CN101317126A - Liquid crystal panel and liquid crystal display device - Google Patents

Abstract

It is possible to provide a liquid crystal panel having an excellent screen contrast, a small color shift, and little display irregularities. The liquid crystal panel includes a liquid crystal cell, a first polarizer, a second polarizer, a protection layer, a first optical compensation layer, and a second optical compensation layer. A layer to be protected satisfies the relationships: 0 nm<=delta nd(550)<=10 nm and 0 nm<=Rth (550)<=20 nm. The first optical compensation layer has an absolute value of the optical elastic coefficient equal to or below 40*10<-12> (m<2>/N) and satisfies the relationships: delta nd(380) < delta nd(550) <delta nd(780), nx>ny>=nz and 90 nm<=delta nd(550)<=200 nm. The second optical compensation layer satisfies the relationships: Rth (380)> Rth(550)>Rth (780) and nx=ny>nz.

Description

Liquid crystal panel and liquid crystal indicator

Technical field

The present invention relates to liquid crystal panel and liquid crystal indicator, more detailed Yan Eryan relates to the liquid crystal panel and the liquid crystal indicator that have 2 layers of optical compensating layer between the 1st polaroid and the 2nd polaroid at least.

Background technology

In the liquid crystal cells of VA pattern or ocb mode, liquid crystal molecular orientation is a vertical direction when nothing applies voltage.Therefore, watching from tilted direction under the situation of liquid crystal panel, in appearance, liquid crystal molecule becomes the state that is oriented in tilted direction, will change because of the birefringence of liquid crystal from the polarized state of light of this tilted direction, and light leak from polarization plates takes place.Again, polarization plates is the orthogonal thereto blocking light of its absorption axes by laminated configuration, and when watching the polarization plates of this stacked state by tilted direction, in appearance, the absorption axes of polarization plates becomes non-orthogonal states, and the light leak from polarization plates takes place.

In order to address the above problem, announcement has use to have nx＞ny＞nz, and (nx is the mutually axial refractive index that lags behind, ny is the axial refractive index of leading phase, nz is the refractive index of thickness direction) relation the biaxial optical compensating plate, technology (for example, with reference to patent documentation 1～5) with the influence of an inclined to one side light leak that is caused of compensation liquid crystal birefringence and polarization plates.Yet these technology are in the attenuating of the raising of picture contrast, aberration and suppress to show aspect unequal all inadequate.

The special hope of (patent documentation 1) Jap.P. 2003-926 communique

The special hope of (patent documentation 2) Jap.P. 2003-27488 communique

The special hope of (patent documentation 3) Jap.P. 2003-38734 communique

The special hope of (patent documentation 4) Jap.P. 2002-63796 communique

The special hope of (patent documentation 5) Jap.P. 2002-222830 communique

Summary of the invention

The present invention is in order to solve the invention of above-mentioned problem, and its purpose is not to provide and need applies complicated means, and picture contrast is good, aberration is little and show uneven less liquid crystal panel and liquid crystal indicator.

Liquid crystal panel of the present invention possesses: liquid crystal cells, be configured in a side of this liquid crystal cells the 1st polaroid, be configured in the opposite side of this liquid crystal cells the 2nd polaroid, be configured in the 1st polaroid or the 2nd polaroid this liquid crystal cell side protective seam and be configured in the 1st polaroid and the 2nd polaroid between the 1st optical compensating layer and the 2nd optical compensating layer.This protective seam is the relation with following formula (1) and (2), and the 1st optical compensating layer is configured in the liquid crystal cell side of this protective seam, and the absolute value of photoelasticity modulus is 40 * 10 ^-12(m ²/ N) below, and have the relation of following formula (3), (4) and (5), the 2nd optical compensating layer has the relation of following formula (6) and (7).

0nm≤Δnd(550)≤10nm......(1)

0nm≤Rth(550)≤20nm......(2)

Δnd(380)＜Δnd(550)＜Δnd(780)......(3)

nx＞ny≥nz......(4)

90nm≤Δnd(550)≤200nm......(5)

Rth(380)＞Rth(550)＞Rth(780)......(6)

nx＝ny＞nz......(7)

At this, Δ nd (380), Δ nd (550) and Δ nd (780) are illustrated respectively in phase differential in the face of being measured with wavelength 380nm, 550nm, 780nm under 23 ℃, Rth (380), Rth (550) and Rth (780) are illustrated respectively in the phase differential of the thickness direction of being measured with wavelength 380nm, 550nm and 780nm under 23 ℃, nx, ny and nz represent respectively the to lag behind refractive index of phase direction of principal axis, leading phase direction of principal axis and thickness direction.

In preferred embodiment, above-mentioned the 1st optical compensating layer and above-mentioned the 2nd optical compensating layer are benchmark with above-mentioned liquid crystal cells, are configured in not homonymy respectively.

In preferred embodiment, above-mentioned the 1st optical compensating layer has the relation of Δ nd (780)/Δ nd (550)＞1.10.

In preferred embodiment, above-mentioned the 1st optical compensating layer contains cellulose-based material.

In preferred embodiment, degree of substitution with acetyl group of above-mentioned cellulose-based material (DSac) and propiono substituting group (DSpr) are 2.0≤DSac+DSpr≤3.0,1.0≤DSpr≤3.0.

In preferred embodiment, above-mentioned the 2nd optical compensating layer has the relation of Rth (780)/Rth (550)＜0.95.

In preferred embodiment, the material that constitutes above-mentioned the 2nd optical compensating layer is at least a kind of non-liquid-crystalline polymer selecting from the group that is made of polyamide, polyimide, polyester, polyetherketone, polyamidoimide and polyester-imide.

In preferred embodiment, above-mentioned liquid crystal cells is VA pattern or ocb mode.

According to other aspects of the invention, provide liquid crystal indicator.This liquid crystal indicator contains above-mentioned liquid crystal panel.

As mentioned above, according to the present invention, the 1st optical compensating layer and the 2nd optical compensating layer by configuration between the 1st polaroid and the 2nd polaroid has above-mentioned optical characteristics then can improve picture contrast, and lower aberration.Moreover, be 40 * 10 by the absolute value that the photoelasticity modulus is set ^-12(m ²/ N) following the 1st optical compensating layer, then can prevent because of the hot caused phase differential inequality of the differential contraction stress of polaroid or backlight uneven to suppress to show.The result can provide the complicated means that do not apply, and picture contrast is superior, aberration is less and show uneven less liquid crystal panel and liquid crystal indicator

Description of drawings

Fig. 1 is the summary section of the liquid crystal panel of the preferred embodiment for the present invention.

Fig. 2 is the summary section of the liquid crystal panel of other preferred implementation of the present invention.

Fig. 3 adopts under the situation of liquid crystal cells of VA pattern at liquid crystal indicator of the present invention, and the summary section of state of orientation of the liquid crystal molecule of liquid crystal layer is described.

Fig. 4 adopts under the situation of liquid crystal cells of ocb mode at liquid crystal indicator of the present invention, and the summary section of state of orientation of the liquid crystal molecule of liquid crystal layer is described.

Fig. 5 (a) and (b) be the measurement result of aberration of the liquid crystal panel of the embodiment of the invention 1 (c) is the radar map of contrast visual angle interdependence of the liquid crystal panel of the expression embodiment of the invention 1.

Fig. 6 (a) and (b) be the measurement result of aberration of the liquid crystal panel of comparative example 1 (c) is the radar map of contrast visual angle interdependence of the liquid crystal panel of expression comparative example 1.

Fig. 7 (a) and (b) be the measurement result of aberration of the liquid crystal panel of comparative example 2 (c) is the radar map of contrast visual angle interdependence of the liquid crystal panel of expression comparative example 2.

Fig. 8 (a) and (b) be the measurement result of aberration of the liquid crystal panel of comparative example 3 (c) is the radar map of contrast visual angle interdependence of the liquid crystal panel of expression comparative example 3.

Fig. 9 (a) and (b) be the measurement result of aberration of the liquid crystal panel of comparative example 4 (c) is the radar map of contrast visual angle interdependence of the liquid crystal panel of expression comparative example 4.

Figure 10 (a) is the observation photo of the picture black of the liquid crystal indicator of the embodiment of the invention 1 when showing, (b) is the picture black of the liquid crystal indicator of the comparative example 4 observation photo when showing.

Among the figure, 10-liquid crystal cells, 20-the 1st polaroid, 20 '-Di, 2 polaroids, 30-the 1st optical compensating layer, 40-the 2nd optical compensating layer, 50-protective seam, 11,11 '-substrate, 12-liquid crystal layer, 100-liquid crystal panel.

Embodiment

Below, describe at preferred implementation of the present invention, but the present invention is not limited to these embodiments.

(definition of term and symbol)

Term in this instructions and symbol are defined as follows to be stated:

(1) " nx " () refractive index also promptly, hysteresis phase direction of principal axis, " ny " be that () refractive index also promptly, the leading phase direction of principal axis, " nz " is the refractive index of thickness direction perpendicular to the direction that lags behind mutually spool in the face for refractive index in the face becomes maximum direction.Again, for example " nx=ny " not only comprises the situation that nx and ny equate fully, also comprises the situation that nx and ny equate in fact.In this instructions, " equal in fact " is also included within not the polarization characteristic with the polarization plates integral body of optical compensating layer caused in the scope of the influence in the practicality situation that nx and ny are different.

(2) " phase difference nd (550) in the face " is meant the phase difference value in layer (film) face of being measured with the light of wavelength 550nm under 23 ℃.Δ nd (550) is that hysteresis phase direction of principal axis, the axial refractive index of leading phase with the layer (film) among the wavelength 550nm is made as nx, ny respectively, and when d (nm) is made as the thickness of layer (film), by formula: Δ nd=(nx-ny) * d tries to achieve.Again, " phase difference nd (380) in the face " is meant the phase difference value in layer (film) face of being measured with the light of wavelength 380nm under 23 ℃, and " phase difference nd (780) in the face " is meant the phase difference value in layer (film) face of being measured with the light of wavelength 780nm under 23 ℃.

(3) " the phase differential Rth (550) of thickness direction " is meant the phase difference value of the thickness direction of being measured with the light of wavelength 550nm under 23 ℃.Rth (550) is made as nx, nz respectively with the hysteresis phase direction of principal axis of the layer (film) among the wavelength 550nm, the refractive index of thickness direction, when d (nm) is made as the thickness of layer (film), is tried to achieve by formula: Rth=(nx-nz) * d.Again, " the phase differential Rth (380) of thickness direction " is meant the phase difference value of the thickness direction of being measured with the light of wavelength 380nm under 23 ℃, and " the phase differential Rth (780) of thickness direction " is meant the phase difference value of the thickness direction of being measured with the light of wavelength 780nm under 23 ℃.

A. the integral body of liquid crystal panel constitutes

Fig. 1 is the summary section of the liquid crystal panel of an embodiment of the present invention.This liquid crystal panel 100 possesses: liquid crystal cells 10, be configured in a side (recognizing side for looking in the illustrated example) of liquid crystal cells 10 the 1st polaroid 20, be configured in the opposite side (illustrated example is the backlight side) of liquid crystal cells 10 the 2nd polaroid 20 ', and liquid crystal cells 10 sides of the 1st polaroid 20 in abutting connection with the protective seam 50 that disposes, be configured at least 2 layers of optical compensating layer between the 1st polaroid 20 and the 2nd polaroid 20 '.This optical compensating layer of at least 2 layers contains the 1st optical compensating layer 30 and the 2nd optical compensating layer 40.The 1st optical compensating layer 30 is in abutting connection with liquid crystal cells 10 sides of protective seam 50 and dispose.The 2nd optical compensating layer 40 is configured between the 2nd polaroid 20 ' and the liquid crystal cells 10.The deterioration of polaroid can be significantly prevented by protective seam 50 is set, and the liquid crystal panel of superior durability can be obtained.Again, protective seam 50 disposes in abutting connection with liquid crystal cells 10 sides of the 2nd polaroid 20 ', and the 1st optical compensating layer 30 is configured in the backlight side, and the 2nd optical compensating layer 40 is configured in to look recognizes side, but the 1st optical compensating layer 30 preferably as shown general configuration recognize side looking.This is because the influence that heat caused that can lower backlight can be brought into play effect of the present invention more.

Fig. 2 is the summary section of the liquid crystal panel of other preferred implementation of the present invention.In this embodiment, the 1st optical compensating layer 30 and the 2nd optical compensating layer 40 are configured between the 1st polaroid 20 and the liquid crystal cells 10.As shown in Figure 1, the 1st optical compensating layer 30 and 2 optical compensating layers 40 are that benchmark is configured in not homonymy respectively with liquid crystal cells 10 preferably.This is promptly to carry out the goods design because can not consider the laminating method of the 1st optical compensating layer 30 and 2 optical compensating layers 40, and highly productive.Again, about each formation portion material and each layer details of Figure 1 and Figure 2, will be in B-1 item described later～B-4 item explanation.

Among the present invention, optionally can between the 1st polaroid 20 or the 2nd polaroid 20 ' and 2 optical compensating layers 40, the protective film (not shown) that is fit to arbitrarily be set.Moreover, optionally,, the protective film that is fit to arbitrarily can be set in a side that does not form optical compensating layer of the 1st polaroid 20 and/or the 2nd polaroid 20 '.By protective film is set, can prevent the deterioration of polaroid.Among the present invention, other optical compensating layer (not icon) can be set also again.Visual purpose such as the kind of this optical compensating layer, quantity, allocation position and suitably selecting.

Liquid crystal cells 10 is to have a pair of substrate 11,11 ', and seizes between substrate 11,11 ' liquid crystal layer 12 as display medium on both sides by the arms.On a substrate (colour filtering chip basic board) 11, color filter and black matrix (all not shown) are set.On another substrate (active-matrix substrate) 11 ', be provided with the control liquid crystal electrooptical learn the on-off element (that representative is TFT) (not shown) of characteristic, to this on-off element give the scanning linear (not icon) of gate signal and give source signal signal wire (not icon), with pixel electrode (not shown).Again, color filter also can be arranged on active-matrix substrate 11 ' side. Aforesaid substrate 11,11 ' interval (cell gap) are to control by introns (spacer).In aforesaid substrate 11,11 ' a side of joining with liquid crystal layer 12, be provided with the alignment films (not shown) that for example constitutes by polyimide.

As the drive pattern of liquid crystal cells 10, under the precursor that can obtain effect of the present invention, can adopt the drive pattern that is fit to arbitrarily.As the concrete example of drive pattern, can give an example as STN (SuperTwisted Nematic) pattern, TN (Twisted Nematic) pattern, IPS (In-Plane Switching) pattern, VA (Vertical Aligned) pattern, OCB (Optically Aligned B irefringence) pattern, HAN (Hybrid Aligned Nematic) pattern and ASM (Axially SymmetricAligned Microcell) pattern.Be preferably VA pattern and ocb mode.

Fig. 3 is the summary section of the liquid crystal molecular orientation state in the explanation VA pattern.Shown in Fig. 3 (a), when not applying voltage, liquid crystal molecular orientation is perpendicular to substrate 11,11 ' face.This vertical orientated, can have the anisotropic nematic crystal of negative permittivity by configuration between the substrate that is formed with vertical alignment layer (not shown) and realize.In this state,, then be incident upon the light of the straight line polarization of liquid crystal layer 12, will advance along the long axis direction of vertical orientated liquid crystal molecule by the 1st polaroid 20 if the face of the substrate 11 of My World is injected light.Owing to do not produce birefringence on the long axis direction of liquid crystal molecule, so incident light does not change the polarization direction and advances, the 2nd polaroid 20 ' that quilt has with the polarizing axis of the 1st polaroid 20 quadratures absorbs.Can when not applying voltage, obtain the demonstration (normal showing deceived pattern) of dark state thus.Shown in Fig. 3 (b), if apply voltage between electrode, then the major axis of liquid crystal molecule is oriented to and is parallel to real estate.For the rectilinearly polarized light of the liquid crystal layer 12 that is incident to this state, liquid crystal molecule shows birefringence, and the polarization of incident light state cooperates the degree of tilt of liquid crystal molecule and changes.When applying the maximum voltage of regulation, by the light of liquid crystal layer, for example become the rectilinearly polarized light of its polarization direction half-twist, so see through the demonstration that the 2nd polaroid 20 ' obtains bright state.If be made as the state that does not apply voltage once more, then can be back to the demonstration of dark state by orientation adjusting power.Again, change to apply voltage and make the intensity variation that sees through from the 2nd polaroid 20 ' with the degree of tilt of control liquid crystal molecule, GTG will be shown becomes possibility.

Fig. 4 is the summary section of the liquid crystal cells state of orientation of explanation ocb mode.Ocb mode is the drive pattern that constitutes liquid crystal layer 12 by the orientation of so-called curved orientation.Curved orientation is meant shown in Fig. 4 (c), the nematic crystal molecule be oriented in substrate near have almost parallel angle (angle of orientation), the angle of orientation with along with will be vertical angle with respect to base plan towards the liquid crystal layer center, along with the mode that will be orientated with opposed substrate surface away from the liquid crystal layer center changes gradually continuously, and do not have the state of orientation of helical structure in liquid crystal layer integral body.This curved orientation forms as described below.Shown in Fig. 4 (a), under the state (original state) of not giving any electric field etc., liquid crystal molecule is even orientation in fact.Wherein, liquid crystal molecule has tilt angle, and near the tilt angle the substrate with its near the tilt angle of opposed substrate different.If (representative is 1.5V～1.9V) (when applying low-voltage), then passes through the injection orientation shown in Fig. 4 (b), can realize the transfer to the curved orientation shown in Fig. 4 (c) to apply the regulation bias voltage at this.If (representative is 5V～7V) (when applying high voltage), and liquid crystal molecule erects with respect to substrate surface as will be shown in Fig. 4 (d) and is almost vertical further to apply display voltage by the curved orientation state.In normal white display mode, by the 1st polaroid 20, and when applying high voltage, be incident to the light of the liquid crystal layer of the state that belongs to Fig. 4 (d), will not change the polarization orientation and advance, absorbed by the 2nd polaroid 20 '.Thereby, become the demonstration of dark state.If display voltage reduces, then regulate power by the orientation of friction treatment, curved orientation will be returned back to, and the demonstration of bright state can be returned back to.By display voltage being changed control the inclination of liquid crystal molecule and make the intensity variation that sees through, then can carry out the GTG demonstration from polaroid again.Again, the liquid crystal indicator that possesses the liquid crystal cells of ocb mode, because but self-injection (spray) state of orientation is with the phase transfer of very high speed switching to the curved orientation state, so the liquid crystal indicator compared to other drive patterns such as TN pattern and IPS patterns will have the feature of animation display excellent.

B-1. the 1st optical compensating layer

The absolute value of the photoelasticity modulus of the 1st optical compensating layer is 40 * 10 ^-12(m ²/ N) below, preferred 0.2 * 10 ^-12～35 * 10 ^-12, more preferably 0.2 * 10-12～30 * 10 ^-12, and then preferred 0.2 * 10 ^-12～30 * 10 ^-12If it is uneven that the absolute value of photoelasticity modulus in this scope, then can suppress to show effectively.

The 1st optical compensating layer has the index distribution of nx＞ny 〉=nz.Moreover the 1st optical compensating layer has so-called contrary wavelength interdependence of disperseing.Particularly, phase differential has the relation of Δ nd (380)＜Δ nd (550)＜Δ nd (780) in its face.The relation that preferably has Δ nd (780)/Δ nd (550)＞1.10.By having this relation, can in the wide region of visible light, realize the good optical compensation.One of feature of the present invention has been to realize to have the liquid crystal panel of the optical compensating layer that has above-mentioned low light elastic modulus and contrary dispersion wavelength interdependence concurrently.

The following of phase difference nd (550) is limited to more than above, the preferred 120nm of 90nm, more preferably more than the 130nm in the face of the 1st optical compensating layer.On the other hand, Δ nd (550) on be limited to following, the preferred 170nm of 200nm following, more preferably below 160.

The lower limit of the thickness direction phase differential Rth (550) of the 1st optical compensating layer, be preferably 90nm above, more preferably more than the above and then preferred 130nm of 120nm.On the other hand, the upper limit of Rth (550) be preferably 200nm following, more preferably below the following and then preferred 160nm of 170nm.

The thickness of the 1st optical compensating layer can adopt the thickness that is fit to arbitrarily under the precursor that can bring into play effect of the present invention.Particularly, thickness is preferably 5～200 μ m, more preferably 40～170 μ m and then preferred 60～140 μ m.

What the 1st optical compensating layer was representative is to form by thin polymer film is carried out stretch processing.For example, by suitable selective polymerization species, stretching condition, drawing process etc., then can obtain having above-mentioned optical characteristics the 1st optical compensating layer of (phase differential, photoelasticity modulus in the index distribution, face).

As the material that contains in the above-mentioned thin polymer film, can adopt suitable material arbitrarily, preferably contain cellulose-based material.

As above-mentioned cellulose-based material, preferably by the cellulose-based material of acetyl group and propiono replacement.The lower limit of the degree of substitution of this cellulose-based material " (DSac) (degree of substitution with acetyl group)+(DSpr) (propiono substituting group) " (3 alkyl that expression is present in the cellulose repetitive on average with which kind of degree are replaced by acetyl group or propiono) is preferably more than 2, more preferably more than 2.3 and then preferred more than 2.6.The upper limit of " DSac+DSpr " is preferably below 3, more preferably below 2.9 and then preferred below 2.8.Be made as above-mentioned scope by degree of substitution, then can obtain having the optical compensating layer of above-mentioned required index distribution cellulose-based material.

The lower limit of above-mentioned DSpr (propiono substituting group) is preferably more than 1, more preferably more than 2 and then preferred more than 2.5.The upper limit of DSpr is preferably below 3, more preferably below 2.9 and then preferred below 2.8.By making DSpr be made as above-mentioned scope, then the dissolubility for cellulose-based material will improve, and control the thickness of the 1st optical compensating layer of gained easily.Moreover, by " DSac+DSpr " is made as above-mentioned scope, and make DSpr be made as above-mentioned scope, then can obtain having above-mentioned optical characteristics and have the contrary optical compensating layer that disperses the wavelength interdependence.

Above-mentioned DSac (degree of substitution with acetyl group) and DSpr (propiono substituting group) can open the method for putting down in writing in 2003-315538 communique [0016]～[0019] by the Jap.P. spy and try to achieve.

Above-mentioned cellulose-based material can have other substituting group beyond acetyl group and the propiono.As other substituting group, can give an example as ethers such as ester groups such as butyric ester, alkylether radicals, arylmethylene alkyl ether etc.

The number-average molecular weight of above-mentioned cellulose-based material is preferably 5,000～100,000, more preferably 10,000～70,000.By being made as above-mentioned scope, then productivity is superior, and can obtain excellent mechanical intensity.

As substitution technique, can adopt the method that is fit to arbitrarily to acetyl group and propiono.For example, cellulose is handled as alkali cellulose with strong caustic solution, it undertaken acyl groupization by the acetic anhydride of ormal weight and the potpourri of propionic andydride.By with the hydrolysis of acyl moiety ground, and adjust degree of substitution " DSac+DSpr ".

Above-mentioned thin polymer film can contain the macromolecular material that is fit to arbitrarily.As this macromolecular material, can give an example as cellulose esters such as cellulose butylates; Cellulose ether such as methylcellulose, ethyl cellulose etc.Optionally, thin polymer film also can contain adjuvants such as plastifier, thermal stabilizer, ultra-violet stabilizer.

B-2. the 2nd optical compensating layer

The 2nd optical compensating layer has the index distribution of nx=ny＞nz.Moreover the thickness direction phase differential of the 2nd optical compensating layer has the relation of Rth (380)＞Rth (550)＞Rth (780).Preferred thickness direction phase differential has the relation of Rth (780)/Rth (550)＜0.95.

The lower limit of the thickness direction phase differential Rth (550) of the 2nd optical compensating layer, be preferably 10nm above, more preferably more than the above and then preferred 50nm of 20nm.On the other hand, the upper limit of Rth (550) be preferably 1000nm following, more preferably below the following and then preferred 250nm of 500nm.

Be limited to below the 10nm on the interior phase difference nd (550) of the face of the 2nd optical compensating layer, below the preferred 5nm, and then below the preferred 3nm.

The 2nd optical compensating layer can be individual layer, also can be the duplexer more than 2 layers.Under the situation of duplexer, have in duplexer integral body under the prerequisite of above-mentioned optical characteristics, can suitably set material of each layer of formation and the thickness of each layer.

The thickness of the 2nd optical compensating layer can adopt the thickness that is fit to arbitrarily under the precursor that can bring into play effect of the present invention.Particularly, thickness is preferably 0.1～50 μ m, more preferably 0.5～30 μ m and then preferred 1～10 μ m.

As the material that constitutes the 2nd optical compensating layer, under the precursor that can obtain above-mentioned optical characteristics, can adopt the material that is fit to arbitrarily.For example, can give an example as non-liquid crystal liquid crystal property material as this material.Be preferably non-liquid-crystalline polymer especially.This non-liquid crystal liquid crystal property material is different with the liquid crystal liquid crystal property material, can form irrelevant and show the film of the optics uniaxiality of nx=ny＞nz by itself character with the substrate orientation.As a result, not only can use orientation substrate also can use non-oriented substrate.Even using under the situation of non-oriented substrate, also can omit the operation that is coated with alignment films in its surface and the operation of stacked alignment films etc.

As above-mentioned non-liquid crystal liquid crystal property material, aspects such as for example superior from thermotolerance, resistance to chemical reagents, the transparency, rich rigidity are preferably polymkeric substance such as polyamide, polyimide, polyester, polyetherketone, polyamidoimide, polyester-imide.These polymkeric substance can use arbitrary kind separately, also can use the potpourri more than 2 kinds with different functional groups as the potpourri of for example PAEK and polyamide.In these polymkeric substance, from the angle of high transparent, high orientation, high stretch, preferred especially polyimide.

There is no particular restriction for the molecular weight of above-mentioned polymkeric substance, and for example, weight-average molecular weight (Mw) is preferably 1,000～1,000,000 scope, more preferably 2,000～500,000 scope.

As above-mentioned polyimide, be preferably orientation height in the face for example, dissolve in the polyimide of organic solvent.Particularly, for example can using, the Jap.P. spy shows the polymkeric substance that the 2000-511296 communique is disclosed, it is to contain 9, the polycondensation product of two (aminoaryl) fluorenes of 9-and aromatic tetracarboxylic acid's dianhydride, and contain the polymkeric substance of repetitive shown in the above following formula (1).

[changing 1]

In the following formula (1), R ³～R ⁶Respectively independent be hydrogen, halogen, phenyl, by 1～4 halogen atom or C _1～10The phenyl that alkyl replaced, and from by C _1～10At least a substituting group of selecting in the group that alkyl constitutes.Preferred R ³～R ⁶Respectively independent be halogen, phenyl, by 1～4 halogen atom or C _1～10The phenyl that alkyl replaced, and from by C _1～10At least a substituting group of selecting in the group that alkyl constitutes.

In the following formula (1), Z is for example C _6～204 valency aromatic series bases, be preferably the derivant of pyromellitic acid base, polycycle aromatic series base, polycycle aromatic series base or with the group shown in the following formula (2).

[changing 2]

In the following formula (2), Z ' is for example covalent bond, C (R ⁷) ₂Base, basic, the O atom of CO, S atom, SO ₂Base, Si (C ₂H ₅) ₂Base or NR ⁸Base, under a plurality of situations, respectively can be identical or different.Again, w is 1 to 10 integer.R ⁷Independent respectively is hydrogen or C (R ⁹) ₃R ⁸Alkyl or C for hydrogen, carbon number 1～about 20 _6～20Aryl, under a plurality of situations, respectively can be identical or different.R ⁹Independent respectively is hydrogen, fluorine or chlorine.

As above-mentioned polycycle aromatic series base, can give an example as the 4 valency groups of deriving by naphthalene, fluorenes, benzofluorene or anthracene.As the substitutive derivative of above-mentioned polycycle aromatic series base, can give an example as by from by C again, _1～10Alkyl, its fluorinated derivatives, and the group that constitutes of halogens such as F or Cl in the above-mentioned polycycle aromatic series base that at least one group replaced selected.

In addition, the repetitive of putting down in writing as the flat 8-511812 communique of the special table of Jap.P. of can giving an example is that homopolymer shown in following formula (3) or (4) or repetitive are the polyimide shown in the following formula (5) etc.Again, the polyimide of following formula (5) is the preferred configuration of the homopolymer of following formula (3).

[changing 3]

[changing 4]

[changing 5]

In above-mentioned general formula (3)～(5), G and G ' are independent of respectively for example from by covalent bond, CH ₂Base, C (CH ₃) ₂Base, C (CF ₃) ₂Base, C (CX ₃) ₂Base (at this, X is a halogen), CO base, O atom, S atom, SO ₂Base, Si (CH ₂CH ₃) ₂Base, and N (CH ₃) group selected in the group that constitutes of base, respectively can be identical or different.

In following formula (3) and (5), L is a substituting group, and d and e represent that it replaces number.L is for example halogen, C _1-3Alkyl, C _1-10Halogenated alkyl, phenyl or substituted-phenyl, under a plurality of situations, respectively can be identical or different.As above-mentioned substituted-phenyl, can give an example as having from halogen, C _1-3Alkyl, and C _1-3At least a substituent substituted-phenyl of selecting in the group that halogenated alkyl constitutes.As above-mentioned halogen, can give an example as fluorine, chlorine, bromine or iodine again.D is 0 to 2 integer, and e is 0 to 3 integer.

In following formula (3)～(5), Q is a substituting group, and f represents that it replaces number.As Q, for for example from by hydrogen, halogen, alkyl, substituted alkyl, nitro, cyano group, sulfane base, alkoxy, aryl, substituted aryl, alkyl ester group, and the group that constitutes of substituted alkyl ester group atom or the group selected, under Q is a plurality of situation, respectively can be identical or different.As above-mentioned halogen, can give an example as fluorine, chlorine, bromine or iodine.As above-mentioned substituted alkyl, can give an example as halogenated alkyl.As above-mentioned substituted aryl, can give an example as halogenated aryl.F is 0 to 4 integer, and g is 0 to 3 integer, and h is 1 to 3 integer.Again, g and h are preferably greater than 1.

In the following formula (4), R ¹⁰And R ¹¹Independent respectively for from by hydrogen, halogen, phenyl, substituted-phenyl, alkyl, and the group that constitutes of substituted alkyl the group selected.Wherein, R ¹⁰And R ¹¹Preferred is halogenated alkyl independently respectively.

In the following formula (5), M ¹And M ²Independent respectively is halogen, C _1-3Alkyl, C _1-3Halogenated alkyl, phenyl or substituted-phenyl.As above-mentioned halogen, can give an example as fluorine, chlorine, bromine or iodine.As above-mentioned substituted-phenyl, can give an example as having from by halogen, C again, _1-3Alkyl, and C _1-3At least a substituent substituted-phenyl of selecting in the group that halogenated alkyl constitutes.

As the concrete example of the polyimide shown in the following formula (3), can give an example as with polyimide shown in the following formula (6) etc.

[changing 6]

Moreover, as above-mentioned polyimide, can give an example as making above-mentioned skeleton (repetitive) acid dianhydride or the diamines multipolymer that suitably carries out copolymerization in addition.

As above-mentioned acid dianhydride, can give an example as aromatic tetracarboxylic acid's dianhydride.As above-mentioned aromatic tetracarboxylic acid's dianhydride, can give an example as pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, naphthalene tetracarboxylic acid dianhydride, hetero ring type aromatic tetracarboxylic acid dianhydride, 2,2 '-substituted biphenyl base tetracarboxylic dianhydride etc.

As above-mentioned pyromellitic dianhydride, can give an example as pyromellitic dianhydride, 3 6-diphenyl pyromellitic dianhydride, 3, two (trifluoromethyl) pyromellitic dianhydride, 3 of 6-, 6-dibromo pyromellitic dianhydride, 3,6-dichloro pyromellitic dianhydride etc.As above-mentioned benzophenone tetracarboxylic dianhydride, can give an example as 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride etc.As above-mentioned naphthalene tetracarboxylic acid dianhydride, can give an example as 2,3,6 7-naphthalene-tetracarboxylic dianhydride, 1,2,5,6-naphthalene-tetracarboxylic dianhydride, 2,6-two chloro-naphthalenes-1,4,5,8-tetracarboxylic dianhydride etc.As above-mentioned hetero ring type aromatic tetracarboxylic acid dianhydride, can give an example as thiophene-2,3,4 5-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyridine-2,3,5,6-tetracarboxylic dianhydride etc.As above-mentioned 2,2 '-substituted biphenyl base tetracarboxylic dianhydride can give an example as 2,2 '-two bromo-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride, 2,2 '-two chloro-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride, 2,2 '-two (trifluoromethyl)-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride etc.

In addition, as other example of above-mentioned aromatic tetracarboxylic acid's dianhydride, can give an example as 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride, two (2,5,6-three fluoro-3,4-dicarboxyl phenyl) methane dianhydride, 2, two (3,4-dicarboxyl phenyl)-1 of 2-, 1,1,3,3, the 3-hexafluoropropane dianhydride, 4,4 '-two (3,4-dicarboxyl phenyl)-2,2-diphenyl propane dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, 4,4 '-oxygen base, two phthalic acid dianhydrides, two (3,4-dicarboxyl phenyl) sulfonic acid dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 4,4 '-[4,4 '-isopropylidene-two (to phenylene oxygen base)] two (phthalate anhydrides), N, N-(3,4-dicarboxyl phenyl)-N-methyl amine dianhydride, two (3,4-dicarboxyl phenyl) diethylsilane dianhydride etc.

Wherein, preferred 2 as above-mentioned aromatic tetracarboxylic acid's dianhydride, 2 '-substituted biphenyl base tetracarboxylic dianhydride, more preferably 2,2 '-two (trihalomethyl)-4,4 '-5,5 '-biphenyl tetracarboxylic dianhydride, and then preferred 2,2 '-two (trifluoromethyl)-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride.

As above-mentioned diamines, can give an example as aromatic diamine, its concrete example can be given an example as phenylenediamine, diaminobenzophenone, naphthylenediamine, hetero ring type aromatic diamine, be reached other aromatic diamine.

As above-mentioned phenylenediamine, can give an example as from by adjacent-,-and p-phenylenediamine, 2,4-diaminotoluene, 1,4-diamido-2-methoxybenzene, 1, the diamines of selecting in the group that phenylenediamine as the 4-diamido-2-phenyl benzene, and 1,3-diamido-4-chlorobenzene constitutes etc.As the example of above-mentioned diaminobenzophenone, can give an example as 22 '-diaminobenzophenone and 3,3 '-diaminobenzophenone etc.As above-mentioned naphthylenediamine, can give an example as 1 8-diaminonaphthalene and 1,5-diaminonaphthalene etc.As the example of above-mentioned hetero ring type aromatic diamine, can give an example as 2 6-diamino-pyridine, 2,4-diamino-pyridine, and 2,4-diamido-S-triazine etc.

Again, as aromatic diamine, except above-mentioned, also can give an example as 4,4 '-benzidine, 4,4 '-diaminodiphenyl-methane, 4,4 '-(9-fluorenylidene)-diphenylamine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 2,2 '-two chloro-4,4 '-benzidine, 2,2 ', 5,5 '-tetrachloro benzidine, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 2, two (4-aminophenyl) propane of 2-, 2, two (the 4-aminophenyls)-1,1 of 2-, 1,3,3, the 3-HFC-236fa, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl]-1 of 2-, 1,1,3,3, the 3-HFC-236fa, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone etc.

As above-mentioned polyetherketone, can give an example as the Jap.P. spy open that the 2001-49110 communique put down in writing with the PAEK shown in the following general formula (7).

[changing 7]

In the following formula (7), X represents substituting group, and q represents that it replaces number.X is for example halogen atom, low alkyl group, halogenated alkyl, lower alkoxy or halogenated alkoxy, under X is a plurality of situation, and respectively can be identical or different.

As above-mentioned halogen atom, can give an example as fluorine atom, bromine atoms, chlorine atom and iodine atom, wherein, be preferably fluorine atom.As above-mentioned low alkyl group, for example be preferably C _1～6Straight chain or have the alkyl of side chain, C more preferably _1～4The alkyl of straight or branched.Particularly, be preferably methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl and the tert-butyl group, special preferable methyl and ethyl.As above-mentioned halogenated alkyl, can give an example as the halogenide of the above-mentioned low alkyl group of trifluoromethyl etc.As above-mentioned lower alkoxy, for example be preferably C _1～6The alkoxy of straight or branched, C more preferably _1～4The alkoxy of straight or branched.Particularly, more preferably methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy are preferably methoxyl and ethoxy especially.As above-mentioned halogenated alkoxy, can give an example as the halogenide of above-mentioned lower alkoxies such as trifluoromethoxy.

In the following formula (7), q is 0 to 4 integer.In the following formula (7), preferred q=0 and be combined in the carbonyl at phenyl ring two ends and the oxygen atom of ether is present in the contraposition mutually.

In addition, in the following formula (7), R ¹Be the group shown in the following formula (8), m is 0 or 1 integer.

[changing 8]

In the following formula (8), X ' represents substituting group, for example is identical with X in the following formula (7).In the following formula (8), under X ' is a plurality of situation, respectively can be identical or different.Q ' represents the replacement number of above-mentioned X ', is 0 to 4 integer, and preferred q '=0.Again, p is 0 or 1 integer.

In the following formula (8), R ²The aromatic series base of expression divalent.As the aromatic series base of this divalent, can give an example as adjacent-, or right-phenylene, or by naphthalene, biphenyl, anthracene, neighbour-,-or right-terphenyl, phenanthrene, dibenzofurans, xenyl ether or the xenyl sulfone divalent group of deriving etc.In the aromatic series base of these divalents, directly be combined in aromatic hydrogen, also can be replaced by halogen atom, low alkyl group or lower alkoxy.Wherein, as above-mentioned R ², the preferred aromatic series base of from the group that constitutes by following formula (9)～(15), selecting.

[changing 9]

In the following formula (7), as R ¹, the group shown in the preferred following formula (16), in following formula (16), R ²And p and following formula (8) synonym.

[changing 10]

Moreover in the following formula (7), n represents the degree of polymerization, for example is 2～5000 scope, is preferably 5～500 scope.Again, the polymkeric substance that this polymerization can constitute for the repetitive by same structure, the also polymkeric substance that can constitute for repetitive by different structure.In the latter case, the polymeric species of repetitive can be block polymerization, also can be atactic polymerization.

And then the end of the PAEK shown in the following formula (7) is a fluorine to tetrafluoro benzoylene side preferably, and oxygen base alkylidene side is a hydrogen atom, and this aryl ether ketones can for example be represented with following formula (17).Again, in the following formula, n represents and the identical degree of polymerization of following formula (7).

[changing 11]

The concrete example of the aryl ether ketones shown in the following formula (7) can be exemplified below the structure shown in formula (18)～(21) etc., following various in, n represents and the identical degree of polymerization of following formula (7).

[changing 12]

[changing 13]

[changing 14]

[changing 15]

In addition, beyond these, as above-mentioned polyamide or polyester, polyamide or the polyester that can give an example and be put down in writing as the flat 10-508048 communique of the special table of Jap.P., these repetitives can for example be represented with following general formula (22).

[changing 16]

In the following formula (22), Y is O or NH.Again, E is for for example from by covalent bond, C ₂Alkylidene, halogenation C ₂Alkylidene, CH ₂Base, C (CX ₃) ₂Base (at this, X is halogen or hydrogen), CO base, O atom, S atom, SO ₂Base, Si (R) ₂Base, and the group that constitutes of N (R) base at least a group selected, respectively can be identical or different.Among the above-mentioned E, R is C _1-3Alkyl and C _1-3Halogenated alkyl at least a, and between being positioned at respect to carbonyl functional group or Y base in position or the contraposition.

In addition, in the following formula (22), A and A ' are substituting group, and t and z represent replacement number separately.Again, p is 0 to 3 integer, and q is 1 to 3 integer, and r is 0 to 3 integer.

Above-mentioned A is for example from by hydrogen, halogen, C _1-3Alkyl, C _1-3Alkoxy shown in halogenated alkyl, the OR (at this, R and above-mentioned synonym), aryl, substituted aryl, C by halogenation etc. _1-9Alkoxy carbonyl, C _1-9Alkyl-carbonyl oxygen base, C _1-12Aryloxy carbonyl, C _1-12Aryl carbonyl oxygen base and substitutive derivative thereof, C _1-12Aryl-amino-carbonyl, and C _1-12Select in the group that aryl carbonyl amino and substitutive derivative thereof constitute, under a plurality of situations, respectively can be identical or different.Above-mentioned A ' is for example from by halogen, C _1-3Alkyl, C _1-3Select in the group that halogenated alkyl, phenyl and substituted-phenyl constitute, under a plurality of situations, respectively can be identical or different.As the substituting group on the phenyl ring of above-mentioned substituted-phenyl, can give an example as halogen, C _1-3Alkyl, C _1-3Halogenated alkyl and these combination.Above-mentioned t is 0 to 4 integer, and above-mentioned z is 0 to 3 integer.

In the repetitive of polyamide shown in the following formula (22) or polyester, the structure shown in the preferred following general formula (23).

[changing 17]

In the following formula (23), as A, A ' and Y such as following formula (22) defined, v was 0 to 3 integer, is preferably 0 to 2 integer.X and y are respectively 0 or 1, but are not 0 simultaneously.

Then, the representational manufacture method at above-mentioned the 2nd optical compensating layer describes.As the manufacture method of the 2nd optical compensating layer, under the precursor that can obtain effect of the present invention, can adopt suitable method arbitrarily.

The 2nd optical compensating layer preferably forms by following: will from by polyamide, polyimide, polyester, polyetherketone, polyamidoimide, and the group that constitutes of polyester-imide the solution of at least a kind of polymkeric substance selecting, be coated on the transparent polymer film, give drying then, on the transparent polymer film, form this polymeric layer, and this transparent polymer film and this polymeric layer stretched integratedly or shrink.

The solvent of above-mentioned coating solution (being coated on the polymer solution on the transparent polymer film), there is no particular restriction, can give an example as the halogenated hydrocarbons of chloroform, methylene chloride, phenixin, ethylene dichloride, tetrachloroethane, triclene, zellon, chlorobenzene, o-dichlorobenzene etc.; The phenol of phenol, parachlorophenol etc.; Benzene,toluene,xylene, methoxybenzene, 1,2-dimethoxy benzene etc. aromatic hydrocarbon based; The ketone series solvent of acetone, MEK, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-etc.; Ester such as ethyl acetate, butyl acetate series solvent; The tert-butyl alcohol, glycerine, ethylene glycol, triethylene glycol, glycol monomethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2, the pure series solvent of 4-pentanediol and so on; The acid amides series solvent of dimethyl formamide, dimethyl acetamide and so on; The nitrile series solvent of acetonitrile, butyronitrile and so on; The ether series solvent of diethyl ether, butyl oxide, tetrahydrofuran and so on; Or carbon disulphide, ethyl cellosolve, butyl cellosolve etc.Wherein, preferable methyl isobutyl ketone.This is because it shows highly dissoluble for non-liquid crystal material, and does not corrode substrate.These solvents can use separately, or make up more than 2 kinds and use.

The concentration of the above-mentioned non-liquid-crystalline polymer in the above-mentioned coating solution as long as can obtain above-mentioned optical compensating layer, and can be coated with, and then can adopt the concentration that is fit to arbitrarily.For example, this solution is with respect to solvent 100 weight portions, preferably contains non-liquid-crystalline polymer 5～50 weight portions, more preferably 10～40 weight portions.The solution of this concentration range has the viscosity of easy coating.

Above-mentioned coating solution optionally can contain various adjuvants such as stabilizing agent, plastifier, metal species again.

Above-mentioned coating fluid optionally can contain other different resins again.As this other resin, can give an example as various resins for universal use, engineering plastics, thermoplastic resin, thermoset resin etc.By also using this resin, then can form the optical compensating layer that has suitable physical strength and permanance according to purpose.

As above-mentioned resins for universal use, can give an example as tygon (PE), polypropylene (PP), polystyrene (PS), polymethylmethacrylate (PMMA), ABS resin, reach AS resin etc.Nylon), polyethylene terephthalate (PET), and polybutylene terephthalate (PBT) etc. as above-mentioned engineering plastics, can give an example as poly-acetate (POM), polycarbonate (PC), polyamide (PA:.As above-mentioned thermoplastic resin, can give an example as polyphenylene sulfide (PSP), polyethersulfone (PES), polyketone (PK), polyimide (PI), poly-cyclohexanedimethanol terephthalate (PCT), polyarylate (PAR), reach liquid crystal polymer (LCP) etc.As above-mentioned thermoset resin, can give an example as epoxy resin, novolac resin etc.

The kind and the amount of the above-mentioned different resins that is added in the above-mentioned coating solution can suitably be set according to purpose.For example, this resin can be with respect to above-mentioned non-liquid-crystalline polymer, with preferred 0～50 quality %, more preferably the ratio of 0～30 quality % is added.

As the coating process of above-mentioned solution, can give an example is coated with method, woodburytype etc. as spin-coating method, rolling method, flow coat method, print process, dip coating, casting filming therapy, rod.Optionally also can adopt the overlap mode of polymeric layer during coating again.

After the coating, for example by the drying of air dry, air-dry, heat drying (for example 60～250 ℃) etc., the solvent evaporation in the above-mentioned solution is removed, and form the optical compensating layer of film like.

As above-mentioned transparent polymer film, can use and the identical film of protective seam described later (the B-4 item is illustrated).

The 2nd optical compensating layer can be peeled off the back with the 1st optical compensating layer and be used from the duplexer (having formed the duplexer of the 1st optical compensating layer on the transparent polymer film) of above-mentioned gained, also can directly use duplexer.Further carry out when stacked with polaroid directly using duplexer, the transparent polymer film in the duplexer also can be brought into play the function as polarizer protection film described later.

B-3. polaroid

As above-mentioned the 1st polaroid and the 2nd polaroid, visual purpose adopts the polaroid that is fit to arbitrarily.Can give an example as: at polyvinyl alcohol film, the formalized polyvinyl alcohol film of part, ethylene vinyl acetate co-polymer pastern divides on the hydrophilic macromolecule film of saponification film etc., make dichroic substance absorption such as iodine or dichroic dye after uniaxial tension and polaroid; Polyenoid such as the desalination acid treatment thing of the processed thing of polyvinyl alcohol (PVA) or Polyvinylchloride are oriented film etc.Wherein, dichroic substance such as iodine are adsorbed on the polyvinyl alcohol film and through the polaroid of uniaxial tension, its polarisation dichroic ratio is higher, so preferred especially.The thickness of these polaroids does not have special restriction, is generally about 5～80 μ m.

Iodine is adsorbed on the polyvinyl alcohol film and through the polaroid of uniaxial tension, can be for example by dyeing in the aqueous solution that polyvinyl alcohol (PVA) be impregnated in iodine, and be stretched to 3～7 times of raw footage and make.Optionally, also can contain boric acid and zinc sulfate, zinc chloride etc., and can impregnated in the aqueous solution of potassium iodide etc.Moreover, optionally also can be before dyeing polyvinyl alcohol film be impregnated in the water and wash.By polyvinyl alcohol film is washed, not only can clean the dirt or the anti blocking agent on polyvinyl alcohol film surface, also have and prevent the unequal uneven effect of the dyeing that is caused because of the polyvinyl alcohol film swelling.Stretching can be carried out after utilizing iodine staining, stretches while also can dye, and again, also can utilize iodine to dye after stretching.Also can or stretch in the water-bath in the aqueous solution of boric acid and potassium iodide etc.

B-4. protective seam

Protective seam 50 is transparent, is preferably non-coloring.Phase difference nd (550) is more than the 0nm and below the 10nm in the face of protective seam 50, is preferably more than the 0nm and below the 6nm, more preferably more than the 0nm and below the 3nm.The phase differential Rth (550) of the thickness direction of protective seam 50 is more than the 0nm and below the 20nm, more than the preferred 0nm and below the 10nm, more preferably more than the 0nm and below the 6nm, and then more than the preferred 0nm and below the 3nm.

The visual purpose of the thickness of above-mentioned protective seam 50 is suitably set.Particularly, thickness is preferably 20～200 μ m, more preferably 30～100 μ m and then preferred 35～95 μ m.

As protective seam 50, representationally be to use cellulose-based film.Usually as the cellulose-based film of protective film use, for example under the situation of tri acetyl cellulose film, thickness direction phase differential (Rth) is about 40nm under thickness 40 μ m.Thereby,, can't directly adopt the bigger cellulose-based film of this thickness direction phase differential (Rth) as protective seam 50 of the present invention.Among the present invention,, can then can preferably obtain the protective seam 50 among the present invention by the suitable processing of implementing thickness direction phase differential (Rth) is reduced for the bigger cellulose-based film of thickness direction phase differential (Rth).

As the above-mentioned processing that is used to thickness direction phase differential (Rth) is reduced, can adopt the disposal route that is fit to arbitrarily.Can give an example as the base material such as polyethylene terephthalate, polypropylene, stainless steel that will be coated with cyclopentanone, MEK equal solvent, conform to common cellulose-based film, behind heat drying (for example about 80～150 ℃ down about 3～10 minutes), the method that base film is peeled off; Norbornene resin, acrylic resin etc. is dissolved in cyclopentanone, the MEK equal solvent, with the solution coat that obtains at common cellulose-based film, behind heat drying (for example about 80～150 ℃ down about 3～10 minutes), the method that coated thin film is peeled off.

As the material that constitutes cellulose-based film, preferably can give an example as fatty acid substituted cellulose based polymers such as diacetyl cellulose, tri acetyl celluloses.The acetic acid degree of substitution of common employed tri acetyl cellulose is about 2.8, but by preferably the acetic acid degree of substitution being controlled at 1.8～2.7, more preferably the propionic acid degree of substitution being controlled at 0.1～1, then can be controlled to be less with thickness direction phase differential (Rth).

By in above-mentioned fatty acid substituted cellulose based polymer; add dibutyl terephthalate, to plastifier such as toluene sulfone anilide (p-toluenesulfonanilide), acetyl triethyl citrates, then can be controlled to be less with thickness direction phase differential (Rth).The addition of plastifier is with respect to fatty acid substituted cellulose based polymer 100 weight portions, is preferably 40 weight portions following, more preferably 1～20 weight portion and then preferred 1～15 weight portion.

Be used for above-mentioned thickness direction phase differential (Rth) is controlled to be less technology, also can give appropriate combination and use.

As other preferred concrete example that can satisfy above-mentioned optical characteristics (phase difference nd (550), thickness direction phase differential Rth (550) in the face), also can enumerate the acryl resin film.As the acryl resin film, be preferably the Jap.P. spy and open the acryl resin film that the 2005-314534 communique is put down in writing, as will to contain the glutaric anhydride unit shown in the following structural formula (24) acryl resin (A) comprises as major component.By containing the glutaric anhydride unit shown in the following structural formula (24), thermotolerance is risen.In the following structural formula (24), R ¹, R ²Represent the identical or different hydrogen atom or the alkyl of carbon number 1～5, be preferably hydrogen atom or methyl, more preferably methyl.

[changing 18]

In the aforesaid propylene acid resin (A), containing of the glutaric anhydride unit shown in the said structure formula (24) is proportional, is preferably 20～40 weight %, more preferably 25～35 weight %.

In the aforesaid propylene acid resin (A), except the glutaric anhydride unit shown in the said structure formula (24), also can contain the monomeric unit more than a kind or 2 kinds that is fit to arbitrarily.As this monomeric unit, preferably can give an example as vinyl carboxylic acid Arrcostab unit.In the aforesaid propylene acid resin (A), containing of vinyl carboxylic acid Arrcostab unit is proportional, is preferably 60～80 weight %, more preferably 65～75 weight %.

As above-mentioned vinyl carboxylic acid Arrcostab unit, can be exemplified below and state the unit shown in the general formula (25).In the following general formula (25), R ³The aliphatics or the ester ring type hydrocarbon of expression hydrogen atom or carbon number 1～5, R ⁴The aliphatic hydrocarbon of expression carbon number 1～5.

[changing 19]

The weight-average molecular weight of aforesaid propylene acid resin (A) is preferably 80000～150000.

Containing of aforesaid propylene acid resin (A) in the aforesaid propylene acid resin film is proportional, is preferably 60～90 weight %.

In the aforesaid propylene acid resin film, except aforesaid propylene acid resin (A), also can contain the composition that is fit to arbitrarily more than a kind or 2 kinds.As this composition, in the scope that does not undermine the object of the invention, can adopt the composition that is fit to arbitrarily.Can give an example as in addition resin of above-mentioned acryl resin (A), ultraviolet light absorber, antioxidant, lubricant, plastifier, release agent, anti-coloring agent, fire retardant, nucleator, antistatic agent, pigment, colorant etc.

As mentioned above, liquid crystal panel of the present invention also can have protective film except having above-mentioned protective seam.As protective film, can use the film identical with protective seam.

For above-mentioned each layer (film) stacked, give stacked via the adhesive phase that is fit to arbitrarily or adhesive layer.

Below, be described more specifically the present invention by embodiment, but the present invention is not limited to these embodiment.The assay method of each characteristic among the embodiment is as described below.

(1) mensuration of phase differential

(Japanese beam split Co., Ltd. system M-220) is calculated with beam split elliptically polarized light analyzer with phase difference nd in the face and thickness direction phase differential Rth.Measuring temperature is 23 ℃, and the mensuration wavelength is 380nm, 550nm and 780nm.

(2) mensuration of photoelasticity modulus

(Japanese beam split Co., Ltd. system M-220) is measured by beam split elliptically polarized light analyzer with the photoelasticity modulus of sample film.

(3) mensuration of aberration

Use the trade name " EZ Contrast160D " of ELDIM corporate system, on the 45 ° of directions in position angle, make polar angle be changed to 0 °～80 ° and measure the tone of liquid crystal indicator, on the XY chromatic diagram, draw.Moreover, on 60 ° of directions of polar angle, to make azimuthal variation be 0 °～360 ° tones of measuring liquid crystal indicator.

(4) mensuration of contrast

Make liquid crystal indicator show white image and picture black, measure by the trade name " EZ Contrast160D " of ELDIM corporate system.

[embodiment 1]

(formation of the 1st optical compensating layer)

Film [Kaneka system with the cellulose ester of thickness 110 μ m; trade name: KA, DSac (degree of substitution with acetyl group)=0.04, DSpr (propiono degree of substitution)=2.76]; under 145 ℃, carry out free end and be stretched to 1.5 times, and obtain the 1st optical compensating layer of thickness 108 μ m.The photoelasticity modulus of the 1st optical compensating layer of gained is 25 * 10 ^-12(m ²/ N).Phase differential is Δ nd (380)=102nm, Δ nd (550)=140nm, Δ nd (780)=163nm in the face of the 1st optical compensating layer of gained, and the thickness direction phase differential is Rth (380)=105nm, Rth (550)=145nm, Rth (780)=169nm.The index distribution of 550nm is

(having the making of the polarization plates of the 1st optical compensating layer)

After polyvinyl alcohol film dyeed, in borated aqueous solution, between the different roller of speed ratio,, obtain polaroid with its uniaxial tension to 6 times in containing the aqueous solution of iodine.One side of the polaroid that obtains carrying out like this, via polyethenol series tackifier (thickness 0.1 μ m), applying tri acetyl cellulose film (thickness 80 μ m) [Fujiphoto system, trade name: ZRF80S].Phase differential is Δ nd (550)=0.9nm in the face of this protective seam, and the thickness direction phase differential is Rth (550)=1.2nm.At the opposite side of polaroid, via polyethenol series tackifier (thickness 0.1 μ m), applying TAC protective film (thickness 80 μ m) [Fujiphoto system, trade name: TF80UL].Phase differential is Δ nd (550)=1nm in the face of this protective film, and the thickness direction phase differential is Rth (550)=60nm.Then, the 1st optical compensating layer with above-mentioned gained conforms on the protective seam via acrylic adhesive (thickness 20 μ m).At this moment, with the hysteresis of the 1st optical compensating layer mutually the tensile axis (absorption axes) of axle and polaroid be in fact the mode of quadrature mutually and carry out stackedly, and obtain having the polarization plates of the 1st optical compensating layer.

(formation of the 2nd optical compensating layer)

Will be by 2, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides (6FDA) and 2,2 '-two (trifluoromethyl)-4 of 2-, the synthetic polyimide of 4 '-benzidine (TFMB) is dissolved in the cyclohexanone, modulates the polyimide solution of 15 quality %.The thickness of this solution with 30 μ m is coated on the tri acetyl cellulose base material (transparent polymer film).100 ℃ following dried 10 minute, obtain 2nd optical compensating layer of thickness about 4 μ ms thereafter.Phase differential is Δ nd (380)=0.3nm, Δ nd (550)=0.2nm, Δ nd (780)=0.2nm in the face of the 2nd optical compensating layer of gained, and the thickness direction phase differential is Rth (380)=193nm, Rth (550)=130nm, Rth (780)=119nm.The index distribution of 550nm is

(having the making of the polarization plates of the 2nd optical compensating layer)

The 2nd optical compensating layer with above-mentioned gained; be pasted to via bonding agent (thickness 20 μ m) and have TAC protective film (Fujiphoto system; trade name: TF80UL)/polaroid/TAC protective film (trade name: the polarization plates of formation TF80UL) [Nitto Denko Corp's system; trade name: SEG1224] on, polarization plates obtained with the 2nd optical compensating layer.

(making of liquid crystal panel)

Remove liquid crystal cells from HappyWEGA32 cun LCD TV of Sony system (carrying VA mode liquid crystal unit), recognize on the side, attach the above-mentioned polarization plates of having the 1st optical compensating layer via acrylic adhesive (thickness 20 μ m) looking of this liquid crystal cells.At this moment, the 1st optical compensating layer is to attach with the method that becomes liquid crystal cell side.In backlight one side of liquid crystal cells, attach the above-mentioned polarization plates of having the 2nd optical compensating layer via acrylic adhesive (thickness 20 μ m).At this moment, the 2nd optical compensating layer is to attach with the method that becomes liquid crystal cell side.Again, carry out stackedly, and obtain liquid crystal panel spool to be in fact the mode of quadrature mutually with the stretching (absorption) of stretching (absorptions) axle of the polaroid of the polarization plates of the 1st optical compensating layer and the polaroid of the polarization plates of having the 2nd optical compensating layer.In the liquid crystal indicator that the liquid crystal panel that uses gained is made, the measurement result of the aberration in the time of will making polar angle be changed to 0 °～80 ° on the 45 ° of directions in position angle is shown in Fig. 5 (a), and the measurement result of the aberration in the time of will making azimuthal variation be 0 °～360 ° on 60 ° of directions of polar angle is shown in Fig. 5 (b).The visual angle interdependence of contrast is shown in the radar map of Fig. 5 (c) again.

(comparative example 1)

In the formation of the 2nd optical compensating layer; after polyimide solution being applied on the tri acetyl cellulose base material; 100 ℃ of following dried 10 minutes; under 155 ℃, be stretched as 1.2 times and form the 2nd optical compensating layer; and do not use the 1st optical compensating layer and recognize side looking of liquid crystal cells and attach polarization plates [Nitto Denko Corp's system; trade name: SEG1224] in addition, all the other carry out similarly to Example 1, obtain liquid crystal panel.Again, the index distribution of the 550nm of the 2nd optical compensating layer of gained is nx＞ny＞nz.In the liquid crystal indicator that the liquid crystal panel that uses gained is made, the measurement result of the aberration in the time of will making polar angle be changed to 0 °～80 ° on the 45 ° of directions in position angle is shown in Fig. 6 (a), and the measurement result of the aberration in the time of will making azimuthal variation be 0 °～360 ° on 60 ° of directions of polar angle is shown in Fig. 6 (b).The visual angle interdependence of contrast is shown in the radar map of Fig. 6 (c) again.

(comparative example 2)

With norbornene resin film [Japanese Zeon system, trade name: Zeonor ZF14-100] under 135 ℃ stretch on the X-direction 1.25 times, on Y direction, stretch 1.03 times and use as the 2nd optical compensating layer.Phase differential is Δ nd (380)=75nm, Δ nd (550)=68nm, Δ nd (780)=67nm in the face of the 2nd optical compensating layer of gained, and the thickness direction phase differential is Rth (380)=188nm, Rth (550)=170nm, Rth (780)=168nm.The index distribution of 550nm is nx＞ny＞nz.The 2nd optical compensating layer of gained is pasted to polarization plates [Nitto Denko Corp's system, trade name: SEG1224] via bonding agent (thickness 20 μ m), and obtains polarization plates with the 2nd optical compensating layer.

Recognize side the looking identical of liquid crystal cells, attach polarization plates [Nitto Denko Corp's system, trade name: SEG1224] via acrylic adhesive (thickness 20 μ m) with employed liquid crystal cells among the embodiment 1.In the backlight side of liquid crystal cells, the 2nd optical compensating layer of above-mentioned gained is attached via acrylic adhesive (thickness 20 μ m).At this moment, the mode that becomes liquid crystal cell side with the 2nd optical compensating layer attaches.Again, be mutually in fact the mode of quadrature with each stretching (absorption) axle of the polaroid of seizing liquid crystal cells on both sides by the arms and carry out stackedly, and obtain liquid crystal panel.In the liquid crystal indicator that the liquid crystal panel that uses gained is made, the measurement result of the aberration in the time of will making polar angle be changed to 0 °～80 ° on the 45 ° of directions in position angle is shown in Fig. 7 (a), and the measurement result of the aberration in the time of will making azimuthal variation be 0 °～360 ° on 60 ° of directions of polar angle is shown in Fig. 7 (b).The visual angle interdependence of contrast is shown in the radar map of Fig. 7 (c) again.

(comparative example 3)

Use cellulose-based resin film [KONICA MINOLTA system, trade name: KC8NYACS] as the 1st optical compensating layer and the 2nd optical compensating layer.Phase differential is Δ nd (380)=37nm, Δ nd (550)=45nm, Δ nd (780)=49nm in the face of this cellulose-based resin film, and the thickness direction phase differential is Rth (380)=120nm, Rth (550)=145nm, Rth (780)=157nm.The index distribution of 550nm is nx＞ny＞nz.

Above-mentioned cellulose-based resin film is pasted to polarization plates [Nitto Denko Corp's system, trade name: SEG1224] via bonding agent (thickness 20 μ m), obtains reaching the polarization plates of having the 2nd optical compensating layer with the polarization plates of the 1st optical compensating layer.

Except using the above-mentioned polarization plates of having the 1st optical compensating layer to reach with the polarization plates of the 2nd optical compensating layer, all the other carry out similarly to Example 1, obtain liquid crystal panel.In the liquid crystal indicator that the liquid crystal panel that uses gained is made, the measurement result of the aberration in the time of will making polar angle be changed to 0 °～80 ° on the 45 ° of directions in position angle is shown in Fig. 8 (a), and the measurement result of the aberration in the time of will making azimuthal variation be 0 °～360 ° on 60 ° of directions of polar angle is shown in Fig. 8 (b).The visual angle interdependence of contrast is shown in the radar map of Fig. 8 (c) again.

(comparative example 4)

Use polycarbonate-based resin [Supreme Being people's system, trade name: PUREACE] as the 1st optical compensating layer.The photoelasticity modulus of this polycarbonate based resin film is 61 * 10 ^-12(m ²/ N), phase differential is Δ nd (380)=101nm, Δ nd (550)=145nm, Δ nd (780)=153nm in the face, the thickness direction phase differential is Rth (380)=99nm, Rth (550)=141nm, Rth (780)=149nm.The index distribution of 550nm is

Above-mentioned the 1st optical compensating layer is pasted on the polarization plates [Nitto Denko Corp's system, trade name: SEG1224] via bonding agent (thickness 20 μ m), obtains polarization plates with the 1st optical compensating layer.At this moment, with the hysteresis of the 1st optical compensating layer mutually the tensile axis (absorption axes) of axle and polaroid be in fact the mode of quadrature mutually and carry out stacked.

Norbornene resin film [JSR system, trade name: ARTON] is biaxial stretch-formedly used as the 2nd optical compensating layer to 1.3 times to carrying out in length and breadth under 175 ℃.Phase differential is Δ nd (380)=2nm, Δ nd (550)=2nm, Δ nd (780)=2nm in the face of the 2nd optical compensating layer, and the thickness direction phase differential is Rth (380)=244nm, Rth (550)=220nm, Rth (780)=218nm.The index distribution of 550nm is

Except using the above-mentioned polarization plates and the 2nd optical compensating layer of having the 1st optical compensating layer, all the other carry out similarly to Example 1, obtain liquid crystal panel.In the liquid crystal indicator that the liquid crystal panel that uses gained is made, the measurement result of the aberration in the time of will making polar angle be changed to 0 °～80 ° on the 45 ° of directions in position angle is shown in Fig. 9 (a), and the measurement result of the aberration in the time of will making azimuthal variation be 0 °～360 ° on 60 ° of directions of polar angle is shown in Fig. 9 (b).The visual angle interdependence of contrast is shown in the radar map of Fig. 9 (c) again.

By Fig. 5～9 obviously as can be known, the liquid crystal panel of gained in the comparative example 1～4, the aberration of the liquid crystal panel of gained is outstanding among the embodiment 1.

By Fig. 5～9 obviously as can be known, compared to the liquid crystal indicator of comparative example of the present invention, the liquid crystal indicator of the embodiment of the invention is all outstanding aspect positive contrast and tilted direction contrast two.

Use the liquid crystal panel of embodiment 1 and comparative example 4 to make liquid crystal indicator, observe whether inequality takes place to show when picture black shows.It is observed photo and is shown in Figure 10.Shown in Figure 10 (a), the liquid crystal indicator of embodiment 1 suppresses to show uneven well.On the other hand, shown in Figure 10 (b), the liquid crystal indicator of comparative example 4 is in the whole inequality (idol has light leak) that takes place of picture.Again, by the photo of Figure 10 as can be known, liquid crystal indicator of the present invention is than the liquid crystal indicator of comparative example, its with blueness faint extraordinarily.

(utilizability on the industry)

Liquid crystal panel of the present invention and liquid crystal indicator can be fit to be applied to LCD TV, mobile phone etc.

Claims (9)

1. liquid crystal panel; it has: liquid crystal cells, be configured in a side of this liquid crystal cells the 1st polaroid, be configured in the opposite side of this liquid crystal cells the 2nd polaroid, be configured in the 1st polaroid or the 2nd polaroid this liquid crystal cell side protective seam and be configured in the 1st polaroid and the 2nd polaroid between the 1st optical compensating layer and the 2nd optical compensating layer

This protective seam has the relation of following formula (1) and (2),

The 1st optical compensating layer is configured in the liquid crystal cell side of this protective seam, and the absolute value of photoelasticity modulus is 40 * 10 ^-12(m ²/ N) below, and have the relation of following formula (3), (4) and (5),

The 2nd optical compensating layer has the relation of following formula (6) and (7),

0nm≤Δnd(550)≤10nm ......(1)

0nm≤Rth(550)≤20nm ......(2)

Δnd(380)＜Δnd(550)＜Δnd(780)......(3)

nx＞ny≥nz ......(4)

90nm≤Δnd(550)≤200nm ......(5)

Rth(380)＞Rth(550)＞Rth(780) ......(6)

nx＝ny＞nz ......(7)

At this, Δ nd (380), Δ nd (550) and Δ nd (780) are illustrated respectively in phase differential in the face of being measured with wavelength 380nm, 550nm and 780nm under 23 ℃, Rth (380), Rth (550) and Rth (780) are illustrated respectively in the phase differential of the thickness direction of being measured with wavelength 380nm, 550nm and 780nm under 23 ℃, nx, ny and nz represent respectively the to lag behind refractive index of phase direction of principal axis, leading phase direction of principal axis and thickness direction.

2. liquid crystal panel according to claim 1, wherein,

Above-mentioned the 1st optical compensating layer and above-mentioned the 2nd optical compensating layer are benchmark with above-mentioned liquid crystal cells, are configured in not homonymy respectively.

3. liquid crystal panel according to claim 1 and 2, wherein,

Above-mentioned the 1st optical compensating layer has the relation of Δ nd (780)/Δ nd (550)＞1.10.

4. according to any described liquid crystal panel in the claim 1～3, wherein,

Above-mentioned the 1st optical compensating layer contains cellulose-based material.

5. liquid crystal panel according to claim 4, wherein,

Degree of substitution with acetyl group of above-mentioned cellulose-based material (DSac) and propiono degree of substitution (DSpr) are 2.0≤DSac+DSpr≤3.0,1.0≤DSpr≤3.0.

6. according to any described liquid crystal panel in the claim 1～5, wherein,

Above-mentioned the 2nd optical compensating layer has the relation of Rth (780)/Rth (550)＜0.95.

7. according to any described liquid crystal panel in the claim 1～6, wherein,

The material that constitutes above-mentioned the 2nd optical compensating layer is at least a kind of non-liquid-crystalline polymer selecting from the group that is made of polyamide, polyimide, polyester, polyetherketone, polyamidoimide and polyester-imide.

8. according to any described liquid crystal panel in the claim 1～7, wherein,

Above-mentioned liquid crystal cells is VA pattern or ocb mode.

9. liquid crystal indicator, it comprises: any described liquid crystal panel in the claim 1～8.

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