CN1869743A - Optical film, liquid crystal panel, and liquid crystal display apparatus - Google Patents

Abstract

The present invention can provide an optical film suitable for a liquid crystal display apparatus providing colorless neutral display in all azimuth angle directions, a liquid crystal panel employing the optical film, and a liquid crystal display apparatus employing the liquid crystal panel. The optical film of the present invention includes a first transparent protective film, a polarizer, a second transparent protective film, and a birefringent layer having a relationship of nx>ny=nz and positive uniaxial property in the stated order, in which the second transparent protective film has a thickness direction retardation (Rth) represented by the formula (1) of 10 nm or less.

Description

Blooming, liquid crystal panel and liquid crystal indicator

The application is based on the 35th piece the 119th of federal code joint, requires the right of priority of Japanese patent application 2006-044888 number of Japanese patent application 2005-152311 number submitted on May 25th, 2005 and submission on February 22nd, 2006, and it is hereby incorporated by.

Technical field

The present invention relates to blooming, liquid crystal panel and liquid crystal indicator.More particularly, the present invention relates to be applicable to the blooming that the colourless neutral liquid crystal indicator that shows is provided at all azimuth directions, also relate to liquid crystal panel that uses this blooming and the liquid crystal indicator that uses this liquid crystal panel.

Background technology

Fig. 5 A is the schematic cross-section of typical traditional liquid crystal indicator, and Fig. 5 B is the schematic cross-section that is used for the liquid crystal cells of this liquid crystal indicator.Liquid crystal indicator 900 disposes: liquid crystal cells 910, be configured in the polarizer 920 and 920 of liquid crystal cells 910 both sides ' and be configured in respectively the Polarizer 930 and 930 in polarizer 920 and 920 ' outside '.Usually, Polarizer 930 and 930 ' be configured to make its absorption axes separately to be perpendicular to one another.Liquid crystal cells 910 comprises: a pair of substrate 911 and 911 ' and be configured between the substrate liquid crystal layer 912 as display medium.A substrate 911 disposes: be used to control liquid crystal electro-optical characteristic on-off element (being generally TFT) and be used to this on-off element that the sweep trace of gate signal is provided and be used to this on-off element that the signal wire (element and line do not show) of source signal is provided.Another substrate 911 ' dispose: color layer 913R, the 913G and the 913B that constitute chromatic filter; And light shield layer (black-matrix layer) 914.Substrate 911 and 911 ' between distance (cell gap) control with the spacer (not shown).

Polarizer is used for the optical compensation of liquid crystal indicator.For obtaining optimized optical compensation (for example, the improvement of viewing angle properties, gamut and contrast aspect), aspect the optimization of the optical characteristics of polarizer and/or the configuration of the polarizer in the liquid crystal indicator, various trials have been carried out.Shown in Fig. 5 A, polarizer be configured in respectively usually liquid crystal cells 910 and Polarizer 930 or 930 ' between (referring to JP 11-95208A, for example).

In recent years, high definition and high performance liquid crystal indicator require further improvement screen uniformity coefficient and display quality.But traditional liquid crystal indicator almost can not develop colourless neutral demonstration the on all azimuth directions.And, along with the development of small portable liquid crystal indicator, to reducing the increase that needs of liquid crystal indicator thickness.

Summary of the invention

Finish the present invention in order to solve above-mentioned traditional problem, therefore the purpose of this invention is to provide: blooming, it is applicable to provides the colourless neutral liquid crystal indicator that shows on each azimuth direction; Adopt the liquid crystal panel of this blooming; With the optical display that adopts this liquid crystal panel.

The birefringent layers that blooming of the present invention comprises first transparent protective film, polaroid, second transparent protective film successively and has nx＞ny=nz relation and positive single shaft character; wherein the phase differential of the thickness direction of second transparent protective film (Rth) represents that with relational expression (1) it is less than or equal to 10nm.

Rth＝(nx-nz)×d …(1)

In preferred implementation of the present invention, first transparent protective film is any one in cellulose family film and the norborene class film.

In preferred implementation of the present invention, the phase differential of the thickness direction of second transparent protective film (Rth) is less than or equal to 6nm.

In preferred implementation of the present invention, the phase differential of the thickness direction of second transparent protective film (Rth) is less than or equal to 3nm.

Of the present invention preferred embodiment in, phase differential (Δ nd) represents that with relational expression (2) it is less than or equal to 2nm in the face of second transparent protective film.

Δnd＝(nx-ny)×d …(2)

In preferred implementation of the present invention, phase differential (Δ nd) is less than or equal to 1nm in the face of second transparent protective film.

In preferred implementation of the present invention, second transparent protective film is the cellulose family film.

In preferred implementation of the present invention, the absorption axes of polaroid and the slow axis of birefringent layers are perpendicular to one another substantially.

In preferred implementation of the present invention, birefringent layers is λ/4 plates.

In preferred implementation of the present invention, the absolute value of the difference of phase differential (Δ nd) and thickness direction phase differential (Rth) is less than or equal to 10nm in the face of birefringent layers.

In preferred implementation of the present invention, the absolute value that birefringent layers contains photoelastic coefficient is less than or equal to 2 * 10 ^-11m ²The resin of/N.

In preferred implementation of the present invention, resin is a cycloolefin resin.

According to another aspect of the present invention, provide liquid crystal panel.This liquid crystal panel comprises liquid crystal cells and is configured in the blooming of the present invention of this liquid crystal cells one side.

In preferred implementation of the present invention, liquid crystal cells is any one in VA pattern and the ocb mode.

In preferred implementation of the present invention, liquid crystal cells comprises and is configured in the blooming of the present invention of watching side; And this liquid crystal cells comprises the birefringent layers with nx 〉=ny＞nz relation that is configured in backlight side.

In preferred implementation of the present invention, the birefringent layers with nx 〉=ny＞nz relation is formed by non-liquid crystal material.

In preferred implementation of the present invention, non-liquid crystal material is to be selected from least a in polyamide, polyimide, polyester, polyetherketone, polyamidoimide or the polyester-imide.

According to another aspect of the present invention, provide liquid crystal indicator.Liquid crystal indicator of the present invention comprises liquid crystal panel of the present invention.

The present invention can provide and be applicable to blooming that the colourless neutral liquid crystal indicator that shows is provided on each azimuth direction, adopt the liquid crystal panel of this blooming and adopt the optical display of this liquid crystal panel.Such effect can be configured in first polaroid and have between the birefringent layers of nx＞ny=nz relation and positive single shaft character and provide significantly by second transparent protective film that will have the specific physical performance.

Description of drawings

In the accompanying drawings:

Fig. 1 is the schematic cross-section according to the liquid crystal panel of preferred implementation of the present invention;

Fig. 2 A and 2B have respectively illustrated the schematic cross-section of the liquid crystal alignment state of liquid crystal layer under the situation of the liquid crystal cells of liquid crystal indicator employing VA pattern of the present invention naturally;

Each has illustrated the schematic cross-section of the liquid crystal alignment state of liquid crystal layer under the situation of liquid crystal indicator employing ocb mode liquid crystal of the present invention unit to Fig. 3 A naturally to 3D;

Fig. 4 explains the position angle in gamut is measured and the synoptic diagram of polar angle;

Fig. 5 A is the schematic cross-section of typical traditional liquid crystal indicator, and Fig. 5 B is the schematic cross-section that is used for the liquid crystal cells of this liquid crystal indicator;

Fig. 6 is that polar angle is 60 ° and the position angle changes to 360 ° XY chromatic diagram from 0 in the embodiments of the invention 1;

Fig. 7 is that polar angle is 60 ° and the position angle changes to 360 ° XY chromatic diagram from 0 in the embodiments of the invention 2;

Fig. 8 is that polar angle is 60 ° and the position angle changes to 360 ° XY chromatic diagram from 0 in the embodiments of the invention 3;

Fig. 9 is that polar angle is 60 ° and the position angle changes to 360 ° XY chromatic diagram from 0 in the embodiments of the invention 4;

Figure 10 is that polar angle is 60 ° and the position angle changes to 360 ° XY chromatic diagram from 0 in the comparing embodiment 1 of the present invention;

Figure 11 is that polar angle is 60 ° and the position angle changes to 360 ° XY chromatic diagram from 0 in the comparing embodiment 2 of the present invention;

Figure 12 is that polar angle is 60 ° and the position angle changes to 360 ° XY chromatic diagram from 0 in the comparing embodiment 3 of the present invention.

Embodiment

(definition of term and symbol)

The term in the instructions of the present invention and the definition of symbol are described below.

(1) symbol " nx " refers to direction that refractive index in the largest face is provided (that is) refractive index, slow-axis direction, symbol " ny " refers in identical face the refractive index perpendicular to the direction (that is quick shaft direction) of slow axis.Symbol " nz " refers to the refractive index of thickness direction.And for example expression formula " nx=ny " not only refers to nx and the equal fully situation of ny, also comprises the situation that nx and ny equate substantially.In instructions of the present invention, phrase " equal substantially " comprises the different situation in the scope that the whole polarization property of blooming is not exerted an influence of nx and ny in actual use.

(2) term " face in phase differential (Δ nd) " refer to 23 ℃ use down wavelength as the face of the film (layer) of the photo measure of 590nm in phase difference value.Δ nd can determine that nx and ny represent the slow-axis direction of film under the wavelength of 590nm (layer) and the refractive index of quick shaft direction respectively from equation Δ nd=(nx-ny) * d here, and d (nm) represents the thickness of film (layer).

(3) term " the phase differential Rth of thickness direction " refers at 23 ℃ and uses the phase difference value of wavelength as the thickness direction of the film (layer) of the photo measure of 590nm down.Rth can determine that nx and nz represent the slow-axis direction of film under the wavelength of 590nm (layer) and the refractive index of thickness direction respectively from equation Rth=(nx-nz) * d here, and d (nm) represents the thickness of film (layer).

A. liquid crystal panel and comprise the structure of the liquid crystal indicator of this liquid crystal panel

Fig. 1 is the schematic cross-section of the preferred implementation of explanation liquid crystal panel of the present invention.Liquid crystal panel 100 disposes successively: first transparent protective film 10, first polaroid 30, second transparent protective film 11, first birefringent layers 60, liquid crystal cells 40, second birefringent layers 70, the 3rd transparent protective film 12, second polaroid 50 and the 4th transparent protective film 13.What first transparent protective film, first polaroid, second transparent protective film and first birefringent layers can be configured in liquid crystal cells watches side or backlight side, but preferred disposition is in the side of watching of liquid crystal cells.

First birefringent layers 60 is the birefringent layers with nx＞ny=nz relation and positive single shaft character.Second birefringent layers 70 is the birefringent layers with nx 〉=ny＞nz relation.Describe first birefringent layers 60 and second birefringent layers 70 below in detail.

In Fig. 1, the laminate of first transparent protective film 10, first polaroid 30, second transparent protective film 11 and first birefringent layers 60 is preferred example of blooming of the present invention.In blooming of the present invention, second transparent protective film 11 that importantly has specific physical property is configured between first polaroid 30 and first birefringent layers 60.Therefore, can provide the blooming that is applicable to the liquid crystal indicator that colourless neutral demonstration is provided in all azimuth directions.

The slow axis of the absorption axes of first polaroid 30 and first birefringent layers 60 is perpendicular to one another substantially.

Liquid crystal cells 40 comprises: a pair of glass substrate 41 and 42 and be configured between the substrate liquid crystal layer 43 as display medium.A substrate (active-matrix substrate) 41 disposes: be used to control the on-off element (being generally TFT) of liquid crystal electrooptical characteristic and be used to this on-off element that the sweep trace of gate signal is provided and be used to this on-off element that the signal wire (line does not show) of source signal is provided.Another glass substrate (base plate of color light filter) 42 disposes the chromatic filter (not shown).Be noted that chromatic filter also can be configured on the active-matrix substrate 41.Distance between the substrate 41 and 42 (cell gap) is controlled by spacer 44.By the formed alignment film (not shown) of for example polyimide be configured in substrate 41 and 42 separately with liquid crystal layer 43 contacted sides.

As long as can obtain effect of the present invention, any suitable drive pattern can be used for the drive pattern of liquid crystal cells 40.The object lesson of drive pattern comprises STN (super-twist nematic) pattern, TN (twisted nematic) pattern, IPS (switching in the face) pattern, VA (vertical orientation) pattern, OCB (optics orientation birefringence) pattern, HAN (mixed orientation is to row) pattern and ASM (rotational symmetry orientation micella) pattern.Since its obvious improvement to gamut, preferred VA pattern and ocb mode.

Each has illustrated the schematic cross-section of liquid crystal alignment state in the VA pattern naturally Fig. 2 A and 2B.Shown in Fig. 2 A, do not applying under the voltage condition, liquid crystal molecule is perpendicular to substrate 41 and 42 orientations.This vertical orientation can form by the nematic crystal with negative dielectric anisotropic is disposed between the substrate that is formed with vertical orientation film (not shown) thereon separately.Light enters from a surface that is in the substrate 41 such state, is allowed to by second polaroid 50 and linearly polarized photon vertically the advancing along the vertical orientation liquid crystal molecule that enter liquid crystal layer 43.The birefringence that vertically do not have at liquid crystal molecule takes place, so the incident light Shi Buhui that advances changes the polarization direction, and first polaroid 30 that is had perpendicular to the polarizing axis of second polaroid 50 absorbs.Like this, do not applying under the voltage condition, obtaining showing slinkingly and show (normal black mode).Shown in Fig. 2 B, when applying between the electrode under the voltage condition, the major axis of liquid crystal molecule is parallel to the substrate surface orientation.Liquid crystal molecule demonstrates birefringence with respect to the linearly polarized photon that enters the liquid crystal layer 43 that is in such state, and the polarization of incident light state changes according to the inclination angle of liquid crystal molecule.For example, applying under the situation of predetermined maximum voltage, the polarisation of light direction that is allowed to pass through liquid crystal layer has been rotated 90 ° becomes linearly polarized photon, passes first polaroid 30 then, thereby bright demonstration is provided.Turn back to and do not apply under the voltage condition, provide once more to show slinkingly by the orientation control and show.Change and apply the inclination angle of voltage with the control liquid crystal molecule.Therefore, can change from the transmission light intensity of first polaroid 30, thereby classification display is provided.

Each has illustrated the schematic cross-section of liquid crystal alignment state in the ocb mode to Fig. 3 A naturally to 3D.Ocb mode refers to the drive pattern that liquid crystal layer 43 wherein constitutes by so-called crooked orientation.Shown in Fig. 3 C, crooked orientation refers to such orientation state, wherein: the nematic crystal molecule near substrate with substantially parallel angle (orientation angle) orientation; The orientation angle forms vertical angle at the liquid crystal layer center with respect to base plan; Along with the center away from liquid crystal layer, orientation is contended gradually to change into continuously and is parallel to the opposing substrates surface; On whole liquid crystal layer, there is not distorted-structure.The following formation of crooked orientation like this.As shown in Figure 3A, liquid crystal molecule is in the basic down evenly orientation of the state that does not apply electric field (original state).Yet liquid crystal molecule has tilt angle separately, and near the tilt angle the substrate is different with near the tilt angle the opposing substrates.Apply predetermined bias voltage (being generally 1.5V) (low-voltage applies) to 1.9V, liquid crystal molecule experience shown in Fig. 3 B injection orientation (spray alignment) and be transformed into crooked orientation shown in Fig. 3 C.Subsequently, shown in Fig. 3 D, apply display voltage (being generally 5V to 7V) (high voltage applies), the liquid crystal molecule in the crooked orientation state is basically perpendicular to the substrate surface orientation.In normal white display mode, be allowed under the situation that does not change the polarization direction, advance by second polaroid 50 and the light that enters at the liquid crystal layer that applies the state shown in Fig. 3 D that is under the high-tension situation, and absorbed by first polaroid 30, show thereby provide to show slinkingly.Reduce display voltage, the orientation control by friction treatment makes liquid crystal molecule be returned to case of bending, thereby bright demonstration is provided once more.Control the inclination angle of liquid crystal molecule by changing display voltage.Therefore, can change from the transmission light intensity of polaroid, thereby classification display is provided.The liquid crystal indicator that disposes the ocb mode liquid crystal unit allows to switch to the transformation mutually of crooked orientation state from spraying the orientation state with very high speed, has excellent animation display characteristic thereby compare with those liquid crystal indicators of liquid crystal cells that dispose other drive pattern of TN pattern for example or IPS pattern.

The display mode of the liquid crystal cells of ocb mode can be: applying the normal black mode that shows the normal white pattern of dark state (black display) under the high-tension situation or applying the bright state of demonstration (white shows) under the high-tension situation.

The cell gap of the liquid crystal cells of preferred ocb mode be 2 μ m to 10 μ m, more preferably 3 μ m are to 9 μ m, preferred especially 4 μ m are to 8 μ m.Cell gap is in and can reduces the response time in the above-mentioned scope and good display performance is provided.

The nematic crystal that is preferred for the liquid crystal cells of ocb mode has positive dielectric anisotropy.Object lesson with nematic crystal of positive dielectric anisotropy comprises those that describe among the JP 09-176645A.And commercially available nematic crystal also can use according to its former state.The example of commercially available nematic crystal comprises " ZLI-4535 " and " ZLI-1132 " (trade name, Japanese Merck company makes).Difference between ordinary refraction index of nematic crystal (no) and the extraordinary ray refractive index (ne), that is, and birefraction (Δ n _LC) can suitably set according to response speed of liquid crystal, transmissivity etc.Yet preferred birefraction is 0.05 to 0.30, more preferably 0.10 to 0.30, further preferred 0.12 to 0.30.The tilt angle that such nematic crystal has separately is preferably 1 ° to 10 °, and more preferably 2 ° to 8 °, preferred especially 3 ° to 6 °.Tilt angle is in and can reduces the response time in the above-mentioned scope and good display performance is provided.

Aforesaid liquid crystal panel goes for liquid crystal indicator, for example personal computer, LCD TV, portable phone or PDA(Personal Digital Assistant) or projector.

B. polaroid

Polaroid of the present invention (first polaroid 30, second polaroid 50) forms by polyvinyl alcohol resin.Polaroid of the present invention is preferably preparation in the following manner all: how pure resin film with dichroic substance (being typically iodine or dichroic dye) dyeing, is carried out uniaxial tension to dyeing resin then.The degree of polymerization that is used to form the polyvinyl alcohol resin of polyvinyl alcohol resin film is preferably 100 to 5,000, and more preferably 1,400 to 4,000.The polyvinyl alcohol resin film that is used to form polaroid can form (for example wherein being used for forming by curtain coating The tape casting, casting method or the extrusion molding of film in water or organic solvent by the solution that resin dissolves is prepared) by the method for any appropriate.The thickness of polaroid can suitably be set according to the purpose of liquid crystal indicator that will use or image display device or purposes, but preferred 5 to 80 μ m.

The preparation method of polaroid comprises the production run that makes polyvinyl alcohol resin film experience comprise staining procedure, cross-linking step, stretching step, cleaning step and drying steps.In each step except that drying steps, each processing all is to be undertaken by polyvinyl alcohol resin being immersed in the bath that contains the solution that will be used for each step.The enforcement of the order of staining procedure, cross-linking step, stretching step, cleaning step and drying steps, quantity and processing and omission all can suitably be set according to purpose, employed material, condition etc.For example, several processing can be carried out in a step simultaneously, perhaps can omit specific processing.Specifically, for example stretch processing can be after dyeing be handled, before or dyeing handle and the process of crosslinking Treatment in carry out.In addition, for example the dyeing processing was preferably carried out before or after stretch processing.And cleaning treatment can all be carried out after various processing, perhaps carries out after particular procedure.Particularly preferably be, staining procedure, cross-linking step, stretching step, cleaning step and drying steps preferably carry out successively.And as preferred pattern, the swelling step can be carried out before staining procedure.

(swelling step)

The swelling step refers to the step with polyvinyl alcohol resin film swelling.Typically, the swelling step is undertaken by the polyvinyl alcohol resin film being immersed in the water-filled processing bath (swelling bath).This processing is washed off the pollutant on polyvinyl alcohol resin film surface or detackifier, and by making polyvinyl alcohol resin film swelling prevent the inhomogeneous of uneven dyeing and so on for example.Can suitably in bathing, swelling add glycerine or potassium iodide.Preferred 20 to 60 ℃ of the temperature that swelling is bathed, more preferably 20 to 50 ℃.Preferred 0.1 to 10 minute of Immersion time during swelling is bathed, more preferably 1 to 7 minute.Note, the polyvinyl alcohol resin film can be in staining procedure as described below swelling, thereby can omit the swelling step.

When film is pulled out from swelling is bathed, can use the roller (for example pinch roll) that prevents the liquid drippage of any appropriate to fall as required, or unnecessary water be removed by the method for removing liquid with air knife etc. to prevent fluid drips.

(staining procedure)

Staining procedure is usually by carrying out polyvinyl alcohol resin film submergence (being also referred to as absorption or contact) in the processing bath (dye bath) that contains the dichroic substance of iodine and so on for example.Water is usually with the solvent that acts on dye bath solution, but can also add an amount of and organic solvent water compatible.As 100 weight portions, the usage ratio of dichroic substance is preferably 0.01 to 10 weight portion with solvent, more preferably 0.02 to 7 weight portion, further preferred 0.025 to 5 weight portion.

The material that is applicable to any appropriate of the present invention can be used as dichroic substance, and this examples of substances comprises iodine and organic dyestuff.The example of organic dyestuff comprises red BR, red LR, red R, pink LB, pinkish red BL, purplish red GS, sky blue LG, lemon yellow, blue BR, blue 2R, dark blue RY, green LG, violet LB, violet B, black H, black B, black GSP, yellow 3G, yellow R, orange LR, orange 3R, dark red GL, dark red KGL, Congo red, blue G, the Supra orange of brilliant violet BK, Supra GL, direct sky blue, directly everbright fast orange S (Direct Fast Orange S) and sun-proof are deceived (Fast Black).

In staining procedure, can use one type dichroic substance, perhaps be used in combination the dichroic substance of two or more types.Using under the situation of organic dyestuff (neutralization) visible region of for example preferably using the dichroic substance of two or more types to neutralize.The object lesson of this combination comprises: blue G, Supra orange GL of Congo red and Supra and direct sky blue and direct sky blue and sun-proof are black.

Using under the situation of iodine as dichroic substance, the solution of dye bath preferably further contains the auxiliary agent of iodide for example to improve dyeing efficient.The object lesson of iodide comprises potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide and titanium iodide.Wherein, preferred potassium iodide.As 100 weight portions, the usage ratio of auxiliary agent is preferably 0.02 to 20 weight portion with solvent, more preferably 0.01 to 10 weight portion, further preferred 0.1 to 5 weight portion.The ratio (weight ratio) of iodine and auxiliary agent (preferred potassium iodide) is preferably 1: 5 to 1: 100, and more preferably 1: 6 to 1: 80, further preferred 1: 7 to 1: 70.

The temperature of dye bath is preferably 5 to 70 ℃, and more preferably 5 to 42 ℃, further preferred 10 to 35 ℃.Immersion time in the dye bath is preferably 1 to 20 minute, more preferably 2 to 10 minutes.

In staining procedure, film can stretch in dye bath.At this moment, total accumulation draw ratio is preferably 1.1 to 4.0 times.

Except above-mentioned comprising resin molding being immersed in the method in the dye bath, the dyeing in the staining procedure is handled and can be adopted the aqueous solution that will contain dichroic substance to apply or be injected in method on the polyvinyl alcohol resin film.And dichroic substance formerly is blended in the film in the film forming procedure in the step.In this case, previous step and staining procedure can carry out simultaneously.

When film is pulled out from dye bath, can use the roller (for example pinch roll) that prevents liquid drippage of any appropriate to fall as required, or unnecessary water be removed by the method for removing liquid with air knife etc. to prevent fluid drips.

(cross-linking step)

The polyvinyl alcohol resin film that cross-linking step will be handled by living through dyeing usually is immersed in the processing bath (crosslinked bath) that contains crosslinking chemical and carries out.Suitable crosslinking chemical can be used as crosslinking chemical arbitrarily.The object lesson of crosslinking chemical comprises boron compound, glyoxal and the glutaraldehyde of boric acid for example or borax.The crosslinking chemical of type can be used alone, perhaps multiple crosslinking chemical can be used in combination.Under the situation of the crosslinking chemical that is used in combination two or more types, for example, the combination of preferred boric acid and borax.The ratio of this combination (mol ratio) is preferably 4: 6 to 9: 1, and more preferably 5.5: 4.5 to 7: 3, further preferred 5.5: 4.5 to 6.5: 3.5.

Usually make water as the solvent that is used for crosslinked bath solution, but can also add the organic solvent of an amount of and water compatible.As 100 weight portions, the usage ratio of crosslinking chemical typically is 1 to 10 weight portion with solvent.When the concentration of crosslinking chemical is lower than 1 weight portion, can't provide enough optical characteristics.When the concentration of crosslinking chemical surpasses 10 weight portions, in drawing process, can increase the tensile force on the film and the Polarizer of acquisition is shunk, for example.

The solution of crosslinked bath preferably further contain comprise potassium iodide as the auxiliary agent of basis so that the uniform properties in the membrane plane to be provided.The concentration of auxiliary agent is preferably 0.05 to 15wt%, more preferably 0.1 arrives 10wt%, further preferred 0.5 arrives 8wt%.Except potassium iodide, the example of auxiliary agent comprises lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide and titanium iodide.Can use one type auxiliary agent, perhaps can be used in combination the auxiliary agent of two or more types.

The temperature of crosslinked bath is preferably 20 to 70 ℃, more preferably 40 to 60 ℃.Immersion time in the crosslinked bath is preferably 1 second to 15 minutes, more preferably 5 seconds to 10 minutes.

Be similar to staining procedure, cross-linking step can adopt the solution that will contain crosslinking chemical to apply or be injected in method on the film.In cross-linking step, film can stretch in crosslinked bath.At this moment, total accumulation draw ratio is preferably 1.1 to 4.0 times.

When film is pulled out from crosslinked bath, can use the roller (for example pinch roll) that prevents liquid drippage of any appropriate to fall as required, or unnecessary water be removed by the method for removing liquid with air knife etc. to prevent fluid drips.

(stretching step)

Stretching step refers to the step of stretching polyethylene alcohol resin film.Stretching step can be carried out in aforesaid polaroid preparation method's any stage.Specifically, stretching step can be after dyeing be handled or before, in the process of swelling treatment, dyeing processing or crosslinking Treatment, or after crosslinking Treatment, carry out.

The accumulation total drawing ratio of polyvinyl alcohol resin film is preferably 2 to 7 times, and more preferably 5 to 7 times, further preferred 5 to 6.5 times.The accumulation total drawing ratio is lower than 2 times of Polarizers that may cause being difficult to obtain to have high-polarization.The accumulation total drawing ratio is higher than 7 times and may causes polyvinyl alcohol resin film (polaroid) to be torn easily.The thickness of the film after the stretching is preferably 3 to 75 μ m, more preferably 5 to 50 μ m.

Can adopt suitable arbitrarily method as concrete drawing process.Its example comprises: the wet method pulling method, and wherein the polyvinyl alcohol resin film stretches in the aqueous solution of heat; And the dry method tension method, wherein moisture polyvinyl alcohol resin film stretches in air.Under the situation that adopts the wet method pulling method, the polyvinyl alcohol resin film is stretched to predefined ratio in handling bath (stretch bath).

Employed stretch bath solution is preferably such solution: it contains potassium iodide as basis in the solvent of for example water or organic solvent (for example, ethanol).Solution can contain the compound of a type or two or more types, except potassium iodide, this compound is selected from different metal salt, boron or zinc compound, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide and titanium iodide.Wherein, preferably contain boric acid.The concentration of potassium iodide is preferably 0.05 to 15wt%, more preferably 0.1 arrives 10wt%, further preferred 0.5 arrives 8wt%.Under the situation that boric acid and potassium iodide are used in combination, the ratio of this combination (weight ratio) is preferably 1: 0.1 to 1: 4, more preferably 1: 0.5 to 1: 3.

The temperature of stretch bath is preferably 30 to 70 ℃, and more preferably 40 to 67 ℃, further preferred 50 to 62 ℃.The dry method tension method is preferably carried out under 50 to 180 ℃.

When film is pulled out from stretch bath, can use the roller (for example pinch roll) that prevents liquid drippage of any appropriate to fall as required, or unnecessary water be removed by the method for removing liquid with air knife etc. to prevent fluid drips.

(cleaning step)

Cleaning step carries out through various processing by the polyvinyl alcohol resin film being immersed in handle to bathe in (washing is bathed).Cleaning step makes that unwanted residue is washed off on the polyvinyl alcohol resin film.Cleaner bath contains and comprises the aqueous solution of potassium iodide as basis.Aqueous solution can contain the compound of a type or two or more types, and except that potassium iodide, this compound is selected from lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide and titanium iodide.The concentration of potassium iodide is preferably 0.05 to 15wt%, more preferably 0.1 to 10wt%, further preferred 3 arrives 8wt%, preferred especially 0.5 to 8wt%.The iodide aqueous solution can add the auxiliary agent of zinc sulfate for example or zinc chloride and so on.

The temperature of cleaner bath is preferably 10 to 60 ℃, and more preferably 15 to 40 ℃, further preferred 30 to 40 ℃.Immersion time in the cleaner bath is preferably 1 second to 1 minute.Cleaning step can only carry out once as required, perhaps can carry out several.Carry out under the situation type and the concentration that can suitably regulate the adjuvant of the cleaner bath that is used for handling each time for several times at cleaning step.For example, cleaning step comprises: polymer film is immersed in the potassium iodide aqueous solution (0.1 to 10wt%, 10 to 60 ℃) 1 second to 1 minute step; And the step of cleaning this polymer film with pure water.

When film is pulled out from cleaner bath, can use the roller (for example pinch roll) that prevents liquid drippage of any appropriate to fall as required, or unnecessary water be removed by the method for removing liquid with air knife etc. to prevent fluid drips.

(drying steps)

Suitable drying means (for example air dry, air-dry or heat drying) can be used for drying steps arbitrarily.The preferred heat drying that adopts.When heat drying, baking temperature is preferably 20 to 80 ℃, and more preferably 20 to 60 ℃, further preferred 20 to 45 ℃.Preferred 1 to 10 minute of drying time.Obtain polaroid as mentioned above.

C. transparent protective film

As mentioned above, first transparent protective film (first transparent protective film 10 among Fig. 1) can be configured in a side that does not dispose first birefringent layers 60 on first polaroid 30.Second transparent protective film (second transparent protective film 11 among Fig. 1) can be configured in a side (being between first polaroid 30 and first birefringent layers 60) that disposes first birefringent layers 60 on first polaroid 30.And, as shown in Figure 1, comprise at liquid crystal panel of the present invention under the situation of second polaroid 50 that transparent protective film (the 3rd transparent protective film 12 among Fig. 1 or the 4th transparent protective film 13) can be configured at least one side of second polaroid 50.Thereby dispose this transparent protective film and prevent the polaroid deterioration.

As the preference pattern of the laminate of first polaroid or second polaroid and transparent protective film, first polaroid or second polaroid adhere on the transparent protective film by bonding coat.

Preferred bonding coat is formed by the polyvinyl alcohol bonding agent.The polyvinyl alcohol bonding agent contains polyvinyl alcohol resin and crosslinking chemical.

The example of above-mentioned polyvinyl alcohol resin includes but not limited to: by the polyvinyl alcohol (PVA) that the polyvinyl acetate saponification is obtained; Its derivant; By making vinyl acetate and having the saponification resultant of the multipolymer that the monomer copolymerization with the ability of vinyl acetate copolymerization obtains; And modified polyvinylalcohol by polyvinyl alcohol modification being become acetal, urethanes, ether, grafting (graft) or phosphate (phosphate) obtain.The example of monomer comprises: maleic acid (acid anhydride), fumaric acid, crotonic acid, itaconic acid and for example (methyl) acrylic acid unsaturated carboxylic acid and ester thereof; Alpha-olefin, for example ethene and propylene; (methyl) allyl sulphonic acid (sodium); Sodium sulfonate monoalkyl malate (sodium sulfonate (mono alkylmalate)); Sodium disulfonate alkyl malate (sodium disulfonate alkylmalate); N hydroxymethyl acrylamide; The alkali metal salt of acrylamide alkyl sulfonic acids; The N-vinyl pyrrolidone; And the derivant of N-vinyl pyrrolidone.Polyvinyl alcohol resin can use separately, and perhaps two or more are used in combination.

Consider that from the angle of adhesion characteristic the average degree of polymerization of polyvinyl alcohol resin is preferably 100 to 3,000, more preferably 500 to 3,000, and average saponification degree is 85 to 100mol%, more preferably 90 to 100mol%.

Polyvinyl alcohol resin with acetoacetyl can be used as above-mentioned polyvinyl alcohol resin.Polyvinyl alcohol resin with acetoacetyl is the polyvinyl alcohol bonding agent with high response functional group, and considers that from the angle of the permanance of improving the blooming that will obtain it is preferred.

Polyvinyl alcohol resin with acetoacetyl is obtained by reaction between polyvinyl alcohol resin and the diketen by known method.The example of known method comprises: comprise polyvinyl alcohol resin is dispersed in the solvent of acetate for example, then to the method that wherein adds diketen; And comprise polyvinyl alcohol resin is dissolved in the solvent of dimethyl formamide for example or dioxane and so on, then to the method that wherein adds diketen.Another example of known method is to comprise the method that diketen gas or liquid diketen are contacted with polyvinyl alcohol (PVA).

As long as more than or equal to 0.1mol%, the acetoacetyl modification degree with polyvinyl alcohol resin of acetoacetyl is not particularly limited.Acetoacetyl modification degree is during less than 0.1mol%, and the water proofing property of the bonding coat that is provided is not enough, is inappropriate therefore.Acetoacetyl modification degree is preferably 0.1 to 40mol%, more preferably 1 arrives 20mol%.Acetoacetyl modification degree surpasses 40mol% can reduce reflecting point with crosslinking chemical, and the water proofing property that is given to improve effect faint.Acetoacetyl modification degree is the value of measuring by NMR.

The crosslinking chemical that is used for the polyvinyl alcohol bonding agent can use and be not particularly limited.

Have at least two compounds that have separately with reactive functional group of polyvinyl alcohol resin and can be used as crosslinking chemical.The example of this compound comprises: have the alkylene diamines of alkylene and two amino, for example ethylenediamine, triethylenediamine and hexane diamine (wherein, preferred hexane diamine); Isocyanates, for example toluene diisocyanate of toluene diisocyanate, hydrogenation, trimethylene propane toluene diisocyanate adduct, triphenylmethane triisocyanate, di-2-ethylhexylphosphine oxide (4-phenylmethane) triisocyanate, isophorone diisocyanate or its ketoxime block compound or phenol block compound; Epoxide, for example ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol, polyglycol diglycidyl ether, glycerol diglycidyl ether or glycerine three Synthesis of Oligo Ethylene Glycol, 1,6-hexanediol diglycidyl ether, trimethylolpropane tris Synthesis of Oligo Ethylene Glycol, 2-glycidyl aniline and 2-glycidyl amine; Single aldehyde, for example formaldehyde, acetaldehyde, propionic aldehyde and butyraldehyde; Dialdehyde, for example glyoxal, MDA, butanedial, glutaraldehyde, malealdehyde and phthalaldehyde; Amino/formaldehyde resin, for example condensation product of formaldehyde and methylolurea, methylol melamine, alkylating methylolurea, alkylating methylol melamine, acetylguanamine or benzoguanamine; And the salt of divalent metal or trivalent metal, for example sodium, potassium, magnesium, calcium, aluminium, iron, nickel and oxide thereof.Preferred melamine class crosslinking chemical is as crosslinking chemical, preferred especially methylol melamine.

As 100 weight portions, the combined amount of preferred crosslinking chemical is 0.1 to 35 weight portion, more preferably 10 to 25 weight portions with polyvinyl alcohol resin.Simultaneously, in order to improve permanance, as 100 weight portions, the blend range of crosslinking chemical can and be less than 46 weight portions more than 30 weight portions with polyvinyl alcohol resin.Particularly, have in use under the situation of polyvinyl alcohol resin of acetoacetyl, the use amount of preferred crosslinking chemical is more than 30 weight portions.The crosslinking chemical blend range can and be less than 46 weight portions more than 30 weight portions, thereby improves water resistance.

Notice that above-mentioned polyvinyl alcohol bonding agent can further contain: coupling agent, for example silane coupling agent or titanium coupling agent; Various tackifier; Ultraviolet light absorber; Antioxidant; And stabilizing agent, for example heat-resisting stabilizing agent or stabilizer against hydrolysis.

Can carry out easily sticking the processing with first polaroid 30 or second polaroid, 50 contacted surfaces to improve bond property.This easily sticking example of handling comprises corona treatment, plasma treatment, the surface treatment that the low pressure ultraviolet is handled, for example saponification is handled and the method that forms back-up coat (anchorlayer), and these processing can be used in combination.Wherein, corona treatment, form the method for back-up coat and with corona treatment with to form the method that the method for back-up coat combines be preferred.

The example of back-up coat is the silicone layer with reactive functional groups.Material with silicone layer of reactive functional groups is not particularly limited.But its example comprises: the alkoxyl silicone alkanol that contains the isocyanates group; Contain amino alkoxyl silicone alkanol; The alkoxyl silicone alkanol that contains sulfydryl; The alkoxyl silicone alkanol that contains carboxyl; The alkoxyl silicone alkanol that contains epoxy radicals; The alkoxyl silicone alkanol that contains the unsaturated ethylene thiazolinyl; The alkoxyl silicone alkanol that contains halogen group; And the alkoxyl silicone alkanol that contains the isocyanates group.Preferred amino eka-silicon alkanol.Can add titanium class catalyzer or tin class catalyzer with effectively with silanol reaction, thereby enhancing adhesive strength.Polysiloxane with reactive functional groups can contain other adjuvant of adding.Its operable object lesson comprises: the tackifier that formed by terpene resin (terpene resin), phenol resin (phenolresion), terpene/phenol resin, abietic resin, xylene resin etc.; Ultraviolet light absorber; Antioxidant; And the stabilizing agent of heat-resisting stabilizing agent for example.

Silicone layer with reactive functional groups applies by known method and dry formation.The thickness of dried silicone layer preferably 1 arrives 100nm, more preferably 10 arrives 50nm.For applying, the polysiloxane with reactive functional groups can be used solvent dilution.Diluting solvent is not particularly limited, but its example comprises alcohols.Dilute concentration is not particularly limited, but preferred 1 to 5wt%, more preferably 1 arrive 3wt%.

Bonding coat is preferably by being coated to bonding agent transparent protective film on the adhesive surface of polaroid, is coated to polaroid on the adhesive surface of transparent protective film or be coated on the adhesive surface of polaroid and transparent protective film and form.After polaroid and transparent protective film adhere to each other, it is wholely formed by the bonding coat that applies and dry layer forms through drying steps.Bonding coat can form subsequently and adhere to.Adhesion can use roll-type laminating machine or similar devices to carry out.Can suitably determine heat drying temperature and drying time according to the type of bonding agent.

The thickness of bonding coat is preferably 0.01 to 10 μ m, and more preferably 0.03 to 5 μ m is because consider that from the angle of adhesion characteristic not preferred dried thickness is excessive.

Can use suitable arbitrarily diaphragm as transparent protective film.The examples of material of forming transparent protective film comprises having for example thermoplastic resin of the excellent properties of transparency, physical strength, thermal stability, water resistance, isotropy etc.The object lesson of this thermoplastic resin comprises: the celluosic resin of triacetyl cellulose (TAC) for example; Vibrin; Polyethersulfone resin; Polysulfone resin; Polycarbonate resin; Polyamide; Polyimide resin; Polyolefin resin; Acryl resin; The polynorbornene resin; Celluosic resin; The poly-allylat resin; Polystyrene resin; Polyvinyl alcohol resin; Polyacrylic resin; And composition thereof.In addition, can use acrylic compounds, urethanes class, urethane acrylate class, epoxies or polysiloxane-based etc. thermoset resin or ultraviolet curable resin.Consider polarization characteristic and persistence, preferred cellulose class film (for example the TAC film that saponification is handled was carried out with alkali etc. in the surface) or norborene class film (for example polynorbornene resin molding).

And for example, the polymer film that is formed by the disclosed resin combination of JP 2001-343529A (WO 01/37007) can be used as diaphragm.Specifically, this resin combination refers to the potpourri of following material: have the thermoplastic resin that has substituted-phenyl or non-substituted-phenyl and cyano group on the thermoplastic resin of substituted imides base or non-substituted imides base and the side chain on the side chain.Its object lesson is the resin combination that contains following material: the alternating copolymer of isobutylene and N-methylene maleimide; And vinyl cyanide/styrol copolymer.For example, can use the extrusion molding product of such resin combination.

Shown in its title, transparent protective film is transparent, and preferably colourless.Specifically, the phase differential Rth of transparency protected film thickness direction is preferably-90nm is to+75nm, more preferably-80nm is to+60nm, and most preferably-70nm is to+45nm.The phase differential Rth of transparency protected film thickness direction can eliminate the optical clouration of the polaroid that is caused by transparent protective film in above-mentioned scope.

The thickness of transparent protective film can suitably be set according to purpose.The thickness of transparent protective film is less than or equal to 500 μ m usually, preferred 5 to 300 μ m, more preferably 5 to 150 μ m.

The phase differential of the second transparency protected film thickness direction (Rth) is by relational expression (1) expression, and it is less than or equal to 10nm, preferably is less than or equal to 6nm, is more preferably less than or equals 3nm.The lower limit of the phase differential of thickness direction (Rth) is preferably greater than or equals 0nm, and the phase differential of thickness direction is preferably greater than 0nm.

Rth＝(nx-nz)×d …(1)

In liquid crystal panel of the present invention and liquid crystal indicator; second transparent protective film that the phase differential of thickness direction (Rth) is very little can be configured between first polaroid and the specific birefringent layers as mentioned above, thereby each self-supporting with excellent viewing angle compensation is provided and has excellent oblique contrast and the liquid crystal panel and the liquid crystal indicator of little oblique gamut.

In the present invention, phase differential (Δ nd) is by relational expression (2) expression in the face of second transparent protective film, and it preferably is less than or equal to 2nm, is more preferably less than or equals 1nm.The lower limit of the interior phase differential (Δ nd) of face is preferably greater than or equals 0nm, and phase differential (Δ nd) preferably surpasses 0nm in the face.

Δnd＝(nx-ny)×d …(2)

In liquid crystal panel of the present invention and liquid crystal indicator; the second very little transparent protective film of phase differential (Δ nd) can be configured between first polaroid and the specific birefringent layers in the face as mentioned above, thereby each self-supporting with excellent viewing angle compensation is provided and has excellent oblique contrast and the liquid crystal panel and the liquid crystal indicator of little oblique gamut.

Suitable arbitrarily material can be as the material of second transparent protective film, and its example comprises cellulose material and norborene class material.The preferred example of cellulose material is the cellulosic polymer that fatty acid replaces, for example diacetyl cellulose or triacetyl cellulose.

For example the thickness that is generally used for transparent protective film of tri acetyl cellulose membrane is that the phase differential (Rth) of thickness direction of the cellulose family film of 40 μ m is about 40nm.Therefore, second transparent protective film of the present invention can not adopt the cellulose family film with aforesaid big thickness direction phase differential (Rth) according to its former state.In the present invention, the cellulose family film with big thickness direction phase differential (Rth) is handled so that the phase differential of thickness direction (Rth) reduces through suitable, thereby second transparent protective film of the present invention preferably is provided.

Can adopt suitable arbitrarily disposal route as the processing that thickness direction phase differential (Rth) is reduced.Its example comprises: comprise that the substrate that is formed by polyethylene terephthalate, polypropylene, stainless steel etc. that will be coated with the solvent of cyclopentanone for example or methyl ethyl ketone and so on it adheres on the common cellulose family film, whole heat drying (for example, about 80 to 150 ℃ about 3 to 10 minutes down), peel off the method for substrate film then; And comprise and to be coated on the common cellulose family film by the solution for preparing in the solvent that norbornene resin, acryl resin etc. is dissolved in cyclopentanone for example or methyl ethyl ketone and so on, whole heat drying (for example, about 80 to 150 ℃ about 3 to 10 minutes down), peel off the method for coated film then.

The cellulosic polymer that fatty acid that the fatty acid degree of substitution can be regulated replaces can be with the material that acts on second transparent protective film.The acetic acid substituted degree of triacetyl cellulose commonly used is about 2.8.But preferred acetic acid substituted degree is controlled at 1.8 to 2.7, and more preferably the propionic acid degree of substitution is controlled at 0.1 to 1, thereby makes the phase differential (Rth) of thickness direction be controlled as little value.

For example the plastifier of dibutyl phthalate, tolysulfonyl aniline or acetyl triethyl citrate can join the cellulosic polymer that fatty acid replaces, thereby makes the phase differential (Rth) of thickness direction be controlled as little value.The cellulosic polymer that fatty acid is replaced is as 100 weight portions, and the addition of plastifier preferably is less than or equal to 40 weight portions, more preferably 1 to 20 weight portion, further preferred 1 to 15 weight portion.

The method that the above-mentioned phase differential (Rth) that makes thickness direction is reduced to little value can suitably be used in combination.

The preferred object lesson of another of second transparent protective film is an acrylic resin film.The preferred example of acrylic resin film has the glutaric anhydride unit of representing with following structural (1) and the acryl resin of describing (A) acrylic resin film as principal ingredient for containing in JP 2005-314534 A.Acryl resin (A) with glutaric anhydride unit of representing with following structural (1) can have improved thermotolerance.In following structural (1), R ¹And R ²Can be mutually the same or different, and represent hydrogen atom separately or have the alkyl of 1 to 5 carbon atom, more preferably hydrogen atom or methyl, further preferable methyl.

In acryl resin (A), be preferably 20 to 40wt% with the ratio of the glutaric anhydride unit of structural formula (1) expression, more preferably 25 to 35wt%.

Except the glutaric anhydride unit with structural formula (1) expression, acryl resin (A) can also contain the monomeric unit that is fit to of one or both or more kinds of types.The preferred example of monomeric unit is vinylcarboxylic acid Arrcostab unit.In acryl resin (A), the ratio of vinylcarboxylic acid Arrcostab unit is preferably 60 to 80wt%, more preferably 65 arrives 75wt%.

The example of vinylcarboxylic acid Arrcostab unit is the unit with following general formula (2) expression.In following general formula (2): R ³Expression hydrogen atom or have the aliphatic hydrocarbon or the alicyclic hydrocarbon of 1 to 5 carbon atom; R ⁴Expression has the aliphatic hydrocarbon of 1 to 5 carbon atom.

The weight-average molecular weight of preferred acrylic resins (A) is 80,000 to 150,000.

The ratio of preferred acrylic resins (A) in acrylic resin film is 60 to 90wt%.

Except acryl resin (A), acrylic resin film can contain the composition that is fit to of one or both or more kinds of types.The composition that is fit to can use in not retraining purpose scope of the present invention arbitrarily.Except acryl resin (A), the example of the composition that is fit to comprises ultraviolet light absorber, antioxidant, lubricant, plastifier, detackifier, color stabilizer, fire retardant, nucleator, antistatic agent, pigment and colorant.

In order to keep film strength and control thickness direction phase differential (Rth) for little value, the thickness of second transparent protective film is preferably 1 to 500 μ m, more preferably 5 to 200 μ m, further preferred 20 to 200 μ m, preferred especially 30 to 100 μ m, most preferably 35 to 95 μ m.D. the birefringent layers (first birefringent layers) that has nx＞ny=nz relation and positive single shaft character

The index distribution of first birefringent layers of the present invention is nx＞ny=nz.

First birefringent layers can be used as λ/4 plates.Phase difference nd is preferably 90 to 160nm in the face of first birefringent layers like this, more preferably 95 arrives 150nm, further preferred 95 arrives 145nm.

In the present invention, the absolute value that phrase " has positive single shaft character " and refer to the difference of phase differential (Δ nd) and thickness direction phase differential (Rth) in the face is less than or equal to 10nm, preferably is less than or equal to the situation of 8nm.

The thickness of first birefringent layers can be set at and make first birefringent layers can be suitable as λ/4 plates most.That is, thickness can be set at phase differential in the face that expection is provided.Specifically, preferred thickness is 40 to 110 μ m, more preferably 50 to 100 μ m, most preferably 60 to 90 μ m.

The absolute value of the photoelastic coefficient of the resin that contains in first birefringent layers is preferably and is less than or equal to 2 * 10 ^-11m ²/ N, more preferably 2.0 * 10 ^-13To 1.0 * 10 ^-11m ²/ N, further preferred 1.0 * 10 ^-12To 1.0 * 10 ^-11m ²/ N.The absolute value of photoelastic coefficient is in and can causes hardly in the above-mentioned scope because the variation that the differential contraction stress under heating condition causes.Therefore, first birefringent layers forms by the resin that use has the absolute value of such photoelastic coefficient, thereby effectively prevents the inhomogeneous heating of the image display device that will obtain.

The exemplary that can satisfy the resin of such photoelastic coefficient comprises cycloolefin resin and cellulosic resin.Preferred especially cycloolefin resin.Cycloolefin resin is the Essential Terms of the resin for preparing as monomer polymerization by cyclenes, and its example comprises the example that JP 1-240517 A, JP3-14882 A, JP 3-122137 A etc. describe.Its object lesson comprises: the open loop of cyclenes (being total to) polymkeric substance; The addition polymer of cyclenes; The multipolymer of the alpha-olefin of cyclenes and for example ethene or propylene and so on (typical, random copolymers); The graft modification product of its each personal unsaturated carboxylic acid or derivatives thereof modification; And hydride.The object lesson of cyclenes is the norborneol vinyl monomer.

The example of norborneol vinyl monomer comprises: norborene and its alkyl and/or alkylidene substituent, for example 5-methyl-2-norborene, 5-dimethyl-2-norborene, 5-ethyl-2-norborene, 5-butyl-2-norborene, 5-ethylidene-2-norborene or its derivant that is replaced by the polar group of for example halogen and so on; Bicyclopentadiene, 2,3-dihydro bicyclopentadiene etc.; The dimethylene octahydro-naphthalene, it is by the derivant of alkyl and/or alkylidene replacement, with and the derivant that replaced by the polar group of halogen and so on for example, 6-methyl isophthalic acid for example, 4:5,8-dimethylene-1,4,4a, 5,6,7,8, the 8a-octahydro-naphthalene, 6-ethyl-1,4:5,8-dimethylene-1,4,4a, 5,6,7,8, the 8a-octahydro-naphthalene, 6-ethylidene-1,4:5,8-dimethylene-1,4,4a, 5,6,7,8, the 8a-octahydro-naphthalene, 6-chloro-1,4:5,8-dimethylene-1,4,4a, 5,6,7,8, the 8a-octahydro-naphthalene, 6-cyano group-1,4:5,8-dimethylene-1,4,4a, 5,6,7,8, the 8a-octahydro-naphthalene, 6-pyridine radicals-1,4:5,8-dimethylene-1,4,4a, 5,6,7,8,8a-octahydro-naphthalene or 6-methoxycarbonyl-1,4:5,8-dimethylene-1,4,4a, 5,6,7,8, the 8a-octahydro-naphthalene; And the trimer of cyclopentadiene or tetramer, for example 4,9:5,8-dimethylene-3a, 4,4a, 5,8,8a, 9,9a-octahydro-1H-benzindene or 4,11:5,10:6,9-trimethylene-3a, 4,4a, 5,5a, 6,9,9a, 10,10a, 11,11a-ten dihydros-1H-encircles five anthracenes.

In the present invention, other cyclenes that can carry out ring-opening polymerization is used in combination in the scope that does not retrain effect of the present invention.The object lesson of such cyclenes is the compound with a reactive double bond, for example cyclopentene, cyclooctene or 5,6-dihydro cyclopentadiene.

Use toluene solvant to be preferably 25,000 to 200,000 by the number-average molecular weight (Mn) of the cycloolefin resin of gel permeation chromatography (GPC) measurement, more preferably 30,000 to 100,000, most preferably 40,000 to 80,000.Number-average molecular weight is in the physical strength that can provide excellent in the above-mentioned scope, good solubleness, mouldability and casting operability.

At cycloolefin resin is that hydrogenation ratio is preferably more than or equals 90% under the hydrogenation of the ring-opening polymerization polymer by the norborneol vinyl monomer situation about preparing, more preferably greater than or equal 95%, most preferably more than or equal to 99%.Hydrogenation ratio is in the heat-resisting degradability and the light degradation resistance that can provide excellent in the above-mentioned scope.

Various cycloolefin resin products all have commercially available.Its object lesson comprises: " ZEONEX " and " ZEONOR ", and trade name is bought from Zeon Corporation; " Arton ", trade name is bought from JSR Corporation; " Topas ", trade name is bought from Ticona; And " APEL ", trade name is bought from Mitsui Chemical Corporation.

The cellulosic resin (typical, the ester of cellulose and acid) that can adopt any appropriate is as cellulosic resin.The preferred ester that forms by cellulose and fatty acid.The object lesson of such cellulosic resin comprises cellulose triacetate (tri acetyl cellulose: TAC), cellulose diacetate, three acid celluloses and dipropionic acid cellulose.Preferred especially cellulose triacetate (tri acetyl cellulose: TAC), because it has low birefringence and high penetrability, preferred especially Triafol T (tri acetyl cellulose: TAC).Multiple commercially available TAC product is arranged, so TAC is having superiority also aspect purchase and the cost.

The object lesson of commercially available TAC product comprises: " UV-50 ", " UV-80 ", " SH-50 ", " SH-80 ", " TD-80U ", " TD-TAC " and " UZ-TAC ", and trade name is bought from Fuji Photo Film Co., Ltd.; " KC series ", trade name is bought from KonicaMinolta Holdings, Inc.; And " tri acetyl cellulose 80 μ m series ", trade name is bought from Lonza Japan.Wherein, because excellent penetrability and permanance and preferred " TD-80U "." TD-80U " has excellent especially adaptability for TFT type liquid crystal indicator.

First birefringent layers preferably obtains by the film that is formed by cycloolefin resin or cellulosic resin that stretches.Any suitable forming method can be as the method from cycloolefin resin or cellulosic resin formation film.Its object lesson comprises compression molding, transfer moudling, injection moulding, extrusion molding method, blow moulding, powdered moulding, FRP method of molding and casting method.Preferred extrusion molding and casting method are because the film that will obtain has the slickness and the good optical homogeneity of raising.Condition of moulding can suitably be set according to the estimated performance of the composition of the resin that will use or type, first birefringent layers etc.The film product of resin is commercially available in multiple cycloolefin resin and the cellulose, and these commercially available films can carry out stretch processing according to its former state.

Phase difference nd preferably controls by the draw ratio and the draft temperature that change cycloolefin resin or cellulosic resin in the face of first birefringent layers.Draw ratio can change according to the thickness of the kind of phase difference value in the expection face of first birefringent layers and thickness, the resin that will use, the film that will use, draft temperature etc.Specifically, preferred draw ratio is 1.1 to 1.6 times, more preferably 1.2 to 1.55 times, and most preferably 1.25 to 1.50 times.The stretching of carrying out with such draw ratio can provide first birefringent layers that has phase differential in the face and suitably demonstrate effect of the present invention.

Draft temperature can change according to the thickness of the kind of phase difference value in the expection face of first birefringent layers and thickness, the resin that will use, the film that will use, draw ratio etc.Specifically, preferred draft temperature is 130 to 180 ℃, more preferably 130 to 170 ℃, and preferred especially 135 to 160 ℃, most preferably 137 to 155 ℃.The stretching of carrying out with such draft temperature can provide first birefringent layers that has phase differential in the face and suitably demonstrate effect of the present invention.

E. the lamination of first birefringent layers and second transparent protective film

As preference pattern of the present invention, a side lamination has first transparent protective film 10 and the opposite side lamination has first polaroid 30 of second transparent protective film 11 to be connected to first birefringent layers 60 by pressure-sensitive adhesive layer.Shown in Figure 1 as an example, second transparent protective film 11 is in the same place by the direct lamination of contact adhesive with second birefringent layers 60.

Lamination has the surface of first birefringent layers of second protective clear layer preferably to carry out easily sticking the processing on it.Preferred easily sticking the processing undertaken by the application of resin material.The example of resin material preferably includes silicon resinoid, urethane esters resin and acryl resin.Easily adhesion coating forms by easily gluing to handle.The preferred easily thickness of adhesion coating is 5 to 100nm, more preferably 10 arrives 80nm.

Second transparent protective film passes through the direct lamination of contact adhesive on first birefringent layers.Carry out easily gluing under the situation about handling at first birefringent layers, carried out the surface of easy sticking first birefringent layers of handling and passed through the direct lamination of contact adhesive on second transparent protective film.Contact adhesive forms pressure-sensitive adhesive layer.Contact adhesive can be coated on second transparent protective film, be coated on first birefringent layers or be coated to second transparent protective film and first birefringent layers on.

The thickness of pressure-sensitive adhesive layer can suitably be set according to the purposes of expection or bond strength.Specifically, the thickness of preferred pressure-sensitive adhesive layer be 1 μ m to 100 μ m, more preferably 5 μ m are to 50 μ m, most preferably 10 μ m are to 30 μ m.

The contact adhesive that is fit to can be as the contact adhesive that forms pressure-sensitive adhesive layer arbitrarily.Its object lesson comprises solvent-borne type contact adhesive, non-water and milk formulation contact adhesive, aqueous pressure sensitive adhesive and hot melt pressure sensitive adhesive.Preferred use contain acrylate copolymer as the solvent-borne type contact adhesive of base polymer showing suitable pressure-sensitive-adhesive (wettability, cohesiveness and cohesive) with respect to second transparent protective film and first birefringent layers, and provide excellent optical clarity, against weather and thermotolerance.

F. the birefringent layers (second birefringent layers) that has nx 〉=ny＞nz relation

Second birefringent layers has nx 〉=ny＞nz relation.That is, second birefringent layers has nx=ny＞nz relation or nx＞ny＞nz relation.Second birefringent layers can be an individual layer, perhaps can be the laminate of two-layer or multilayer.In laminate, being used to form material of each layer and the thickness of each layer can suitably set, as long as laminate has above-mentioned optical property as a whole.

Have at second birefringent layers under the situation of nx=ny＞nz relation, second birefringent layers plays so-called negative electrode C plate.Particularly, second birefringent layers with such index distribution allows the birefringent good compensation of the liquid crystal layer of VA mode liquid crystal unit.As a result, can obtain the obvious improved liquid crystal indicator of viewing angle properties.As mentioned above, expression formula in instructions of the present invention " nx=ny " not only refers to nx and the equal fully situation of ny, also comprises the situation that nx and ny equate substantially.Therefore, second birefringent layers can have phase differential and slow axis in the face.In actual applications, phase difference nd is preferably 0 to 20nm in the face of allowing of negative electrode C plate, more preferably 0 arrives 10nm, further preferred 0 arrives 5nm.

The phase differential Rth of thickness direction with second birefringent layers of nx=ny＞nz relation is preferably 30 to 300nm, and more preferably 60 to 250nm, further preferred 80 to 230nm, most preferably 100 to 200nm.Provide the thickness of second birefringent layers of such thickness direction phase differential to change according to material that will use etc.For example, the thickness of second birefringent layers is preferably 1 to 50 μ m, more preferably 1 to 20 μ m, most preferably 1 to 15 μ m.The thickness of second birefringent layers that is formed separately by cholesteric orientation fixed bed as described below is preferably 1 to 10 μ m, more preferably 1 to 8 μ m, most preferably 1 to 5 μ m.Such thickness is littler than the thickness (for example, more than or equal to 60 μ m) by the biaxial stretch-formed negative electrode C plate that obtains, and greatly helps to reduce the thickness of image display device.Formation has second two-fold of very little thickness and calculates layer thickness, thereby effectively prevents uneven heating.From preventing to the minimizing of the interference of cholesteric orientation or penetrability, the viewpoint of reflecting properties, color protection, productive rate etc. optionally, preferred such optical compensating layer with very little thickness.Second birefringent layers (negative electrode C plate) is formed by the material that is fit to arbitrarily, as long as can obtain above-mentioned thickness and optical property function.The negative electrode C plate that preferred such thickness is very little forms the cholesteric orientation by the use liquid crystal material and fixes this cholesteric orientation and realize, that is to say, realize (hereinafter describing the method that is used to form the material of cholesteric orientation and fixes this cholesteric orientation in detail) by using cholesteric orientation fixed bed.

Second birefringent layers that preferably has nx=ny＞nz relation is formed for the cholesteric orientation fixed bed that is less than or equal to 350nm by the selective wavelength zone.More preferably the upper limit of selective reflecting wavelength region may is less than or equal to 320nm, most preferably is less than or equal to 300nm.Simultaneously, the lower limit of preferred selective reflecting wavelength region may is more than or equal to 100nm, more preferably greater than or equal 150nm.If optionally the reflection wavelength zone is greater than 350nm, then the selective reflecting wavelength region may covers visible-range, and therefore may cause problem for example painted or decolouring.If the selective reflecting wavelength region may is less than 100nm, and excessively increase of the amount of the chiral reagent that will use (following), so accurately control of the temperature in the optical compensating layer forming process.Therefore, almost can not produce Polarizer.

Helicity (helical pitch) in the preferred cholesteric orientation fixed bed is 0.01 to 0.25 μ m, more preferably 0.03 to 0.20 μ m, most preferably 0.05 to 0.15 μ m.For example, helicity provides sufficient orientation performance more than or equal to 0.01 μ m.Helicity is less than or equal to the rotary polarization that 0.25 μ m allows fully to be suppressed at the short wavelength side of visible light, thereby fully prevents light leak etc.Helicity can be controlled by the kind (transverse strength) and the amount of regulating chiral reagent as described below.Can the adjustable screw degree, thus control selective reflecting wavelength region may is in the scope of hope.

Perhaps, second birefringent layers with nx=ny＞nz relation can have cholesteric orientation fixed bed and the absolute value that has nx=ny＞nz relation and contain photoelastic coefficient is less than or equal to 2 * 10 ^-11m ²The laminated structure of the layer of the resin of/N (in instructions of the present invention, being also referred to as plastic membranous layer).The exemplary that can form the material (can satisfy the resin of such photoelastic coefficient) of plastic membranous layer comprises cycloolefin resin and cellulosic resin.Partly describe cycloolefin resin and cellulosic resin in detail at above-mentioned C.Cellulosic resin film (typical, the TAC film) is for having the film of nx=ny＞nz relation.

Second birefringent layers with nx=ny＞nz relation can stretch or shrink, and has nx＞ny＞second birefringent layers of nz relation thereby change into.

Having phase differential (laterally phase differential) Δ nd in the face of second birefringent layers of nx＞ny＞nz relation can optimize corresponding to the display mode of liquid crystal cells.The lower limit of Δ nd is preferably greater than or equals 5nm, more preferably greater than or equal 10nm, most preferably more than or equal to 15nm.Δ nd often provides the oblique contrast of minimizing less than 5nm.Simultaneously, the upper limit of Δ nd preferably is less than or equal to 400nm, is more preferably less than or equals 300nm, further preferably is less than or equal to 200nm, especially preferably is less than or equal to 150nm, especially preferably is less than or equal to 100nm, most preferably is less than or equal to 80nm.Δ nd often provides little visual angle greater than 400nm.Specifically, the Δ nd of VA mode liquid crystal unit is preferably 5 to 150nm, more preferably 10 arrives 100nm, most preferably 15 arrives 80nm.The Δ nd of ocb mode liquid crystal unit is preferably 5 to 400nm, more preferably 10 arrives 300nm, most preferably 15 arrives 200nm.

The phase differential Rth of thickness direction with second birefringent layers of nx＞ny＞nz relation can optimize corresponding to the display mode of liquid crystal cells.The lower limit of Rth is preferably more than or equals 10nm, more preferably greater than or equal 20nm, most preferably more than or equal to 50nm.Rth often provides the oblique contrast of minimizing less than 10nm.Simultaneously, the upper limit of Rth preferably is less than or equal to 1, and 000nm is more preferably less than or equals 500nm, further preferably is less than or equal to 400nm, especially preferably is less than or equal to 300nm, especially preferably is less than or equal to 280nm, most preferably is less than or equal to 260nm.Rth is greater than 1, and 000nm may excessively increase optical compensation, thereby reduces oblique contrast.

The Rth of preferred VA mode liquid crystal unit is 10 to 300nm, more preferably 20 arrives 280nm, most preferably 50 arrives 260nm.

The Rth of preferred ocb mode liquid crystal unit is 10 to 1, and 000nm more preferably 20 arrives 500nm, most preferably 50 arrives 400nm.

Effect of the present invention can adopt the thickness of suitable arbitrarily thickness, as long as can be provided as second birefringent layers with nx＞ny＞nz relation.Typically, thickness with second birefringent layers of nx＞ny＞nz relation is preferably 0.1 to 50 μ m, more preferably 0.5 to 30 μ m, further preferred 1 to 20 μ m shows excellent viewing angle compensation performance function and the optical compensating layer with homogeneous phase potential difference so that help to reduce the thickness of liquid crystal indicator and provide.

The material that can adopt any appropriate is as the material that forms second birefringent layers with nx=ny＞nz or nx＞ny＞nz relation, as long as can obtain above-mentioned optical property.Such examples of material is non-liquid crystal material.Its more preferred example is non-liquid crystal polymer.Non-liquid crystal material like this is different from liquid crystal material, regardless of the orientation performance of substrate, because the character that non-liquid crystal is measured can form the film with optics single shaft performance of being represented by nx＞nz or ny＞nz.As a result, not only alignment substrates can be used, non-alignment substrates can also be used.And, under the situation of using non-alignment substrates, can omit alignment film is coated to the step on non-alignment substrates surface, the step of lamination alignment film etc.

The preferred example of non-liquid crystal material comprises for example polymkeric substance of polyamide, polyimide, polyester, polyetherketone, polyamidoimide or polyester-imide and so on, because such material has chemical resistance, excellent transparency and the enough rigidity of excellent thermotolerance, excellence.Can use one type polymkeric substance, perhaps use two or more types to have the mixture of polymers of different functional groups, for example potpourri of PAEK and polyamide.Wherein, from the angle of the high grade of transparency, high orientation ability and high ductibility, preferred especially polyimide.

The molecular weight of polymkeric substance is not particularly limited.But for example, the weight-average molecular weight of polymkeric substance (Mw) is preferably 1,000 to 1,000, in 000 the scope, more preferably in 2,000 to 500,000 scope.

For example, the polyimide that has orientation ability in the high face and dissolve in organic solvent is preferably as polyimide used in the present invention.In particular, can use that JP2000-511296 A is disclosed to contain 9, the polycondensation product of two (aminoaryl) fluorenes of 9-and fragrant four carboxylic acid's dianhydride and contain at least one polymkeric substance by the represented repetitive of following structural formula (3).

In following formula (3), R ³To R ⁶Represent at least aly to be selected from hydrogen, halogen, phenyl independently, by 1 to 4 halogen atom or 1 to 4 substituting group that has the phenyl that alkyl replaced of 1 to 10 carbon atom separately and have the alkyl of 1 to 10 carbon atom.Preferred R ³To R ⁶Represent independently at least aly to be selected from halogen, phenyl, to be had the phenyl that alkyl replaced of 1 to 10 carbon atom and substituting group separately with alkyl of 1 to 10 carbon atom by 1 to 4 halogen atom or 1 to 4.

In following formula (3), for example, Z represents to have the tetravalence aryl of 6 to 20 carbon atoms, and preferably represents the derivant of equal four bases of benzene, polyaromatic, polyaromatic or by the represented group of following formula (4).

In following formula (4), Z ' expression covalent bond, C (R ⁷) ₂Base, basic, the oxygen atom of CO, sulphur atom, SO ₂Base, Si (C ₂H ₅) ₂Base or NR ⁸Base.A plurality of Z ' can be same to each other or different to each other.W represents 1 to 10 integer.R ⁷Represent hydrogen or C (R independently ⁹) ₃Base.R ⁸Expression hydrogen, have 1 to the alkyl of about 20 carbon atoms or have the aryl of 6 to 20 carbon atoms.A plurality of R ⁸Can be same to each other or different to each other.R ⁹Represent hydrogen, fluorine or chlorine independently.

The example of polyaromatic comprises the quaternary groups derived from naphthalene, fluorenes, benzofluorene or anthracene.The example of the substitutive derivative of polyaromatic comprises by at least one and is selected from alkyl with 1 to 10 carbon atom, its fluorinated derivatives and the above-mentioned polyaromatic that group replaced of the halogen of F or Cl for example.

Other example of polyimide comprises: the disclosed homopolymer that contains by the repetitive of following general formula (5) or (6) expression of JP 08-511812 A; With and the disclosed polyimide that contains by the represented repetitive of following general formula (7).Noting, is preferred form by the homopolymer of following formula (5) expression by the polyimide of following formula (7) expression.

In (7), for example, G and G ' represent covalent bond, CH independently at above general formula (5) ₂Base, C (CH ₃) ₂Base, C (CF ₃) ₂Base, C (CX ₃) ₂Base (wherein, X represents halogen), CO base, oxygen atom, sulphur atom, SO ₂Base, Si (CH ₂CH ₃) ₂Base or N (CH ₃) base.G and G ' can be same to each other or different to each other.

In following formula (5) and (7), L is a substituting group, and d and e represent substituent quantity separately.For example, L represent halogen, have 1 to 3 carbon atom alkyl, have haloalkyl, phenyl or the substituted-phenyl of 1 to 3 carbon atom.A plurality of L can be same to each other or different to each other.For example, the example of substituted-phenyl comprises having and at least aly is selected from halogen, has the alkyl of 1 to 3 carbon atom and has the substituent substituted-phenyl of the haloalkyl of 1 to 3 carbon atom.The example of halogen comprises fluorine, chlorine, bromine and iodine.D represents 0 to 2 integer, and e represents 0 to 3 integer.

In (7), Q is a substituting group at following formula (5), and f represents substituent quantity.For example, Q represents to be selected from hydrogen, halogen, alkyl, substituted alkyl, nitro, cyano group, alkylthio, alkoxy, aryl, substituted aryl, alkyl ester group and substituted alkyl ester group.A plurality of Q can be same to each other or different to each other.The example of halogen comprises fluorine, chlorine, bromine and iodine.The example of substituted alkyl comprises haloalkyl.The example of substituted aryl comprises halogenated aryl.F represents 0 to 4 integer, and g represents 0 to 3 integer.H represents 1 to 3 integer.Preferred g and h are all greater than 1.

In following formula (6), R ¹⁰And R ¹¹Expression is selected from the atom or the group of hydrogen, halogen, phenyl, substituted-phenyl, alkyl and substituted alkyl independently.Preferred R ¹⁰And R ¹¹Represent haloalkyl independently.

In following formula (7), for example, M ¹And M ²Represent halogen independently, have 1 to 3 carbon atom alkyl, have haloalkyl, phenyl or the substituted-phenyl of 1 to 3 carbon atom.The example of halogen comprises fluorine, chlorine, bromine and iodine.The example of substituted-phenyl comprises having and at least aly is selected from halogen, has the alkyl of 1 to 3 carbon atom and has the substituent substituted-phenyl of the haloalkyl of 1 to 3 carbon atom.

Object lesson by the polyimide of following formula (5) expression comprises by the represented compound of following formula (8).

Other example of polyimide comprises by making having the multipolymer for preparing with any copolymerization (arbitrary copolymerization) of the acid dianhydride of above-mentioned different skeleton (repetitive) and diamines.

The example of acid dianhydride comprises fragrant four carboxylic acid's dianhydride.The example of fragrant four carboxylic acid's dianhydride comprise pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, naphthalenetetracarbacidic acidic dianhydride, heteroaromatic tetracarboxylic dianhydride and 2,2 '-biphenyl tetracarboxylic dianhydride that replaces.

The example of pyromellitic dianhydride comprises: pyromellitic dianhydride, 3,6-diphenyl pyromellitic dianhydride, 3, two (trifluoromethyl) pyromellitic dianhydride, 3 of 6-, 6-dibromo pyromellitic dianhydride and 3,6-dichloro pyromellitic dianhydride.The example of benzophenone tetracarboxylic dianhydride comprises: 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride and 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride.The example of naphthalenetetracarbacidic acidic dianhydride comprises: 2,3,6, and 7-naphthalenetetracarbacidic acidic dianhydride; 1,2,5,6-naphthalenetetracarbacidic acidic dianhydride and 2,6-two chloro-naphthalenes-1,4,5,8-tetracarboxylic acid dianhydride.Heteroaromatic tetracarboxylic dianhydride's example comprises: thiophene-2,3,4,5-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride and pyridine-2,3,5,6-tetracarboxylic dianhydride.2,2 '-example of the biphenyl tetracarboxylic dianhydride that replaces comprises: 2,2 '-two bromo-4,4 ' and, 5,5 '-biphenyl tetracarboxylic dianhydride, 2,2 '-two chloro-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride and 2,2 '-two (trifluoromethyl)-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride.

Tetracarboxylic dianhydride's further example comprises: 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride, two (2,5,6-three fluoro-3,4-dicarboxyl phenyl) the methane dianhydride, 2,2-two (3,4-dicarboxyl phenyl)-1,1,1,3,3, 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 connects two O-phthalic acid dianhydrides, two (3,4-dicarboxyl phenyl) sulfonic acid dianhydride, 3,3 ', 4,4 '-diphenylsulfone acid's dianhydride, 4,4 '-[4,4 '-isopropylidene-two (to phenylene oxygen)] two (phthalic anhydrides), N, N-(3,4-dicarboxyl phenyl)-N-methylamine dianhydride and two (3,4-dicarboxyl phenyl) diethylsilane dianhydride.

Wherein, preferred fragrance tetracarboxylic dianhydride is 2,2 '-biphenyltetracarboxylic dianhydride that replaces, more preferably 2,2 '-two (trihalomethyl)-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride, further preferred 2,2 '-two (trifluoromethyl)-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride.

The example of diamines comprises aromatic diamines.The object lesson of aromatic diamines comprises phenylenediamine, diaminobenzophenone, naphthylenediamine, heteroaromatic diamines and other aromatic diamines.

The example of phenylenediamine comprises for example phenylenediamine of o-phenylenediamine, m-phenylene diamine or p-phenylenediamine (PPD), 2, and 4-diaminotoluene, 1,4-diamido-2-methoxybenzene, 1,4-diamido-2-phenyl benzene and 1,3-diamido-4-chlorobenzene.The example of diaminobenzophenone comprises 2,2 '-diaminobenzophenone and 3,3 '-diaminobenzophenone.The example of naphthylenediamine comprises 1,8-naphthylenediamine and 1,5-naphthylenediamine.The example of heteroaromatic diamines comprises 2,6-diamino-pyridine, 2,4-diamino-pyridine and 2,4-diamido-S-triazine.

The further example of aromatic diamines comprises: 4,4 '-benzidine, 4,4 '-diaminodiphenylmethane, 4,4 '-(9-fluorenylidene)-dianiline, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-diaminodiphenylmethane, 2,2 '-two chloro-4,4 '-benzidine, 2,2 ', 5,5 '-the 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 of 2-, 1,1,3,3, the 3-HFC-236fa, 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl 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]-1,1 of 2-, 1,3,3, the 3-HFC-236fa, 4,4 '-diaminodiphenyl sulfide and 4,4 '-diamino-diphenyl sulfone.

The example of polyetherketone comprises disclosed polyaryletherketone by following general formula (9) expression among the JP 2001-049110 A.

In following formula (9), X represents substituting group, and q represents substituent quantity.For example, X represents halogen atom, low alkyl group, haloalkyl, lower alkoxy or halogenated alkoxy.A plurality of X can be same to each other or different to each other.

The example of halogen atom comprises fluorine, chlorine, bromine and iodine.Wherein, preferred fluorine atom.Preferred low alkyl group is the alkyl with straight or branched of 1 to 6 carbon atom, more preferably has the alkyl of the straight or branched of 1 to 4 carbon atom.In particular, preferred low alkyl group is methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl or the tert-butyl group, special preferable methyl or ethyl.The example of haloalkyl comprises the halogenide of above-mentioned low alkyl group, for example trifluoromethyl.Preferred lower alkoxy is the alkoxy with straight or branched of 1 to 6 carbon atom, more preferably has the alkoxy of the straight or branched of 1 to 4 carbon atom.In particular, preferred lower alkoxy is methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy or tert-butoxy, preferred especially methoxy or ethoxy.The example of halogenated alkoxy comprises the halogenide of above-mentioned lower alkoxy, for example trifluoromethoxy.

In following formula (9), q is 0 to 4 integer.In following formula (9), preferred q=0 and the carbonyl and the ether oxygen atom that are connected to the phenyl ring two ends are in contraposition.

In following formula (9), R ¹Be that m is 0 or 1 integer by the represented group of following formula (10).

In following formula (10), for example, the identical substituting group of X in X ' expression and the following formula (9).In following formula (10), a plurality of X ' can be same to each other or different to each other.Q ' expression substituent X ' quantity.Q ' is 0 to 4 integer, and preferred q ' is 0.P is 0 or 1 integer.

In following formula (10), R ²Expression divalence aromatic radical.The example of divalence aromatic radical comprises: adjacent penylene, a penylene or to penylene, and derived from the divalent group of naphthalene, biphenyl, anthracene, ortho-terphenyl, meta-terphenyl or para-terpheny, phenanthrene, dibenzofurans, biphenyl ether (biphenyl ether) or biphenyl sulfone (biphenyl sulfone).In the divalence aromatic group, the hydrogen atom that directly is connected on the aromatic group can be replaced by halogen atom, low alkyl group or lower alkoxy.Wherein, preferred R ²For being selected from by the aryl of following formula (11) to (17) represented group.

In following formula (9), preferred R ¹It is group with following formula (18) expression.In following formula (18), R ²With p such as following formula (10) definition.

In following formula (9), n represents the degree of polymerization.For example, n is in 2 to 5,000 scope, preferably in 5 to 500 scope.Polymerization can comprise the polymerization of the repetitive of the polymerization of repetitive of same structure or different structure.Under latter event, the polymerized form of repetitive can be block polymerization or atactic polymerization.

Preferably the end by the polyaryletherketone of following formula (9) expression is to the fluorine atom of tetrafluoro benzoylene side and the hydrogen atom of oxyalkylene side.For example, such polyaryletherketone can be by following general formula

(19) expression.In following formula (19), n represents and the identical degree of polymerization in following formula (9).

Object lesson by the polyaryletherketone of following formula (9) expression comprises the compound of being represented by following formula (20) to (23).Following various in, n represents and the identical degree of polymerization of following formula (9).

In addition, the example of polyamide or polyester comprises disclosed polyamide or polyester among the JP 10-508048 A.For example, its repetitive can be represented by following general formula (24).

In following formula (24), Y represents O or NH.E represents at least a for example covalent bond, the thiazolinyl with 2 carbon atoms, the haloalkenyl group with 2 carbon atoms, the CH of being selected from ₂Base, C (CX ₃) ₂Base (wherein, X is halogen or hydrogen), CO base, oxygen atom, sulphur atom, SO ₂Base, Si (R) ₂The group of base and N (R) base.A plurality of E can be same to each other or different to each other.In E, R has the alkyl of 1 to 3 carbon atom and has at least a in the haloalkyl of 1 to 3 carbon atom, and with respect to carbonyl functional group or Y group, position or contraposition between it is positioned at.

In following formula (24), A and A ' represent substituting group separately, and t and z represent substituent quantity separately.P represents 0 to 3 integer, and q represents 1 to 3 integer.R represents 0 to 3 integer.

A is selected from for example hydrogen; halogen; alkyl with 1 to 3 carbon atom; haloalkyl with 1 to 3 carbon atom; the alkoxy of representing by OR (wherein, R as defined above); aryl; substituted aryl by preparations such as halogenations; alkoxy carbonyl with 1 to 9 carbon atom; alkyl carbonyl oxy with 1 to 9 carbon atom; aryloxycarbonyl with 1 to 12 carbon atom; aryl-carbonyl oxygen and substitutive derivative thereof with 1 to 12 carbon atom; aryl-amino-carbonyl and aryl carbonyl amino and substitutive derivative thereof with 1 to 12 carbon atom with 1 to 12 carbon atom.A plurality of A can be same to each other or different to each other.A ' is selected from halogen for example, have the alkyl of 1 to 3 carbon atom, have haloalkyl, phenyl and the substituted-phenyl of 1 to 3 carbon atom.A plurality of A ' can be same to each other or different to each other.Substituent example on the phenyl ring of substituted-phenyl comprises halogen, have the alkyl of 1 to 3 carbon atom, have the haloalkyl and the combination thereof of 1 to 3 carbon atom.T represents 0 to 4 integer, and z represents 0 to 3 integer.

Preferably by the serve as reasons repetitive of following general formula (25) expression of the repetitive of the polyamide of following formula (24) expression or polyester.

In following formula (25), A, A ' and Y such as following formula (24) definition.V represents 0 to 3 integer, preferred 0 to 2 integer.X and y respectively do for oneself 0 or 1, but are not 0 simultaneously.

Next, will the method that prepare second birefringent layers be described.As long as effect of the present invention can be provided, can use the method that is fit to arbitrarily as the method for preparing second birefringent layers.

Be coated on the transparent polymer film at least a polymer solution that is selected from polyamide, polyimide, polyester, polyetherketone, polyamidoimide and polyester-imide and drying, thereby on transparent polymer film, form polymeric layer, obtain to have second birefringent layers that nx=ny＞nz concerns thus.Subsequently, integrally stretch or compression transparent polymer film and polymeric layer, thereby obtain to have second birefringent layers that nx＞ny＞nz concerns.

The example of the solvent of coating solution (will be coated in the polymer solution on the transparent polymer film) comprises, but be not limited to: halogenated hydrocarbons, for example chloroform, methylene chloride, phenixin, ethylene dichloride, tetrachloroethane, triclene, zellon, chlorobenzene and o-dichlorobenzene; Phenols, for example phenol and parachlorophenol; Aromatic hydrocarbon, for example benzene,toluene,xylene, methoxybenzene and 1,2-dimethoxy benzene; Ketones solvent, for example acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-Pyrrolidone and N-N-methyl-2-2-pyrrolidone N-; Esters solvent, for example ethyl acetate and butyl acetate; Alcohols solvent, for example tert-butyl alcohol, glycerine, ethylene glycol, triethylene glycol, glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol and 2-methyl-2,4-pentanediol; Amide solvent, for example dimethyl formamide and dimethyl acetamide; Nitrile solvents, for example acetonitrile and butyronitrile; Ether solvent, for example diethyl ether, butyl oxide and tetrahydrofuran; Carbon disulphide; The ethyl cellulose solvent; With the butyl cellulose solvent.Wherein, the preferable methyl isobutyl ketone, because non-liquid crystal material shows highly dissoluble in this solvent, and this solvent can not corrode substrate.These solvents can use separately, perhaps can two or more be used in combination.

Can apply as long as can obtain above-mentioned optical compensating layer and coating solution, coating solution can have the concentration of the non-liquid crystal polymer of any appropriate.For example, as 100 weight portions, the content of non-liquid crystal polymer is preferably 5 to 50 weight portions in the solution with solvent, more preferably 10 to 40 weight portions.Viscosity with solution of such concentration range makes it be easy to apply.

As required, coating solution can further contain various adjuvants, for example stabilizing agent, plastifier and metal.

As required, coating solution can further contain other resin.The example of the resin that other are different comprises various resins for universal use, engineering plastics, thermoplastic resin and thermoset resin.According to purpose, be used in combination such resin, have suitable physical strength or persistent optical compensating layer thereby form.

The example of resins for universal use comprise tygon (PE), polypropylene (PP), polystyrene (PS), poly-(methyl methacrylate) (PMMA), ABS resin and AS resin.Nylon), polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) example of engineering plastics comprises poly-acetic acid esters (POM), polycarbonate (PC), polyamide (PA:.The example of thermoplastic resin comprises polyphenylene sulfide (PPS), polyethersulfone (PES), polyketone (PK), polyimide (PI), poly terephthalic acid cyclohexanedimethanol ester (PCT), polyaryl thing (PAR) and liquid crystal polymer (LCP).The example of thermoset resin comprises epoxy resin and phenol phenolics.

Other kind and consumption that will add the different resin in the coating solution can suitably be set according to purpose.For example, the ratio that such resin joins in the non-liquid crystal polymer is preferably 0 to 50 quality %, more preferably 0 to 30 quality %.

The example of the method for coating solution comprises: spin-coating method, rolling method, flow coat method, print process, dipping method (dip coating method), The tape casting, rod are coated with method and woodburytype.In the practical application, also can use the method for superposition of polymeric layer as required.

After the coating, (under 60 to 250 ℃, dry run evaporation for example) is also removed solvent in the above-mentioned solution, thereby forms membranaceous optical compensating layer by for example air dry, air-dry or heat drying.

Second birefringent layers that preferably has nx=ny＞nz relation obtains in the following manner: at least a polymer solution that is selected from polyamide, polyimide, polyester, polyetherketone, polyamidoimide and polyester-imide is coated on the transparent polymer film; Thereby volume drying forms polymeric layer on transparent polymer film.As mentioned above, can obtain to comprise to have nx=ny＞laminate (being called laminate A hereinafter) of second birefringent layers of nz relation.

Second birefringent layers with nx＞ny＞nz relation can obtain in the following manner: at least a polymer solution that is selected from polyamide, polyimide, polyester, polyetherketone, polyamidoimide and polyester-imide is coated on the transparent polymer film; Thereby its volume drying is formed polymeric layer on transparent polymer film; Integrally stretch then or compression transparent polymer film and polymeric layer.Specifically, for the method that relates to contraction, be coated on the transparent polymer film that lives through stretch processing above-mentioned solution and drying, thereby make transparent polymer film and polymeric layer reduced overall and obtain optics twin shaft characteristic.By relating to the method for stretching, above-mentioned solution is coated on the transparent polymer film that does not stretch and dry, wholely subsequently under heating, stretch, thereby with transparent polymer film and polymeric layer integrally stretching and obtain optics twin shaft characteristic.Like this, can obtain to comprise to have nx＞ny＞laminate (being called laminate B hereinafter) of second birefringent layers of nz relation.

The film similar with the diaphragm (transparent protective film) of polaroid can be used as transparent polymer film.

Second birefringent layers can perhaps use as laminate A or B by this second birefringent layers is included in second birefringent layers that transparent polymer film forms and peels off at interior laminate A or B and use from thus obtained.Laminate A or B further with the situation of polaroid lamination under, the transparent polymer film among laminate A or the B can serve as the diaphragm (transparent protective film) of polaroid.

G. the lamination of second birefringent layers and polaroid (second polaroid)

In liquid crystal panel of the present invention, preferred second birefringent layers is in the same place with the second polaroid lamination.As shown in Figure 1, in the preference pattern of liquid crystal panel, the 3rd transparent protective film 12 is arranged a side lamination and the opposite side lamination has the 3rd transparent protective film 12 side laminations of second polaroid 50 of the 4th transparent protective film 13 on second birefringent layers 70.

Can adopt the method for suitable arbitrarily method as lamination second birefringent layers and polaroid (second polaroid).But method for optimizing comprises the transparent polymer film side and the second polaroid lamination of the laminate (laminate A or laminate B) that will contain second birefringent layers that forms on transparent polymer film.In this case, transparent polymer film can serve as the transparent protective film of second polaroid.

Can adopt the method for suitable arbitrarily lamination method (for example bonding) as the lamination transparent polymer film and second polaroid.Bonding can being undertaken by using the bonding agent or the contact adhesive that are fit to arbitrarily.The kind of bonding agent or contact adhesive can suitably be selected according to the kind of adherend (that is, transparent protective film and polaroid).The object lesson of bonding agent comprises: acrylic acid, vinyl alcohol, polysiloxane-based, polyesters, polyurethanes and polyethers polymer adhesive; The isocyanates bonding agent; And rubber adhesive.The object lesson of contact adhesive comprises acrylic acid, vinyl alcohol, polysiloxane-based, polyesters, polyurethanes, polyethers; Isocyanates; With the rubber-like contact adhesive.

The thickness of bonding agent or contact adhesive is not particularly limited, but is preferably 10 to 200nm, more preferably 30 arrives 180nm, most preferably 50 arrives 150nm.

In the present invention, continuous transparent polymer film and continuous polaroid (second polaroid) can adhere to each other continuously at the longitudinal direction of orientation separately, thereby obtain blooming with very high production efficiency.In the method, this film need not cut sth. askew with respect to vertical (draw direction) of lamination.As a result, deviation does not take place in the optic axis angle of cutting film, therefore can obtain not have qualitatively the blooming of deviation as product.And, owing to do not produce refuse in the cutting, therefore can obtain this blooming with low cost.In addition, also help to produce large-scale Polarizer.H. the lamination of the liquid crystal cells and first birefringent layers or second birefringent layers

Want lamination on liquid crystal cells first birefringent layers or the surface of second birefringent layers preferably include pressure-sensitive adhesive layer so that be connected with liquid crystal cells.

The contact adhesive that is used to form pressure-sensitive adhesive layer is not particularly limited.Yet, for example, for example containing the polymkeric substance of acrylate copolymer, polysiloxane base polymer, polyester, polyurethane, polyamide, polyethers, fluorine-based polymer or rubber polymer can suitably select and use as the contact adhesive of base polymer.Particularly, the contact adhesive that for example has the acrylic pressure-sensitive adhesive of the pressure-sensitive adhesion character (for example wettability, cohesive and adhesive property) of excellent optical clarity, appropriateness and excellent against weather, thermotolerance etc. can preferably use.Particularly, the acrylic pressure-sensitive adhesive of preferably forming by acrylate copolymer with 4 to 12 carbon atoms.

In addition, from preventing because the foamed phenomenon that caused of suction or peel off phenomenon, prevent that because the distortion of the deterioration of the optical characteristics that difference caused of thermal expansion etc. or liquid crystal cells and the angle that forms the high-quality liquid crystal indicator with excellent durability, preferred pressure-sensitive adhesive layer has low water-intake rate and excellent thermotolerance.

Pressure-sensitive adhesive layer can contain the adjuvant that can join in the pressure-sensitive adhesive layer: for example, the resin of natural materials or synthetic, particularly, tackifying resin, or the filler, pigment, colorant or the antioxidant that form by glass fibre, beaded glass, metal powder or other inorganic powder.

Pressure-sensitive adhesive layer can be the pressure-sensitive adhesive layer that contains molecule, with the display light scattering properties.

Pressure-sensitive adhesive layer can be by suitable arbitrarily method configuration.Its example comprises, comprise that preparation contains dissolving or is dispersed in base polymer in suitable single solvent (for example toluene or ethyl acetate) or its mixed solvent or the concentration of its composition is about 10 to 40wt% pressure-sensitive adhesion agent solution, and the suitable method of deploying by for example The tape casting or cladding process and so on directly is provided at this solution the method on the blooming (for example, first birefringent layers); And openly go up the formation pressure-sensitive adhesive layer at spacer (separator) as described above, then pressure-sensitive adhesive layer is shifted and is attached to the lip-deep method of blooming (for example, first birefringent layers).

Pressure-sensitive adhesive layer can be configured on the one or both sides of blooming (for example, second birefringent layers) as differently form, dissimilar etc. superimposed layer.Be configured at pressure-sensitive adhesive layer under the situation on the two sides of blooming, differently form, the pressure-sensitive adhesive layer of dissimilar, different-thickness etc. can be configured in the front or the back of blooming.

The thickness of pressure-sensitive adhesive layer can suitably be determined according to the purposes of expection or bond strength, is preferably 1 to 40 μ m, more preferably 5 to 30 μ m, preferred especially 10 to 25 μ m.Thickness can make the permanance variation less than 1 μ m, and thickness surpasses 40 μ m then easily because the foaming grade causes and floats or peel off, and provides poor outward appearance.

Back-up coat can be configured between blooming (for example, first birefringent layers) and the pressure-sensitive adhesive layer, so that improve the adhesion characteristic between the two.

The preferred use by being selected from has back-up coat that amino polymkeric substance forms separately as back-up coat in polyurethane, polyester and the molecule.Especially preferably use and have amino polymkeric substance in the molecule separately.Have amino polymkeric substance in the molecule and guaranteed good cohesive, because carboxyl in amino in the molecule and the contact adhesive or the polar group in the conducting polymer react or show for example interaction of ionic interaction and so on.

Having amino polymkeric substance in the molecule separately comprises: the polymer of monomers that contains amino of for example dimethylaminoethyl acrylate of the monomer of poly-Ethylenimine, polyallylamine, polyvinylamine, polyvinylpyridine, polyvinylpyrrolidone/ and described and acrylic pressure-sensitive adhesive copolymerization.

Antistatic agent can be added so that provide antistatic property for back-up coat.For providing the example of the antistatic agent of antistatic property, back-up coat comprises: the nonionic surfactant class antistatic agent; Conducting polymer class antistatic agent, for example polyaniline, polythiophene, polypyrrole and polyquinoxaline; And metal oxide-type antistatic agent, for example tin oxide, antimony oxide and indium oxide.Particularly, the angle of stability of optical characteristics, outward appearance, antistatic effect and antistatic effect under heating and the wet condition is preferably used conducting polymer class antistatic agent.Wherein, especially preferably use the water-soluble conducting polymkeric substance or the water dispersible conducting polymer of polyaniline for example or polythiophene, because under the situation of using water-soluble conducting polymkeric substance or water dispersible conducting polymer as the material that forms antistatic layer, can suppress in the coating step organic solvent to the modification of blooming substrate.

In the present invention, first polaroid 30, first birefringent layers 60, second polaroid 50, second birefringent layers 70, bonding coat, pressure-sensitive adhesive layer etc. all have the uv absorption ability by handling with the ultraviolet absorber of for example salicylate compounds, benzo phenol compound, benzotriazole compound, cyanoacrylate compound or nickel complex compounds separately.

Hereinafter, will describe more specifically the present invention by embodiment.But the present invention is not limited to these embodiment.The method of the measurement character among the embodiment is described below.

＜measure phase difference 〉

With refractive index n x, ny and the nz of automatic birefringence analyser (the automatic refractometric analysis instrument KOBRA 21-ADH that Oji Scientific Instruments makes) measuring samples film, and the phase differential Rth of interior phase difference nd of calculating face and thickness direction.Measuring temperature is 23 ℃, and the measurement wavelength is 590nm.

＜measured X Y colourity 〉

Measure the tone of liquid crystal indicator with " EZ Contrast 160D " (trade name, ELDIM SA makes) at the place, position angle of 60 ° of polar angles and 0 to 360 ° of variation, and be plotted on the XY chromatic diagram.Fig. 4 has shown this position angle and polar angle.

(reference example 1: produce polaroid)

Polyvinyl alcohol film is painted in containing iodine aqueous solution, gains in borated aqueous solution, between the roller of different rates ratio uniaxial tension to 6 double-length degree, thereby produce polaroid.

(reference example 2: produce the polyvinyl alcohol bonding agent)

To pass through acetoacetyl modified polyethylene alcohol resin (degree of acetylation is 13%) as 100 weight portions; the concentration adjustment that will contain the aqueous solution of 20 weight portion methylol melamines arrives the concentration of 0.5wt%, thus the aqueous solution of preparation polyvinyl alcohol bonding agent.

(reference example 3: produce transparent protective film)

Cyclopentanone is coated on the polyethylene terephthalate, (" UZ-TAC ", trade name are bought from Fuji (Fuji) film industry Co., Ltd. then its integral body to be attached to the tri acetyl cellulose membrane that thickness is 40 μ m, Δ nd (590)=3nm is on the Rth (590)=40nm).Gains were descended dry 5 minutes at 100 ℃, after the drying polyethylene terephthalate film is stripped down.The Δ nd (590) of the cellulose family film (hereinafter being called 0TAC) that obtains is 0.2nm, and Rth (590) is 5.4nm.

(embodiment 1)

(producing first birefringent layers)

(" ZEONOR ", trade name are bought from Zeon Corporation, and thickness is 100 μ m, and photoelastic coefficient is 3.10 * 10 with continuous norbornene resin film down at 150 ℃ ^-12m ²/ N) uniaxial tension is to 1.46 double-length degree, thus produce the first continuous birefringent layers.The thickness of first birefringent layers is 80 μ m, and phase difference nd is 140nm in the face, and the phase differential Rth of thickness direction is 140nm.

(production comprises the Polarizer of TAC/ polaroid/0TAC)

Use polyvinyl alcohol resin (0.5 μ m) that the 0TAC that obtains in TAC (thickness is 40 μ m), polaroid and the reference example 3 is adhered to each other, thereby obtain to comprise the Polarizer (A) of TAC/ polaroid/0TAC.

(producing the laminate of TAC/ polaroid/0TAC/ first birefringent layers)

By acrylic pressure-sensitive adhesive (thickness is 20 μ m) first birefringent layers is adhered to the 0TAC side of Polarizer (A), make the absorption axes of polaroid of Polarizer (A) and the slow axis (draw direction) of first birefringent layers be perpendicular to one another.

(producing the laminate of second birefringent layers/TAC)

To use by 2, two (3, the 4-dicarboxyl phenyl) HFC-236fa and 2 of 2-, 2 '-two (trifluoromethyl)-4, the polyimide that 4 '-benzidine is synthetic and as the cyclohexanone of solvent prepare 15

The solution of wt% is coated to that (thickness is 80 μ m) to thickness is 20 μ m on the TAC substrate.Subsequently, integral body was carried out dried 10 minutes under 100 ℃, was second birefringent layers of 2.5 μ m and the laminate of TAC thereby produce thickness.

(" KOBRA-21 ADH ") measures the thus obtained phase differential that has second birefringent layers of substrate to the automatic birefringence analyser that Oi Scientific Instruments makes to use automatic birefringence analyser.Second birefringent layers that has substrate satisfies the relation of nx=ny＞nz, and phase difference nd is 0nm in its face, and the phase differential Rth of thickness direction is 230nm.

(producing the laminate of second birefringent layers/TAC/ polaroid/TAC)

With the polyvinyl alcohol bonding agent (thickness of bonding coat=50nm) with the polaroid lamination on the TAC surface of the laminate of second birefringent layers and TAC.With the polyvinyl alcohol bonding agent (thickness of bonding coat=50nm) with TAC film (thickness is 80 μ m) lamination on the polaroid of the opposition side of second birefringent layers, thereby obtain the laminate of second birefringent layers/TAC/ polaroid/TAC.

(production liquid crystal panel)

By acrylic pressure-sensitive adhesive (thickness is 20 μ m) the second birefringent layers side of the first birefringent layers side of " laminate of TAC/ polaroid/0TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " is adhered to the above and below of liquid crystal cells, make the absorption axes of each polaroid be perpendicular to one another.Liquid crystal cells splits out and uses from commercially available LCD TV (32 inches TVs, BenQ Corporation makes).

(evaluation)

Fig. 6 shows the result of the XY colourity of the TV that the EZ Contrast of use ELDIM SA manufacturing measures.Fig. 6 shows that X ripple part and Y ripple part are similar, and amplitude separately is little.That is, Fig. 6 prompting obtains neutral the demonstration at all azimuth directions.

(embodiment 2)

(production liquid crystal panel)

Except by the thickness in " producing the laminate of second birefringent layers/TAC " among the embodiment 1 is become 2.1 μ m in the acquisition face phase difference nd be that the phase differential Rth of 0nm and thickness direction is second birefringent layers of 190nm, obtain " laminate of TAC/ polaroid/0TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " according to the mode identical with embodiment 1.

By acrylic pressure-sensitive adhesive (thickness is 20 μ m) the second birefringent layers side of the first birefringent layers side of " laminate of TAC/ polaroid/0TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " is adhered to the above and below of liquid crystal cells, make the absorption axes of each polaroid be perpendicular to one another.Liquid crystal cells splits out and uses from commercially available LCD TV (32 inches TVs, SHARP Corporation makes).

(evaluation)

Fig. 7 shows the result of the XY colourity of the TV that the EZ Contrast of use ELDIM SA manufacturing measures.Fig. 7 shows that X ripple part and Y ripple part are similar, and amplitude separately is little.That is, Fig. 7 prompting obtains neutral the demonstration at all azimuth directions.

(embodiment 3)

(production liquid crystal panel)

Except by the thickness in " producing the laminate of second birefringent layers/TAC " among the embodiment 1 is become 2.1 μ m in the acquisition face phase difference nd be that the phase differential Rth of 0nm and thickness direction is second birefringent layers of 195nm, obtain " laminate of TAC/ polaroid/0TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " according to the mode identical with embodiment 1.

By acrylic pressure-sensitive adhesive (thickness is 20 μ m) the second birefringent layers side of the first birefringent layers side of " laminate of TAC/ polaroid/0TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " is adhered to the above and below of liquid crystal cells, make the absorption axes of each polaroid be perpendicular to one another.Liquid crystal cells splits out and uses from commercially available LCD TV (32 inches TVs, SONY Corporation makes).

(evaluation)

Fig. 8 shows the result of the XY colourity of the TV that the EZ Contrast of use ELDIM SA manufacturing measures.Fig. 8 shows that X ripple part and Y ripple part are similar, and amplitude separately is little.That is, Fig. 8 prompting obtains neutral the demonstration at all azimuth directions.

(embodiment 4)

(production liquid crystal panel)

Except: phase difference nd is 30nm in the acquisition face by being stretched longitudinally to 1.05 double-length degree after the dried in " producing the laminate of second birefringent layers/TAC " in embodiment 1 under 150 ℃, the phase differential Rth of thickness direction is 170nm and second birefringent layers that satisfies nx＞ny＞nz relation, and carry out lamination in " second birefringent layers/TAC/ polaroid/TAC " in embodiment 1 so that outside the absorption axes of the slow axis of second birefringent layers and polaroid is substantially parallel to each other, obtain " laminate of TAC/ polaroid/0TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " according to the mode identical with embodiment 1.

By acrylic pressure-sensitive adhesive (thickness is 20 μ m) the second birefringent layers side of the first birefringent layers side of " laminate of TAC/ polaroid/0TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " is adhered to the above and below of liquid crystal cells, make the absorption axes of each polaroid be perpendicular to one another.Liquid crystal cells splits out and uses from commercially available LCD TV (32 inches TVs, SHARP Corporation makes).

(evaluation)

Fig. 9 shows the result of the XY colourity of the TV that the EZ Contrast of use ELDIM SA manufacturing measures.Fig. 9 shows that X ripple part and Y ripple part are similar, and amplitude separately is little.That is, Fig. 9 prompting obtains neutral the demonstration at all azimuth directions.

(comparing embodiment 1)

(producing first birefringent layers)

(" ZEONOR ", trade name are bought from Zeon Corporation, and thickness is 100 μ m, and photoelastic coefficient is 3.10 * 10 with continuous norbornene resin film down at 150 ℃ ^-12m ²/ N) uniaxial tension is to 1.3 double-length degree, thus produce the first continuous birefringent layers.The thickness of first birefringent layers is 85 μ m, and phase difference nd is 100nm in the face, and the phase differential Rth of thickness direction is 100nm.

(producing the laminate of TAC/ polaroid/TAC/ first birefringent layers)

With bonding agent TAC (thickness is 80 μ m), polaroid and TAC (thickness is 80 μ m) lamination are in the same place successively.

By acrylic pressure-sensitive adhesive (thickness is 20nm) with the first birefringent layers lamination of above acquisition a side at the laminate of TAC/ polaroid/TAC.At this moment, carrying out lamination makes the absorption axes of polaroid and the slow axis of first birefringent layers be perpendicular to one another.

Thus, obtain the laminate of TAC/ polaroid/TAC/ first birefringent layers.

(producing the laminate of second birefringent layers/TAC)

Except by the thickness in " producing the laminate of second birefringent layers/TAC " among the embodiment 1 is become 1.6 μ m in the acquisition face phase difference nd be that 0nm and thickness direction phase differential Rth are second birefringent layers of 150nm, obtain " second birefringent layers/TAC/ polaroid/TAC " according to the mode identical with embodiment 1.

(producing the laminate of second birefringent layers/TAC/ polaroid/TAC)

With the polyvinyl alcohol bonding agent (thickness of bonding coat=50nm) with the polaroid lamination on the TAC surface of the laminate of second birefringent layers and TAC.With the polyvinyl alcohol bonding agent (thickness of bonding coat=50nm) TAC film (thickness is 80 μ m) lamination is not had on the surface of lamination at this polaroid, thus obtain the laminate of second birefringent layers/TAC/ polaroid/TAC.

(production liquid crystal panel)

By acrylic pressure-sensitive adhesive (thickness is 20 μ m) the second birefringent layers side of the first birefringent layers side of " laminate of TAC/ polaroid/TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " is adhered to the above and below of liquid crystal cells, make the absorption axes of each polaroid be perpendicular to one another.Liquid crystal cells splits out and uses from commercially available LCD TV (32 inches TVs, BenQ Corporation makes).

(evaluation)

Figure 10 shows the result of the XY colourity of the TV that the EZ Contrast of use ELDIM SA manufacturing measures.Figure 10 shows X ripple part and Y ripple part dissmilarity, and amplitude separately is big.That is, Figure 10 prompting does not obtain neutral the demonstration at all azimuth directions.

(comparing embodiment 2)

(production liquid crystal panel)

Except by the thickness in " producing the laminate of second birefringent layers/TAC " in the comparing embodiment 1 is become 1.3 μ m in the acquisition face phase difference nd be that the phase differential Rth of 0nm and thickness direction is second birefringent layers of 120nm, obtain " laminate of TAC/ polaroid/TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " according to the mode identical with comparing embodiment 1.

By acrylic pressure-sensitive adhesive (thickness is 20 μ m) the second birefringent layers side of the first birefringent layers side of " laminate of TAC/ polaroid/TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " is adhered to the above and below of liquid crystal cells, make the absorption axes of each polaroid be perpendicular to one another.Liquid crystal cells splits out and uses from commercially available LCD TV (32 inches TVs, SHARP Corporation makes).

(evaluation)

Figure 11 shows the result of the XY colourity of the TV that the EZ Contrast of use ELDIM SA manufacturing measures.Figure 11 shows X ripple part and Y ripple part dissmilarity, and amplitude separately is big.That is, Figure 11 prompting does not obtain neutral the demonstration at all azimuth directions.

(comparing embodiment 3)

(production liquid crystal panel)

Except by the thickness in comparing embodiment 1 " producing the laminate of second birefringent layers/TAC " is become 1.4 μ m in the acquisition face phase difference nd be that the phase differential Rth of 0nm and thickness direction is second birefringent layers of 130nm, obtain " laminate of TAC/ polaroid/TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " according to the mode identical with comparing embodiment 1.

By acrylic pressure-sensitive adhesive (thickness is 20 μ m) the second birefringent layers side of the first birefringent layers side of " laminate of TAC/ polaroid/TAC/ first birefringent layers " and " second birefringent layers/TAC/ polaroid/TAC " is adhered to the above and below of liquid crystal cells, make the absorption axes of each polaroid be perpendicular to one another.Liquid crystal cells splits out and uses from commercially available LCD TV (32 inches TVs, SONY Corporation makes).

(evaluation)

Figure 12 shows the result of the XY colourity of the TV that the EZ Contrast of use ELDIM SA manufacturing measures.Figure 12 shows that X ripple part is similar to a certain extent with Y ripple part, but amplitude separately is big.That is, Figure 12 prompting does not obtain neutral the demonstration at all azimuth directions.

Liquid crystal panel of the present invention is applicable to LCD TV, portable phone etc. with the liquid crystal indicator that comprises this liquid crystal panel.

Under the situation that does not depart from scope and spirit of the present invention, many other changes will be readily apparent to persons skilled in the art and are to implement easily.The scope that therefore it should be understood that claims is not limited by the details of instructions should, but explains widely.

Claims (18)

1. blooming, it comprises first transparent protective film, polaroid, second transparent protective film successively and has the birefringent layers of nx＞ny=nz relation and positive single shaft character, wherein

The phase differential Rth of the thickness direction of described second transparent protective film represents that with relational expression (1) it is less than or equal to 10nm,

Rth＝(nx-nz)×d …(1)

2. blooming according to claim 1, wherein said first transparent protective film comprise any one of cellulose family film and norborene class film.

3. blooming according to claim 1, the phase differential Rth of the thickness direction of wherein said second transparent protective film is less than or equal to 6nm.

4. blooming according to claim 1, the phase differential Rth of the thickness direction of wherein said second transparent protective film is less than or equal to 3nm.

5. phase difference nd represents that with relational expression (2) it is less than or equal to 2nm in the blooming according to claim 1, the face of wherein said second transparent protective film,

Δnd＝(nx-ny)×d …(2)

6. phase difference nd is less than or equal to 1nm in the blooming according to claim 5, the face of wherein said second transparent protective film.

7. blooming according to claim 1, wherein said second transparent protective film comprises the cellulose family film.

8. blooming according to claim 1, the absorption axes of wherein said polaroid is perpendicular to one another substantially with the slow axis of described birefringent layers.

9. blooming according to claim 1, wherein said birefringent layers comprise λ/4 plates.

10. the absolute value of the difference in the blooming according to claim 1, the face of wherein said birefringent layers between the phase differential Rth of phase difference nd and thickness direction is less than or equal to 10nm.

11. blooming according to claim 1, the absolute value that wherein said birefringent layers contains photoelastic coefficient is less than or equal to 2 * 10 ^-11m ²The resin of/N.

12. blooming according to claim 11, wherein said resin comprises cycloolefin resin.

13. a liquid crystal panel, the blooming according to claim 1 that it comprises liquid crystal cells and is configured in this liquid crystal cells one side.

14. liquid crystal panel according to claim 13, wherein said liquid crystal cells are a kind of of VA pattern and ocb mode.

15. liquid crystal panel according to claim 13, wherein:

Described liquid crystal cells comprises and is configured in the blooming according to claim 1 of watching side; With

Described liquid crystal cells comprises the birefringent layers with nx 〉=ny＞nz relation that is configured in backlight side.

16. liquid crystal panel according to claim 15, the birefringent layers of the wherein said nx of having 〉=ny＞nz relation is formed by non-liquid crystal material.

17. comprising, liquid crystal panel according to claim 16, wherein said non-liquid crystal material be selected from least a of polyamide, polyimide, polyester, polyetherketone, polyamidoimide or polyester-imide.

18. a liquid crystal indicator, it comprises liquid crystal panel according to claim 13.

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