90 ℃.These operations are made with the line that links up, and are preferred reaching on the production efficiency on the performance.

The performance of＜polarization plate 〉

The optical property of polarization plate of the present invention and permanance (short-term, long-term keeping quality) preferably have and the equal above performance of commercially available superelevation contrast product (for example, the Sang Lizi of Co., Ltd. (サ Application リ Star Star) corporate system HLC2-5618 etc.).

Particularly, visible light transmissivity is more than 42.5%, polarization luminosity { (Tp-Tc)/(Tp+Tc) } ^1/2〉=0.9995 (herein, Tp is parallel transmitance, Tc is the quadrature transmitance), at 60 ℃, place 500 hours and 80 ℃, dry gas atmosphere under the humidity 90%RH atmosphere and place the rate of change of the light transmission rate before and after 500 hours its of occasion down, based on absolute value, preferably below 3%, even more preferably below 1%.Also have, the rate of change of polarization luminosity is based on absolute value, preferably below 1%, even more preferably below 0.1%.

＜surface treatment 〉

Optical compensating film of the present invention can carry out surface treatment according to occasion, thereby improves and the acylated cellulose film of protection polarization plate or the cementability of polarizer layer.

As surface treatment, for example can adopt glow discharge processing, ultraviolet treatment with irradiation, corona treatment, flame treatment, acid or alkali treatment.

Here said glow discharge is handled, and can adopt 10 ^-3The low-temperature plasma that the low-pressure gas of～20Torr produces down also has, and the plasma treatment under the atmospheric pressure also is preferred.

Plasma incentive gas is meant under these conditions the gas by the plasma excitation, can enumerate such freon class of argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane and composition thereof etc.

About these, report public technical ability 2001-1745 number (distribution on March 15 calendar year 2001, invention association) to be documented in p.30-32 in the open skill of invention association.

In addition, the plasma treatment under the atmospheric pressure of being paid close attention to for example adopted 10～1 in recent years, and the irradiation energy of 20～500kGy under the 000keV even more preferably adopts the irradiation energy of 20～300kGy under 30～500keV.

Have, polarization plate involved in the present invention preferably is provided with hard coat, antiglare layer and prevents one deck at least in the reflection horizon on the surface (occasion of the present invention is to watch side surface) of the diaphragm of at least one side of polarization plate again.

Promptly; preferably, when polarization plate is used for liquid crystal indicator, functional membranes such as preventing the reflection horizon is set on the diaphragm of the opposition side that is disposed at liquid crystal cells; as this functional membrane, hard coat, antiglare layer preferably are set and prevent one deck at least in the reflection horizon.

In addition, each layer needn't be provided with as individual course respectively, for example, also can make to prevent that reflection horizon, hard coat have the function of anti-dazzle property, thereby need not be provided with two layers that prevent reflection horizon and antiglare layer, and make it prevent that as anti-dazzle property the reflection horizon from working.

＜prevent the reflection horizon 〉

In the present invention; on the diaphragm of polarization plate, suitably be provided with at least by light scattering layer and low-index layer in this order lamination form prevent the reflection horizon, perhaps on diaphragm, suitably be provided with by middle index layer, high refractive index layer, low-index layer in this order the lamination gained prevent the reflection horizon.Below put down in writing its preference.In addition, in the former formation, generally speaking specular reflectance is more than 1%, is called Low Reflection (LR) film.In the latter's formation, be to realize the thing of specular reflectance below 0.5%, be called Anti Reflection (AR) film.

[LR film]

Below be described in the preference that prevents reflection horizon (LR film) that light scattering layer and low-index layer are set on the diaphragm of polarization plate.

Preferably the delustring particle is scattered in the light scattering layer, the refractive index of the material of the part beyond the delustring particle of light scattering layer is 1.50～2.00 scope preferably, and the refractive index of low-index layer is 1.20～1.49 scope preferably.

In the present invention, light scattering layer has both anti-dazzle property and hard coating, can be made of one deck, also can be by multilayer, and for example two layers～four layers constitute.

For preventing the reflection horizon, as its concave-convex surface shape, being designed to center line average roughness Ra is 0.08～0.40 μ m, 10 mean roughness Rz are below 10 times of Ra, average concavo-convex is 1～100 μ m apart from Sm, standard deviation from the protuberance height in concavo-convex deep is below the 0.5 μ m, is center line below the 20 μ m as average concavo-convex the standard deviation apart from Sm of benchmark, the face that the inclination angle is 0～5 ° is more than 10%, just can reach sufficient anti-dazzle property and visual under uniform delustring sense, thereby be preferred.

Also have, for the catoptrical tone under the illuminant-C, a ^*Value-2～2, b ^*Value-3～3, the minimum value of the reflectivity in the scope of 380～780nm and peaked ratio are 0.5～0.99, just can make catoptrical tone become neutrality, thereby are preferred.

The b that sees through light under the illuminant-C is arranged again ^*Value is made as 0～3, just can reduce the yellow hue of the white demonstration when being applicable to display device, thereby be preferred.

Also have, on the area source and prevent between the reflection horizon to insert the grid of 120 μ m * 40 μ m, the standard deviation of the Luminance Distribution when having measured Luminance Distribution on film is below 20, just can be reduced in the flicker when being suitable for polarization plate of the present invention in the high-resolution panel, thereby be preferred.

The present invention can adopt prevents from as its optical characteristics, to be made as specular reflectance below 2.5% in the reflection horizon, and transmitance is more than 90%, and 60 ° of glossiness just can suppress outer reflection of light below 70%, watching property of raising, thereby be preferred.Particularly, even more preferably specular reflectance is below 1%, more preferably below 0.5%.

Also have, be made as mist degree 20～50%, the ratio of internal haze/full haze value is 0.3～1, haze value till the light scattering layer is to forming being reduced in 15% of haze value behind the low-index layer, comb width (the く レ width of cloth) 0.5mm place sees through picture vividness 20～50%, is 1.5～5.0 through light/from the transmitance ratio of 2 ° of directions of vertical bank vertically, just can prevent the flicker on the high-resolution LCD panel, reduce the apprehensive of literal etc., thereby be preferred.

＜low-index layer 〉

The refractive index of the low-index layer that the present invention can adopt, preferably 1.20～1.49, even more preferably 1.30～1.44.Have, it is preferred aspect antiradar reflectivityization that low-index layer satisfies following mathematical expression (C) again.

(m/4) λ * 0.7＜n _Ld _L＜(m/4) λ * 1.3 mathematical expressions (C)

In the above-mentioned mathematical expression (C), m is positive odd number, n _LBe the refractive index of low-index layer, and, d _LIt is the thickness (nm) of low-index layer.Also have, λ is a wavelength, is the value of the scope of 500～550nm.

(liquid crystal indicator)

Bonding above-mentioned optical compensating film or polarization film (containing polarization plate) and the polarization plate that obtains is advantageously used in liquid crystal indicator, special transmission type liquid crystal display device.

Transmission type liquid crystal display device is made up of liquid crystal cells and two polarization plates being disposed at its both sides.Polarization plate is made up of polarization film and two transparent protective films being disposed at its both sides.Liquid crystal cells is that liquid crystal in clamping between two electrode base boards.

Polarization plate of the present invention is to dispose one on the one side of liquid crystal cells, or disposes two on the two sides of liquid crystal cells.

Liquid crystal cells is VA mode, OCB mode, IPS mode or TN mode preferably.

＜VA mode 〉

In the liquid crystal cells of VA mode, the rod shaped liquid crystal molecule in fact vertically is not orientated during making alive.

The liquid crystal cells of VA mode comprises that (1) makes rod shaped liquid crystal molecule orientation in fact vertically when making alive not, the liquid crystal cells of the VA mode of the narrow sense that when making alive, in fact flatly is orientated (spy opens flat 2-176625 communique record), also have (2) angle of visibility to enlarge, thereby make the change of VA mode multidomain (the MVA mode) liquid crystal cells (SID97, Digest of tech.Papers (giving the original text collection) 28 (1997) 845 records), (3) make rod shaped liquid crystal molecule orientation in fact vertically when making alive not, the liquid crystal cells (delivering in the LCD world 98) of the liquid crystal cells of the mode (n-ASM mode) of distortion multidomain orientation when making alive (Japanese liquid crystal discussion give 58～59 (1998) records of original text collection) and (4) SURVAIVAL mode.

In the occasion of the liquid crystal indicator of VA mode, optical compensating film of the present invention preferably is used to watch the lateral deviation tabula rasa that shakes.

＜OCB mode 〉

The liquid crystal cells of OCB mode is to make the liquid crystal cells of rod shaped liquid crystal molecule in the curved orientation mode of the substantially opposite direction in the upper and lower of liquid crystal cells (symmetrically) orientation.Adopt the liquid crystal indicator of the liquid crystal cells of curved orientation mode be disclosed in United States Patent (USP) No. 4583825, with each instructions of No. 5410422.The rod shaped liquid crystal molecule is to be orientated symmetrically in the upper and lower of liquid crystal cells, thereby the liquid crystal cells of curved orientation mode has self-optical compensation function.

Therefore, this liquid crystal mode is also referred to as OCB (Optically Compensatory Bend) liquid crystal mode.The liquid crystal indicator of curved orientation mode has the fast advantage of response speed.

＜TN mode 〉

In the liquid crystal cells of TN mode, the rod shaped liquid crystal molecule in fact flatly is not orientated during making alive, and by 60 to 120 ° of twisted-oriented.

The liquid crystal cells of TN mode utilizes at most as colored TFT liquid crystal indicator, and a lot of documents are all on the books.

According to the present invention, can provide liquid crystal cells is correctly carried out optical compensation, optical compensating film and the manufacture method and the polarization plate of the colo(u)r bias of the angle of visibility direction when high-contrast and improvement depend on black the demonstration.

Also have,, can provide to prevent that light from leaking, and obtains the liquid crystal indicator of good contrast according to the present invention.

Embodiment

Embodiments of the invention below are described, but, the present invention is not limited by the following example at all.

(embodiment 1)

Take into account and add sodium hydrate aqueous solution and ion exchange water in the reactive tank of circulation refrigeratory possessing stirring machine, temperature, the monomer [B] that the monomer [A] and the following general formula (7) of following general formula (6) expression are represented dissolves with the ratio of 50: 50 (mole %) therein, adds a spot of sulfoxylate.

Secondly, add methylene chloride therein, at 20 ℃ to be blown into phosgene in about 60 minutes.

Add tert-butyl phenol and make after its emulsification, add triethylamine, finish reaction 30 ℃ of stir abouts 3 hours.

After reaction finishes, carry out organic phase and separate, make the methylene chloride evaporation and obtain polycarbonate-copolymerized compound.The ratio of components of the co-polymer that obtains and monomer addition are than roughly the same.

Also have, the water percentage of the polycarbonate-copolymerized compound of acquisition is 0.3%.

[Chemical formula 1 0]

General formula (6)

[Chemical formula 1 1]

General formula (7)

This co-polymer and as the cyanoethyl of Merck (メ Le Network) corporate system be the trade name of mixed liquid crystal " BL007 " respectively with the ratio solvent of 96: 4 (mass parts) in methylene chloride, make dope solution.Adopt casting to make film 101 by this dope solution.

The stretching device (city's metal working industry corporate system trade name " FITZ ") of the operation that the film 101 of above-mentioned acquisition is stretched at Width to the tentering device with the structure that narrows down during adopting the interval of the length direction of tentering device anchor clamps controlling, transporting to continuous long film is sent, film temperature is made as 170 ℃, stretch by beginning after the heating zone after 30 seconds, the film length direction is relaxed with 0.77 times shrinks, by tentering device anchor clamps Width is carried out 1.70 times of stretchings, the optical compensating film 111 of the thickness 60 μ m after obtaining to stretch.

The optical characteristics of＜film 〉

To the wavelength 450,550 of this optical compensating film 111 and the Re and the Rth at 650nm place,, measure with KOBRA 21ADH (prince measures machine (strain) system) according to the method for previous narration.Table 1 ecbatic.

As shown in table 1, can confirm that the value of the wavelength 450,550 of the optical compensating film 111 of the manufacture method manufacturing of employing present embodiment 1, Re, the Rth at 650nm place all satisfies the relation of above-mentioned formula (1)～(4).

Also have, measured Reb, the Rthb of the film 101 before stretching, the result, Reb is 4nm, Rthb is 10nm.

The making of＜polarization plate 〉

" watch lateral deviation shake the making of tabula rasa "

Make the polyvinyl alcohol film absorption iodine that has stretched make polarization film, on a face of this polarization film, paste optical compensating film 111 with bonding agent.

Also have, (multiple guitar can (Off ジ Star Network) TD80UF to commercially available cellulose acetate film, Fuji's photograph film (strain) system) carrying out saponification handles, use the polyethenol series bonding agent, stick on another face of above-mentioned polarization film, carry out drying more than 10 minutes at 70 ℃, make polarization plate 201.

At this moment, be configured to the axle that sees through of above-mentioned polarization film parallel with the slow axis of optical compensating film 111.Also have, above-mentioned polarization film see through spool and the slow axis of above-mentioned commercially available cellulose acetate film is configured to quadrature.

The shake making of tabula rasa of＜back of the body irradiation lateral deviation 〉

" making of optical compensating film "

[formation of optical anisotropic layer]

After commercially available acylated cellulose film (the photograph film system Z-TAC of Fuji) saponification, on this commercially available acylated cellulose film, press 20mL/m with Wei Yaba button tower (ワ イ ヤ one バ one コ one one) ²Be coated with the alignment films coating fluid of following composition.After this, carry out 60 seconds dryings, carry out 120 seconds dryings with 100 ℃ warm wind again, form film with 60 ℃ warm wind.

Secondly, on the film that forms, implement polishing and form alignment films in the direction parallel with the slow axis direction of film.

[composition of alignment films coating fluid]

Modified polyvinyl alcohol 10 mass parts shown in the following general formula (8)

Water 371 mass parts

Methyl alcohol 119 mass parts

Glutaraldehyde 0.5 mass parts

Compound 0.2 mass parts shown in the following general formula (9)

[Chemical formula 1 2]

General formula (8)

[Chemical formula 1 3]

General formula (9)

Secondly, the optical anisotropic layer coating fluid of following composition is coated on the above-mentioned alignment films with Wei Yaba (ワ イ ヤ one バ one), made that the Rth of the thickness direction after solidifying is 200nm.

[optical anisotropic layer coating fluid composition]

The discoid liquid crystal compounds 1.8g of following general formula (10) expression

Oxirane sex change trihydroxymethyl propane triacrylate (エ チ レ Application キ イ De sex change ト リ メ チ ロ one Le プ ロ パ Application ト リ ア Network リ レ one ト)

(V#360, Osaka organic chemistry (strain) system) 0.2g

Photoepolymerizationinitiater initiater (one tunnel loud, high-pitched sound is striden (イ Le ガ キ エ ア one) 907, and chi crust loud, high-pitched sound is striden (チ バ ガ イ ギ one) corporate system) 0.06g

Sensitizer (the inferior loud, high-pitched sound of Ki is striden (カ ヤ キ ユ ア one) DETX, Japanese chemical drug (strain) system) 0.02g

Fluoropolymer (compd A shown in the following general formula (11)) 0.01g

Methyl-ethyl ketone 3.9g

It is pasted on the frame of metal, and 3 fens kinds of heating in 125 ℃ calibration cell make discoid liquid crystal compounds orientation.

Secondly, adopt the 120W/cm high-pressure mercury-vapor lamp, carry out UV irradiation in 30 seconds, make discoid liquid crystal compounds crosslinked.Temperature when UV is solidified is made as 80 ℃, obtains optical anisotropic layer.

The thickness of optical anisotropic layer is 2.8 μ m.After this, put and be as cold as room temperature.Make optical compensating film 120 like this.Measured the optical characteristics of this optical compensating film 120, result, Re (550)=1 (nm), Rth (550)=200 (nm), Rth (450)/Rth (550)=1.09.

[Chemical formula 1 4]

General formula (10)

[Chemical formula 1 5]

General formula (11)

Make the polyvinyl alcohol film absorption iodine that has stretched make polarization film, on a face of this polarization film, paste optical compensating film 120 with bonding agent.

Also have, commercially available cellulose acetate film (but answering guitar TD80UF, Fuji's photograph film (strain) system) is carried out saponification handle, use the polyethenol series bonding agent, stick on another face of above-mentioned polarization film, carry out drying more than 10 minutes, make polarization plate 300 at 70 ℃.

The making of＜liquid crystal cells 〉

Liquid crystal cells is that the cell gap between substrate is made as 3.6 μ m, the liquid crystal material with negative dielectric constant anisotropy (" MLC6608 ", Merck corporate system) is dripped between substrate inject and enclose, and forms liquid crystal layer and make between substrate.(that is the long-pending Δ nd of thickness d of liquid crystal layer (μ m) and refractive index anisotropy Δ n) is made as 300nm the hysteresis of liquid crystal layer.In addition, liquid crystal material is orientated by vertical orientated.

＜to the installation of VA panel 〉

Upside polarization plate (watching side) as the liquid crystal indicator that has used above-mentioned vertical alignment-type liquid crystal unit, the polarization plate 201 that possesses this optical compensating film 111 is arranged such that optical compensating film 111 becomes liquid crystal cell side, as downside polarization plate (back of the body irradiation side), the polarization plate 300 that possesses optical compensating film 120 is arranged such that this optical compensating film 120 becomes liquid crystal cell side.

Upside polarization plate (polarization plate 201) and downside polarization plate (polarization plate 300) are affixed on liquid crystal cells by bonding agent.Make the axle that sees through of upside polarization plate (polarization plate 201) become above-below direction, and the axle that sees through of downside polarization plate (polarization plate 300) becomes left and right directions, thereby become the configuration of cross Niccol.

The evaluation of＜colo(u)r bias 〉

Liquid crystal cells is applied the square-wave voltage of 55Hz.Be made as the common black formula of white demonstration 5V, the black 0V of demonstration.Try to achieve the colo(u)r bias Δ x of position angle 45 degree, the black demonstration transmitance (%) under the polar angle 60 degree direction angle of visibilities and position angle 45 polar angles, 60 degree and position angle 180 polar angles, 60 degree of black demonstration, estimate based on following metewand.Table 1 ecbatic.

[metewand of colo(u)r bias]

Zero: Δ x is less than 0.02

Zero △: Δ x is 0.02～0.04

△: Δ x is 0.04～0.06

*: Δ x is more than 0.06

The evaluation of＜angle of visibility 〉

Also have, the ratio of transmitance (the white demonstration/black the demonstration) is spent as a comparison, with measuring machine (EZ-Contrastl60D, the ELDIM corporate system), (contrast is more than 10 to measure angle of visibility by black demonstration (L1) to 8 grades that show (L8) in vain, the polar angle scope of not deceiving the gray shade scale counter-rotating of side), estimate based on following metewand.Table 1 ecbatic.

[metewand of angle of visibility (contrast is more than 10, not the polar angle scope of the gray shade scale of black side counter-rotating)]

Zero: at polar angle up and down more than 80 °

Zero △; At up and down 3 direction polar angles more than 80 °

△: at up and down 2 direction polar angles more than 80 °

*: at up and down 0～1 direction polar angle more than 80 °

＜evaluation of resistance 〉

Also have, estimate the angle of visibility under the state of liquid crystal indicator after the environment of 30 ℃ of 90%RH is placed 250 hours based on following metewand.Table 1 ecbatic.

[metewand]

Zero: Δ Cu ' v ' is less than 0.02

*: Δ Cu ' v ' is more than 0.02

(embodiment 2)

The resin of the intrinsic birefringence value that＜performance is positive 〉

By secocubane [4,3,0,1 ^2,5] ten-3,7-diene (trivial name: dicyclopentadiene, hereinafter to be referred as " DCP "), Fourth Ring [4,4,0,1 ^2,5, 1 ^7,10] dodecane-3-alkene (trivial name: tetracyclododecane, hereinafter to be referred as " TCD ") and 8-ethidine-Fourth Ring [4,4,0,1 ^2,5, 1 ^7,10] dodecane-3-alkene (trivial name: ethidine tetracyclododecane, hereinafter to be referred as " ETD ") potpourri that mixes in the ratio of 47/28/35 (mass ratio) carries out ring-opening polymerization, and then carry out hydrogen and add and obtain ring-opening polymerization hydrogen additive (hereinafter to be referred as norbornene-based polymer).

This ring-opening polymerization hydrogen additive, its vitrifying point (Tg) that measures with differential scanning type apparatus for measuring amount of heat (DSC) is 130 ℃, 250 ℃ of down cut speed of temperature 180sec ^-1Under the viscosity that dissolves be 980Pas.

This norbornene-based polymer is used as resin (A) with positive intrinsic birefringence value.

＜have a resin of negative intrinsic birefringence value 〉

As the resin with negative intrinsic birefringence value (B), used styrene-anhydrous maleic acid co-polymer (slave stops (ノ バ) chemical company's system, and trade name: DaylaekD332 dissolves viscosity 440PaS, Tg=130 ℃).Below, this styrene-anhydrous maleic acid co-polymer is called " D332 ".

＜lag behind and adjust agent

Adjust agent as the dichromatic hysteresis of expression, used 2,2-di-2-ethylhexylphosphine oxide (4-(1,1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) carbolic acid).This lags behind and adjusts agent, is sold with trade name A Dekasita Be (ア デ カ ス Block) LA-31 by Asahi Denka Kogyo K. K.Below, this hysteresis modulator is called " UVA ".

Adjust agent as the dichromatic hysteresis of expression, used commercially available infrared absorbent (Japanese chemical drug (strain) system, trade name: KAYASORB CY-17, maximum absorption wavelength: 782nm).Below, agent is adjusted in this hysteresis called " IR ".

The 1st layer that forms by above-mentioned norbornene-based polymer, by above-mentioned " D332 " is 100 mass parts, above-mentioned UVA is 4 mass parts, above-mentioned IR is the 2nd layer that 4 mass parts cooperate the potpourri form to form, and become bond layer by ethene-vinyl acetate co-polymer (Mitsubishi Chemical's (strain) system, trade name: the trade enlightening restrains the 3rd layer that (モ デ イ Star Network) (AP A543) forms, sequential lamination by [the 1st layer (75 μ m) the-the 3rd layer (7 μ m) the-the 2nd layer (100 μ m) the-the 3rd layer (7 μ m) the-the 1st layer (75 μ m)], obtain three kinds five layers laminate 102, adopt coextrusion shaping method to make with extrusion shaper (trade name: LABOPLASTOMILI, the smart mechanism of Japan) it.

The stretching device (city's metal working industry corporate system trade name " FITZ ") of the operation that the film of above-mentioned acquisition (laminate 102) is stretched at Width to the tentering device with the structure that narrows down during adopting the interval of the length direction of tentering device anchor clamps controlling, transporting to continuous long film is sent, film temperature is made as 130 ℃, stretch by beginning after the heating zone after 30 seconds, the film length direction is relaxed with 0.70 times shrinks, by tentering device anchor clamps Width is carried out 2.00 times of stretchings, the optical compensating film 112 of the thickness 60 μ m after obtaining to stretch.

The optical characteristics of＜film 〉

To the wavelength 450,550 of this optical compensating film 112 and the Re and the Rth at 650nm place,, measure with KOBRA 21ADH (prince measures machine (strain) system) according to the method for previous narration.Table 1 ecbatic.

As shown in table 1, can confirm that the value of the wavelength 450,550 of the optical compensating film 112 of the manufacture method manufacturing of employing present embodiment 2, Re, the Rth at 650nm place all satisfies the relation of above-mentioned formula (1)～(4).

Also have, measured the Reb and the Rthb of the film 102 before stretching, the result, Reb is 3nm, Rthb is 8nm.

The making of＜polarization plate 〉

" watch lateral deviation shake the making of tabula rasa "

Except the lateral deviation of watching at the foregoing description 1 is shaken in the making of tabula rasa, with optical compensating film 112 replace optical compensating films 111 beyond, the same with embodiment 1, make and watch the lateral deviation tabula rasa (polarization plate 202) that shakes.

The shake making of tabula rasa of＜back of the body irradiation lateral deviation 〉

" making of optical compensating film "

The same with the shake making of tabula rasa of the back of the body irradiation lateral deviation of the foregoing description 1, make the back of the body irradiation lateral deviation tabula rasa (polarization plate 300) that shakes.

The making of＜liquid crystal cells 〉

The same with the foregoing description 1, make liquid crystal cells.

＜to the installation of VA panel 〉

Except the foregoing description 1 in the installation of VA panel, with polarization plate 202 replace polarization plates 201 beyond, the same with embodiment 1, polarization plate 202 and polarization plate 300 are installed on the VA panel.

Also have, the same with the foregoing description 1, estimated angle of visibility, colo(u)r bias and resistance.Table 1 ecbatic.

(comparative example 1)

Adopt the film of making among the embodiment 1 101 the common stretching device that is spaced apart the operation that certain tentering device stretches at Width of the length direction of tentering device anchor clamps to send to having to continuous long film, the optical compensating film 113 of thickness 60 μ m after temperature stretches 1.9 times down for 218 ℃, obtains to stretch.

The optical characteristics of＜film 〉

To the wavelength 450,550 of this optical compensating film 113 and the Re and the Rth at 650nm place,, measure with KOBRA 21ADH (prince measures machine (strain) system) according to the method for previous narration.Table 1 ecbatic.

As shown in table 1, can confirm, adopt wavelength 450,550, the Re at 650nm place and the value of Rth of optical compensating film 113 of the manufacture method manufacturing of this comparative example 1 not satisfy the relation of above-mentioned formula (1)～(4).

The making of＜polarization plate 〉

" watch lateral deviation shake the making of tabula rasa "

Except the lateral deviation of watching at the foregoing description 1 is shaken in the making of tabula rasa, with optical compensating film 113 replace optical compensating films 111 beyond, the same with embodiment 1, make and watch the lateral deviation tabula rasa (polarization plate 203) that shakes.

The shake making of tabula rasa of＜back of the body irradiation lateral deviation 〉

" making of optical compensating film "

The same with the shake making of tabula rasa of the back of the body irradiation lateral deviation of the foregoing description 1, make the back of the body irradiation lateral deviation tabula rasa (polarization plate 300) that shakes.

The making of＜liquid crystal cells 〉

The same with the foregoing description 1, make liquid crystal cells.

＜to the installation of VA panel 〉

Except the foregoing description 1 in the installation of VA panel, with polarization plate 203 replace polarization plates 201 beyond, the same with embodiment 1, polarization plate 203 and polarization plate 300 are installed on the VA panel.

Also have, the same with the foregoing description 1, estimated angle of visibility, colo(u)r bias and resistance.Table 1 ecbatic.

(comparative example 2)

The making of the solution C A-1 of＜acylated cellulose 〉

Dissolve each composition stirring in the following composition input mixing tank, be modulated into the solution C A-1 of acylated cellulose.In addition, Ac=acetyl group.

[acylated cellulose solution C A-1 composition]

Cellulose acetate 100.0 mass parts of Ac degree of exchange 2.81

TPP (triphenyl phosphate) 7.8 mass parts

BDP (phosphoric acid biphenyl diphenyl) 3.9 mass parts

Methylene chloride (the 1st solvent) 402.0 mass parts

Methyl alcohol (the 2nd solvent) 60.0 mass parts

The modulation of＜matting agent solution MT-1 〉

The silica particle of mean grain size 16nm (AEROSIL R972, Japanese Ah Lou Jilou (ア エ ロ ジ Le) (strain) system) 20 mass parts, methyl alcohol 80 mass parts mix 30 fens kinds well, as the silica particle dispersion liquid.This dispersion liquid is dropped into dispersion machine with following composition, stir again more than 30 minutes and dissolve each composition, be modulated into matting agent solution MT-1.

[matting agent solution MT-1 composition]

Silica particle dispersion liquid 10.0 mass parts of mean grain size 16nm

Methylene chloride (the 1st solvent) 76.3 mass parts

Methyl alcohol (the 2nd solvent) 3.4 mass parts

Acylated cellulose solution C A-1 10.3 mass parts

The modulation of＜additive solution 〉

Following composition is dropped in the mixing tank, stir, dissolve each composition, be modulated into additive solution AD-1 while heat.Adopt the hysteresis visualization reagent shown in the following general formula (12) again.

[additive solution AD-1 composition]

Hysteresis visualization reagent 7.6 mass parts shown in the following general formula (12)

Methylene chloride (the 1st solvent) 58.4 mass parts

Methyl alcohol (the 2nd solvent) 8.7 mass parts

Acylated cellulose solution C A-1 12.8 mass parts

[Chemical formula 1 6]

General formula (12)

The making of＜acylated cellulose film 103 〉

Above-mentioned acylated cellulose solution C A-1 is got 94.6 mass parts, and matting agent solution MT-1 gets 1.3 mass parts, and additive solution AD-1 gets 2.3 mass parts, mixes after filtering respectively, adopts the band casting machine to carry out curtain coating.

The hysteresis visualization reagent is 1.0% to the mass ratio of acylated cellulose in above-mentioned composition.

After this, from being with stripping film, make its dry 40 fens kind, make acylated cellulose film 103 at 140 ℃ by residual solvent amount 30%.

The residual solvent amount of the acylated cellulose film 103 that obtains is 0.2%, and thickness is 100 μ m.

The making of＜optical compensating film 114 〉

Adopt the film 103 of above-mentioned acquisition the stretching device that is spaced apart the operation that certain tentering device stretches at Width of the length direction of tentering device anchor clamps to send to having to continuous long film, film temperature is made as 180 ℃, stretch by beginning after the heating zone after 30 seconds, the film length direction is relaxed with 0.85 times shrinks, by tentering device anchor clamps Width is carried out 1.25 times of stretchings, the optical compensating film 114 of the thickness 125 μ m after obtaining to stretch.

The optical characteristics of＜film 〉

To the wavelength 450,550 of this optical compensating film 114 and the Re and the Rth at 650nm place,, measure with KOBRA 21ADH (prince measures machine (strain) system) according to the method for previous narration.Table 1 ecbatic.

As shown in table 1, can confirm, adopt the value of Re, Rth at wavelength 450,550,650nm place of optical compensating film 114 of the manufacture method manufacturing of this comparative example 2 not satisfy the relation of above-mentioned formula (1)～(4).

Also have, measured the Reb and the Rthb of the film 103 before stretching, the result, Reb is 7nm, Rthb is 55nm.

The making of＜polarization plate 〉

" watch lateral deviation shake the making of tabula rasa "

Except the lateral deviation of watching at the foregoing description 1 is shaken in the making of tabula rasa, with optical compensating film 114 replace optical compensating films 111 beyond, the same with embodiment 1, make and watch the lateral deviation tabula rasa (polarization plate 204) that shakes.

The shake making of tabula rasa of＜back of the body irradiation lateral deviation 〉

" making of optical compensating film "

The same with the shake making of tabula rasa of the back of the body irradiation lateral deviation of the foregoing description 1, make the back of the body irradiation lateral deviation tabula rasa (polarization plate 300) that shakes.

The making of＜liquid crystal cells 〉

The same with the foregoing description 1, make liquid crystal cells.

＜to the installation of VA panel 〉

Except the foregoing description 1 in the installation of VA panel, with polarization plate 204 replace polarization plates 201 beyond, the same with embodiment 1, polarization plate 204 and polarization plate 300 are installed on the VA panel.

Also have, the same with the foregoing description 1, estimated angle of visibility, colo(u)r bias and resistance.Table 1 ecbatic.

(comparative example 3)

The making of＜optical compensating film 115 〉

Commercially available polycarbonate resin (other special (パ Application ラ イ ト), Supreme Being people's (strain) system of relying) is dissolved in methylene chloride, makes dope solution.Adopt casting to make film 105 by this dope solution.

The stretching device (city's metal working industry corporate system trade name " FITZ ") of the operation that the film 105 of above-mentioned acquisition is stretched at Width to the tentering device with the structure that narrows down during adopting the interval of the length direction of tentering device anchor clamps controlling, transporting to continuous long film is sent, the optical compensating film 115 of thickness 60 μ m after temperature stretches 1.5 times down for 160 ℃, obtains to stretch.

The optical characteristics of＜optical compensating film 115 〉

To the wavelength 450,550 of this optical compensating film 115 and the Re and the Rth at 650nm place,, measure with KOBRA 21ADH (prince measures machine (strain) system) according to the method for previous narration.Table 1 ecbatic.

The making of＜polarization plate 〉

" watch lateral deviation shake the making of tabula rasa "

Except the lateral deviation of watching at the foregoing description 1 is shaken in the making of tabula rasa, with optical compensating film 115 replace optical compensating films 111 beyond, the same with embodiment 1, make and watch the lateral deviation tabula rasa (polarization plate 205) that shakes.

The shake making of tabula rasa of＜back of the body irradiation lateral deviation 〉

" making of optical compensating film "

The same with the shake making of tabula rasa of the back of the body irradiation lateral deviation of the foregoing description 1, make the back of the body irradiation lateral deviation tabula rasa (polarization plate 300) that shakes.

The making of＜liquid crystal cells 〉

The same with the foregoing description 1, make liquid crystal cells.

＜to the installation of VA panel 〉

Except the foregoing description 1 in the installation of VA panel, with polarization plate 205 replace polarization plates 201 beyond, the same with embodiment 1, polarization plate 205 and polarization plate 300 are installed on the VA panel.

Also have, the same with the foregoing description 1, estimated angle of visibility, colo(u)r bias and resistance.Table 1 ecbatic.

[table 1]

	Re(450)	Re(550)	Re(650)	Rth(550)/ Re(550)	Re(450)/ Re(550)	Re(650) /Re(550 )	Angle of visibility	Colo(u)r bias	Resistance
										Embodiment 1	125	142	151	0.52	0.88	1.06	○	○	○
Embodiment 2	112	137	154	0.49	0.82	1.12	○	○	○
										Relatively fall 1	110	125	133	1.20	0.88	1.06	△	×	○
Comparative example 2	120	154	176	1.42	0.78	1.14	△	×	×
										Comparative example 3	155	145	138	0.55	1.07	0.95	△	×	○

As shown in table 1, the optical compensating film of embodiment 1～2 satisfies mathematical expression (1)～(4), no matter thereby the liquid crystal indicator that is provided with the polarization plate that possesses this optical compensating film can both be realized neutral black demonstration at frontal or in the angle of visibility direction.

On the other hand, the optical compensating film of comparative example 1～3 does not satisfy mathematical expression (1)～(4), no matter thereby at frontal or in the angle of visibility direction, all can produce light and leak, contrast is also bad.

Particularly confirmed liquid crystal indicator in the environment of 30 ℃ of 90%RH and observe under the state after placing 250 hours, the angle of visibility of comparative example 2 worsens significantly.

Therefore, optical compensating film of the present invention and polarization plate can roughly all wavelength particularly carry out view angle compensation for the black state of VA mode, IPS mode, OCB mode.As a result, the light of the tilted direction when liquid crystal indicator of the present invention can alleviate black the demonstration leaks, and improves the angle of visibility contrast significantly.

Also have, the present invention can realize the manufacturing process of volume to volume mode in bonding to polarization plate, thereby can provide productivity very outstanding optical compensating film.

Have, the light of the tilted direction that liquid crystal indicator of the present invention can be when roughly all visible wavelength regions suppress black the demonstration leaks again, thus can improve greatly existing issue depend on black demonstration of angle of visibility the time colo(u)r bias.

According to liquid crystal indicator of the present invention, the display mode because of liquid crystal cells is not limited, in the liquid crystal indicator of liquid crystal layer with any one display modes such as VA mode, IPS mode, ECB mode, TN mode and OCB modes, can both obtain good contrast, applicable to mobile phone, PC monitor, TV, liquid crystal projection apparatus etc.

Claims (12)

1. an optical compensating film is characterized in that, satisfies following mathematical expression (1)～(4):

50≤Re (550)≤200 mathematical expression (1)

0.4≤Rth (550)/Re (550)≤0.6 mathematical expression (2)

0.1＜Re (450)/Re (550)＜0.95 mathematical expression (3)

1.03＜Re (650)/Re (550)＜1.93 mathematical expression (4)

In above-mentioned mathematical expression (1)～(4), Re (450), Re (550), Re (650) are that (unit: nm), Rth (550) is the lagged value (unit: nm) of the thickness direction that arrives of the photo measure with wavelength 550nm to lagged value in the face that arrives with the photo measure of wavelength 450nm, 550nm, 650nm respectively.

2. optical compensating film according to claim 1 is characterized in that, is that polymkeric substance below 1.0% is formed by water percentage.

3. optical compensating film according to claim 1 is characterized in that, forms by having positive intrinsic birefringent resin and having negative intrinsic birefringent mixed with resin, perhaps is made up of their laminate.

4. the manufacture method of an optical compensating film is characterized in that, comprises length direction and the stretching process of any one direction in the Width and the contraction process that another direction is shunk of oriented film.

5. the manufacture method of optical compensating film according to claim 4, it is characterized in that, contraction process is to control, transport film by tentering device anchor clamps, the interval of the carriage direction by narrowing these tentering device anchor clamps makes the operation of its contraction, and stretching process is in the stretch operation of this film of the direction of quadrature roughly therewith.

6. the manufacture method of optical compensating film according to claim 4 is characterized in that, the extensibility in the stretching process is being made as X%, when the shrinkage factor in the contraction process is made as Y%, satisfies following mathematical expression (Z):

[formula 1]

$90-1000/\sqrt{100+x}\&le;Y\&le;110-1000/\sqrt{100+x}$ Mathematical expression (Z).

7. the manufacture method of optical compensating film according to claim 6 is characterized in that, the optical compensating film before stretching satisfies following mathematical expression (5)～(6):

-20≤Reb (550)≤20 mathematical expression (5)

-20≤Rthb (550)≤20 mathematical expression (6)

In above-mentioned mathematical expression (5)～(6), Reb (550) is that (unit: nm), Rthb (550) is the thickness direction lagged value (unit: nm) of the preceding optical compensating film of the stretching of arriving of the photo measure with 550nm to lagged value in the face of the optical compensating film before the stretching of arriving of the photo measure with wavelength 550nm.

8. optical compensating film according to claim 1 is characterized in that, adopts the manufacture method of the described optical compensating film of claim 4 to make.

9. the manufacture method of a polarization plate is characterized in that, comprises the optical compensating film of the described microscler shape of claim 8 and the polarizer are carried out bonding operation by volume to volume.

10. a polarization plate is characterized in that, adopts the manufacture method of the described polarization plate of claim 9 to make.

11. liquid crystal indicator, it is characterized in that having and adopt the polarization plate that comprises polarization plate, the liquid crystal cells of the operation manufacturing of carrying out bonding operation and possess the optical anisotropic layer that satisfies following mathematical expression (7-1) and mathematical expression (7-2):

-10＜Re (550)＜10 mathematical expression (7-1)

100＜| Rth (550) |＜300 mathematical expressions (7-2),

It is above-mentioned that to carry out bonding operation be employing to be comprised the stretching process of the length direction of oriented film and any one direction in the Width and make the optical compensating film and the polarizer of the microscler shape that satisfies above-mentioned mathematical expression (1)～(4) of the manufacture method manufacturing of the contraction process that another direction shrinks carry out bonding operation by volume to volume.

12. liquid crystal indicator according to claim 11 is characterized in that, liquid crystal cells is the VA mode.