CN101393296B - Retardation film, optical functional film, polarizing film, and display apparatus - Google Patents

Abstract

A main object of the present invention is to provide a highly reliable retardation film without the problems of peeling off of the retardation layer from the base material or the like generated in the case of forming the retardation layer, capable of easily obtaining an optional retardation value even for a small amount, and capable of improving the adhering property with a hydrophilic film such as a polarizing layer. In order to achieve the above-mentioned object, the present invention provides a retardation film, comprising a polymer film containing a material having refractive index anisotropy, wherein the material having refractive index anisotropy has a concentration gradient in a thickness direction of the polymer film.

Description

Phase-contrast film, optical functional film, polarized light film and display device

The application divides an application, the application number of its female case application: 200580030417.1, and the applying date: 2005.9.9, denomination of invention: phase-contrast film and manufacture method thereof, optical functional film, polarized light film and display device

Technical field

The present invention relates to be assembled in phase-contrast film and manufacture method, optical functional film, polarized light film and the display device of using in the display device such as liquid crystal indicator.

Background technology

As shown in figure 17, can enumerate to have as existing general liquid crystal indicator and inject side polaroid 102A, emitting side polaroid 102B and liquid crystal cells 104.Polaroid 102A and 102B are the structures that rectilinearly polarized light (schematically representing with arrow among the figure) with regulation direction of vibration vibration plane is seen through, and make separately direction of vibration be in right-angle relationship ground and dispose relatively with the crossed nicols state.Liquid crystal cells 104 comprises a plurality of unit corresponding with pixel, is configured between polaroid 102A and the 102B.

At this, be when adopting the situation of VA (Vertical Alignment) mode (schematically illustrating the director of liquid crystal among the figure with dotted line) that has sealed nematic crystal to be example if lift liquid crystal cells 104 in this liquid crystal indicator 100 with negative induced anisotropy, when then having seen through the cell mesh of the rectilinearly polarized light of injecting side polaroid 102A non-driven state in seeing through liquid crystal cells 104, be to carry out phase-shifts ground to see through and interdicted by emitting side polaroid 102B.Comparatively speaking, in seeing through liquid crystal cells 104, during the cell mesh of driving condition, be that rectilinearly polarized light carries out phase-shifts, with the light transmission emitting side polaroid 102B of this phase-shifts amount respective amount and penetrate.Like this, just can show the image of wishing by the driving voltage of each each unit suitably being controlled liquid crystal cells 104 in emitting side polaroid 102B side.Be not limited to take above-mentioned such light transmission and blocking form as liquid crystal indicator 100, also can consider the cell mesh of non-driven state penetrates from liquid crystal cells 104 on the one hand light transmission emitting side polaroid 102B and ejaculation, the light that penetrates from the cell mesh of driving condition is by emitting side polaroid 102B blocking, the liquid crystal indicator of this spline structure on the other hand.

But when seeing through the situation of the cell mesh of non-driven state attitude in above-mentioned such VA mode liquid crystal cells 104 as if the consideration rectilinearly polarized light, then liquid crystal cells 104 has birefringence, because the refractive index of thickness direction is different with the refractive index of face direction, although, seen through in the rectilinearly polarized light of injecting side polaroid 102A to the light of injecting with the direction of the normal slope of liquid crystal cells 104 and when seeing through liquid crystal cells 104, produce phase differential and become elliptically polarized light so seen through in the rectilinearly polarized light of injecting side polaroid 102A with only not carrying out phase-shifts along not seeing through that the normal of liquid crystal cells 104 is injected.This phenomenon is to cause owing to the liquid crystal molecule that is orientated to vertical direction in liquid crystal cells 104 works as positive C plate.Also be sealed in for the light that sees through liquid crystal cells 104 (seeing through light) the phase place extent that is produced the liquid crystal molecule in the liquid crystal cells 104 birefringence value, liquid crystal cells 104 thickness and see through the influence of optical wavelength etc.

Because above phenomenon, even certain unit in the liquid crystal cells 104 is a non-driven state, should rectilinearly polarized light intactly see through and when interdict by emitting side polaroid 102B, and to having leaked from emitting side polaroid 102B with the part of the light of the direction ejaculation of the normal slope of liquid crystal cells 104.

Therefore in the above-mentioned existing liquid crystal indicator 100, compare with image, have mainly with contrast from the image of observing with the direction of the normal slope of liquid crystal cells 104 to be reduced to the problem (problem of view angle dependency) that the display quality of reason worsens from top view.

In order to improve the view angle dependency problem of above-mentioned available liquid crystal display device 100, various technology had been developed in the past, one of them for example knows that patent documentation 1 or patent documentation 2 are arranged is disclosed: use the phase separation layer (expressing the phase separation layer of birefringence) with the regular molecular structure of cholesterol, by this phase separation layer being configured in the liquid crystal indicator that carries out optical compensation between liquid crystal cells and the polaroid.

At this, have in the phase difference optical element of the regular molecular structure of cholesterol, with λ=navp (p: the spacing of spiral in the helical structure of liquid crystal molecule (spirality), nav: with the screw axis plane orthogonal in mean refractive index) the selection reflection wavelength of expression, for example as patent documentation 1 or patent documentation 2 can be adjusted to than littler or bigger disclosed through light wavelength.

For example know that on the other hand that patent documentation 3 is arranged is disclosed: use the phase separation layer (expressing the phase separation layer of birefringence) that constitutes by discoid compound, by this phase separation layer being configured in the liquid crystal indicator that carries out optical compensation between liquid crystal cells and the polaroid.

Above-mentioned phase difference optical element is identical with the situation of described liquid crystal cells, produces phase differential and become elliptically polarized light when seeing through phase separation layer to the rectilinearly polarized light of injecting with the direction of the normal slope of phase separation layer.This phenomenon causes owing to the regular molecules align of cholesterol or discoid compound self work as negative C plate.Also be subjected to for the light that sees through phase separation layer (seeing through light) the phase place extent that is produced the liquid crystal molecule in the phase separation layer birefringence value, phase separation layer thickness and see through the influence of optical wavelength etc.

Therefore, if use above-mentioned phase separation layer, by designed phase difference layer suitably the VA mode liquid crystal cells phase differential that is produced and the phase differential that phase separation layer produced that works as negative C plate that work as positive C plate are offset, so just can improve the view angle dependency problem of liquid crystal indicator significantly.

As long as at this moment make above-mentioned positive C plate and the lagged value of above-mentioned negative C plate on thickness direction and just be, as long as promptly make above-mentioned negative C plate, just can improve the view angle dependency of polaroid by above-mentioned residual positive C plate composition and the A plate of preparing in addition at the absolute value of lagged value on the thickness direction absolute value less than above-mentioned positive C plate lagged value on thickness direction.The view angle dependency that can improve polaroid with positive C plate and A plate is for example disclosed in non-patent literature 1 and non-patent literature 2.

But above-mentioned phase separation layer has phase separation layer and the matrix material (problem of being adjacent to property between the diaphragm TAC (cellulose triacetate) of polarization photosphere for example.

In order to address this problem, for example as patent documentation 4 is disclosed, there are motion thermal treatment liquid crystal and alignment films to improve being adjacent to property.But when this method is not the low matrix material (for example TAC) of glass substrate but humidity resistance at matrix material, matrix material is flexible by the influence of moisture, sometimes liquid crystal layer is peeled off by this influence, and sufficient method is difficult to say so for the matrix material that is subjected to moisture effects easily.

As the method that not has being adjacent to property problem, for example as patent documentation 5 and patent documentation 6 are disclosed, also consider to be useful in and in cellulose acetate solution, mix the method that (retardation) rising agent that lags behind forms acetyl cellulose film when making acetyl cellulose film.But this method need be sneaked into hysteresis rising agent when the acetate fiber forming thin film, so that a collection of inevitably quantity is wanted is big, for quantity few the problem that is difficult to be lagged behind arbitrarily easily arranged.And because hysteresis rising agent is normally hydrophobic, so by it is mixed to integral body that the tow sides make acetyl cellulose film become is hydrophobic, the fashionable problem that has cementability to reduce of this phase separation layer and the layer of polarizer that constitutes by hydrophilic resins such as polyvinyl alcohol (PVA).

Patent documentation 1: the spy opens flat 3-67219 communique

Patent documentation 2: the spy opens flat 4-322223 communique

Patent documentation 3: the spy opens flat 10-312166 communique

Patent documentation 4: the spy opens the 2003-207644 communique

Patent documentation 5: the spy opens the 2000-111914 communique

Patent documentation 6: the spy opens the 2001-249223 communique

Non-patent literature 1:J.Chen et al., SID98Digest, p315 (1998)

Non-patent literature 2:T.Ishinabe et al., SIDOO Digest, p1094 (2000)

Summary of the invention

The present invention has considered this problem points and has developed, fundamental purpose is to provide a kind of phase-contrast film, it does not have problem that the above-mentioned phase separation layer that produces like that peels off etc. from matrix material and the reliability height when forming phase separation layer, even quantity also can obtain lagged value arbitrarily less easily, and with the cementability of hydrophilic films such as polarization photosphere also can be good.

The present invention is in order to reach described purpose, the phase-contrast film that provides as first form, it contains at macromolecule membrane has the anisotropic material of refractive index (the following refractive index anisotropic material that is called sometimes), the refractive index anisotropic material has concentration gradient described in this phase-contrast film on the thickness direction of described macromolecule membrane, solves described problem like this.

And the present invention is in order to reach described purpose, and as the phase-contrast film that second form provides, it is to have the anisotropic material of refractive index to be soaked in the macromolecule membrane and to form, and solves described problem like this.

And the present invention is in order to reach described purpose, the phase-contrast film that provides as the 3rd form, it contains at macromolecule membrane has the anisotropic material of refractive index, have the anisotropic material of refractive index described in this phase-contrast film and on the thickness direction of described macromolecule membrane, have concentration gradient, and this concentration gradient changes continuously, solves described problem like this.

The present invention for example is coated on the coating liquid that has dissolved the refractive index anisotropic material in the solvent on the surface of macromolecule membrane, just can be easily the refractive index anisotropic material be filled near the macromolecule membrane surface phase-contrast film that can obtain on the thickness direction of described macromolecule membrane, having refractive index anisotropic material concentration gradient like this by making the macromolecule membrane swelling soak into the refractive index anisotropic material.And amount by changing described coating liquid and concentration just can easily change the lagged value as phase-contrast film.Therefore, the advantage that has the phase-contrast film that can short run obtains having any lagged value easily.And not existing on matrix material, it and the phase separation layer of other layers to be carried out the bonding laminated and phase-contrast film of formation like this, therefore so do not produce the problem that phase separation layer is peeled off from matrix material, reliability such as thermotolerance and water tolerance and alkali resistance (alkaline-resistingization processing) and the high advantage of workability (usability repeatedly) again arranged.

When having the anisotropic material of refractive index described in the present invention concentration gradient changing continuously on the thickness direction of described macromolecule membrane, particularly because the stress of specific interface in the layer is concentrated disappearance, so the peel strength grow, reliability such as thermotolerance and water tolerance (repeatedly cold and hot under environment for use or when contacting to the permanance of interface peel) and alkali resistance with water and again workability uprise.

Macromolecule membrane described in the present invention preferably has regularity on refractive index.This is owing to by using this macromolecule membrane can be strengthened the regularity of the refractive index that described macromolecule membrane has by the refractive index anisotropic material of filling, can obtain having the cause of various characteristics phase-contrast film.

The material that the anisotropic material of refractive index described in the present invention preferably has liquid crystal liquid crystal property.If this is because the material with liquid crystal liquid crystal property adopts liquid crystal structure sometimes in the time of then in being filled into macromolecule membrane, can bring into play the cause of effect effectively for macromolecule membrane.

The molecular structure of the anisotropic material of refractive index described in the present invention is preferably bar-shaped.This is just can strengthen the cause of the regularity of the refractive index that described macromolecule membrane had owing to have the refractive index anisotropic material of rodlike molecule structure by use.

The anisotropic material of refractive index described in the present invention preferably has polymerizable functional groups group.After being filled into the refractive index anisotropic material in the macromolecule membrane, use this polymerizable functional groups reunion to close the refractive index anisotropic material and carry out producing high-molecular, can prevent that like this refractive index anisotropic material oozes out after making phase-contrast film, can make stable phase-contrast film.

Have the anisotropic material of refractive index described in the present invention and preferably contain material with polymerizable functional groups group and the material that does not have polymerizable functional groups group.This is owing at this moment can further strengthen phase difference function by the material that does not have polymerizable functional groups group, and by having the cause that material that polymerizable functional groups rolls into a ball improves the film reliability.

Have the concentration gradient of the anisotropic material of refractive index on described macromolecule membrane thickness direction described in the present invention, preferably a face side at described macromolecule membrane is a high concentration, and just becomes the concentration gradient of low concentration towards another face side.This is because by this structure, for the face side of low concentration side not can or rarely by containing or soaking into the intrinsic property that has the anisotropic material of refractive index and influence macromolecule membrane, therefore, when for example directly stickup polarization photosphere is made polarized light film on this phase-contrast film, can be by in this low concentration side, on the surface of not filling refractive index anisotropic material side, paste the polarization photosphere exactly specifically and hinder cementability, can obtain the cause of polarized light film.

Preferably a surface is different with another surface for the contact angle of pure water for described phase-contrast film.This is because by this structure, for example directly pasting with PVA on this phase-contrast film is that the polarization photosphere is when making polarized light film as the hydrophilic resin of matrix material, if being sticked on, the polarization photosphere has on the surface of lower contact angle, even then use the water system bonding agent especially, also can not hinder cementability, also can obtain the cause of polarized light film.

The concentration gradient of the anisotropic material of refractive index described in the present invention on described macromolecule membrane thickness direction also can be that two face side at described macromolecule membrane are high concentrations, and just become the concentration gradient of low concentration towards central portion.This is because by this structure, for example only when a face side has been filled the refractive index anisotropic material, even under the situation of lagged value deficiency, also can form high concentration to two face side systems of macromolecule membrane, can be by filling the cause that the refractive index anisotropic material becomes enough lagged values in two face side.

Preferably have among the present invention: described to have the anisotropic concentration of material gradient of refractive index be mild zone and described to have the anisotropic concentration of material gradient of refractive index be steep anxious zone.This is because the reinforcement of the reinforcement by phase differential and peel strength and thermotolerance, water tolerance in this case, has the cause that can improve reliability when wishing phase differential.

And preferably have and do not contain described zone with the anisotropic material of refractive index.This be since do not contain the zone of refractive index anisotropic material intactly remaining the character that macromolecule membrane had, so for example can utilize the cause of the good cementability of macromolecule membrane self.And the phase differential strengthening region of containing refractive index anisotropic material intensity sometimes reduces, and has the zone of not containing the refractive index anisotropic material like that by above-mentioned, and the benefit that can keep as the intensity of phase-contrast film etc. is then arranged.

Phase-contrast film described in the present invention is if be set at the hysteresis longitudinal refractive index of the interior direction of described pellicular front nx, the leading longitudinal refractive index of direction in the pellicular front is set at ny, the refractive index of film thickness direction is set at nz, is thickness setting d, using Rth[nm]=(nx+ny)/it is thickness direction when lagging behind that Rth that 2-nz} * d represents is set at, the described thickness direction preferably 70～300nm that lags behind.Can enlarge the scope of the lagged value that obtains among the present invention in fact, this is owing to can improve the cause that field angle is improved effect in this case.

Phase-contrast film described in the present invention is being that the turbidity value of benchmark when measuring is preferably below 1% with JIS-K7105.This is because polarized light state is not disorderly in this case, can improve the cause that field angle is improved effect.

Phase-contrast film described in the present invention the lagged value of visible region preferably short wavelength side greater than long wavelength side.This be since in general the lagged value of the employed liquid crystal material of liquid crystal layer in the visible region of liquid crystal indicator be ratio long wavelength side big of short wavelength side.Therefore when phase-contrast film of the present invention for example being used as optical compensation plate, the cause of the advantage that all wavelengths of pair visible region can both compensate is arranged.

On the other hand, the lagged value of phase-contrast film described in the present invention in the visible region also can be long wavelength side greater than short wavelength side.This is because phase-contrast film of the present invention during for example as the polaroid use of fitting with polarized light film, the point with advantage good on light leak compensates sees it is desirable.

Measure described phase-contrast film thickness direction with wavelength 550nm among the present invention and lag behind (Rth) in the deviation of pellicular front direction, preferably with the mean value of Rth as benchmark and in the scope of ± 5nm.This is because little and when for example being useful in this phase-contrast film in the display device as optical compensating film by deviation, can be carrying out uniform optical compensation in the display frame, can obtain the cause of the good display device of display quality such as field angle.

Phase-contrast film described in the present invention preferably can be wound into the reel of minimum diameter below 6 inches.This is owing to preferably phase-contrast film is made band-like film (also the being called thin bar) form of growth size in order to improve property produced in batches and production efficiency, make, check and after when adding keeping beyond man-hour, carrying and processing standby, preferably make the cause of the reel form that is wound on the cylinder.

The invention provides the phase-contrast film that the described phase-contrast film of individual layer is fitted mutually and formed more than two.This is owing to just can realize that so only a slice institute can not realize big or small like that lagged value (optical anisotropy value), can realize only a slice optically anisotropic cause of irrealizable complexity.

The invention provides the optical functional film that the optical functional layer beyond described phase-contrast film and the phase-contrast film is directly fitted and formed.Optical functional film of the present invention is owing to have function that phase-contrast films of the present invention such as for example optical compensation had and other functions of for example preventing to reflect etc. in the lump, so there is unnecessary indivedual setting to have the advantage of function film separately.

The invention provides described phase-contrast film and the direct polarized light film of fitting and forming of polarization photosphere.Usually polarized light film is the upward use of two surfaces that protective film is sticked on the polarization photosphere; but according to the present invention because to set an one protective film for be above-mentioned phase-contrast film; so when for example needing optical compensation plate in addition etc., the polarized light film of the application of the invention and the advantage that does not need to be provided with in addition optical compensation plate is arranged.

And the invention provides any of described phase-contrast film of the present invention, optical functional film or polarized light film is configured in display device on the light path.Can obtain reliability height, the good display device of display quality by the phase-contrast film of the present invention that disposes problems such as not peeling off with suitable hysteresis.In addition, do not need to be provided with respectively optical functional layer and phase separation layer, can obtain the good display device of display quality by disposing optical functional film of the present invention.In addition, do not need to be provided with in addition optical compensation plate, can obtain the good display device of display quality by disposing polarized light film of the present invention.

The invention provides a kind of manufacture method of phase-contrast film, it comprises: painting process, dissolving or disperseed phase differential strengthening region that the refractive index anisotropic material forms to form to be coated at least one surface of macromolecule membrane with coating liquid in its solvent; Soak into operation, it makes the described phase differential strengthening region formation by described painting process coating be soaked in the described macromolecule membrane with the described refractive index anisotropic material in the coating liquid; Drying process, it forms with the described solvent seasoning in the coating liquid the described phase differential strengthening region by described painting process coating.According to the present invention, form with coating liquid and just can easily form phase-contrast film by being coated with described phase differential strengthening region, and only form the lagged value that just can change the phase-contrast film that obtains with the coating weight that applies liquid etc. by changing described phase differential strengthening region.Therefore according to the present invention, also can be had the advantage of any lagged value phase-contrast film easily even have few quantity.

Soaking into operation described in the foregoing invention also can carry out in described drying process.This is owing to also can make the refractive index anisotropic material be soaked in cause in the macromolecule membrane sometimes in drying by adjusting dry humidity etc.And also can control the degree of soaking into of refractive index anisotropic material and the cause of refractive index anisotropy (lagged value) sometimes by the control of drying condition.

And the present invention is preferably in a described refractive index anisotropic material that has behind the described drying process being soaked in the described macromolecule membrane and carries out immobilized immobilization operation.This is owing to be that to have the situation of polymerizable functional groups group inferior at the refractive index anisotropic material for example, after being soaked in the refractive index anisotropic material in the macromolecule membrane, carrying out polymerization makes producing high-molecular just can prevent to make back refractive index anisotropic material to ooze out from the surface, can improve the cause of phase-contrast film stability.

The problem that the phase separation layer that phase-contrast film of the present invention does not produce when forming phase separation layer is peeled off etc. from matrix material, reliability such as thermotolerance and water tolerance and alkali resistance and workability height again, even under the situation of short run, also can easily obtain lagged value arbitrarily, have such effect.And with the cementability of hydrophilic film such as polarization photosphere also can be good, and alkali resistance is also good, therefore is the suitable phase-contrast film that can directly fit with the polarization photosphere.

Description of drawings

Fig. 1 is the schematic cross-sectional views of expression phase-contrast film one example of the present invention;

Fig. 2 is other routine schematic cross-sectional views of expression phase-contrast film of the present invention;

Fig. 3 schematically illustrates the figure that concentration gradient distributes;

Fig. 4 is the schematic cross-sectional views of expression phase-contrast film one example of the present invention;

Fig. 5 is other routine schematic cross-sectional views of expression phase-contrast film of the present invention;

Fig. 6 is the process chart of expression phase-contrast film manufacture method one example of the present invention;

Fig. 7 is the summary exploded perspective view that expression possesses liquid crystal indicator one example of phase-contrast film of the present invention;

Fig. 8 is the summary exploded perspective view that expression possesses liquid crystal indicator one example of optical functional film of the present invention;

Fig. 9 is the summary exploded perspective view that expression possesses liquid crystal indicator one example of polarized light film of the present invention;

Figure 10 is the SEM photo of the phase-contrast film section of expression embodiment 1;

Figure 11 is the TEM photo of the phase-contrast film section of expression embodiment 1;

To be expression carry out TOF-SISM figure by the spectrometric CONCENTRATION DISTRIBUTION of positive secondary ion when measuring to the phase-contrast film of embodiment 1 to Figure 12;

To be expression carry out TOF-SISM figure by the negative spectrometric CONCENTRATION DISTRIBUTION of secondary ion when measuring to embodiment 1 phase-contrast film to Figure 13;

Figure 14 is the coating amount of expression embodiment 5 and the curve of phase differential relation;

Figure 15 is the dependent figure of phase differential angle of expression embodiment 6 and embodiment 7 phase-contrast films;

Figure 16 is the SEM photo of expression embodiment 9 phase-contrast film sections;

Figure 17 is the summary exploded perspective view of expression available liquid crystal display device.

1 macromolecule membrane, 2 phase differential strengthening regions, 3 face side

The face side 5 matrix material zones of 4 opposition sides

6 phase differential strengthening regions form with 7 ultraviolet rays of coating liquid

8 phase-contrast films, 9 zone lines, 10 phase-contrast films

20,30,50 liquid crystal indicators, 40 optical functional films

60 polarized light films

Embodiment

The present invention includes: phase-contrast film and manufacture method thereof, the optical functional film that has used phase-contrast film, polarized light film and used the display device of these films.Below they are described in detail.

A, phase-contrast film

Phase-contrast film of the present invention at first is described.

The phase-contrast film of the present invention's first form is to contain the phase-contrast film that the refractive index anisotropic material forms at macromolecule membrane, and described refractive index anisotropic material has concentration gradient on the thickness direction of described macromolecule membrane.

And the phase-contrast film of the present invention's second form is to have the anisotropic material of refractive index to be soaked in the macromolecule membrane and to form.

And the phase-contrast film of the present invention's the 3rd form is to contain at macromolecule membrane to have the phase-contrast film that the anisotropic material of refractive index forms, described have the anisotropic material of refractive index have concentration gradient on the thickness direction of described macromolecule membrane, and this concentration gradient changes continuously.

Fig. 1 is the sectional drawing of expression phase-contrast film one example of the present invention.Be formed with the phase differential strengthening region 2 of containing the refractive index anisotropic material on macromolecule membrane 1 face side in the example shown in Figure 1.At this moment the concentration gradient of refractive index anisotropic material is the concentration height that is formed with the face side 3 of phase differential strengthening region 2, and does not contain the refractive index anisotropic material in inchoate face side 4.Concentration gradient of the present invention is meant that any 2 at thickness direction locate the concentration difference, and also comprises like this and have the refractive index anisotropic material in a certain subregion, does not have the situation of refractive index anisotropic material in other zones.

The present invention is formed with the phase differential strengthening region that has the refractive index anisotropic material like this in phase-contrast film, formed the concentration gradient of refractive index anisotropic material, so this phase differential strengthening region is reinforced as the effect of phase separation layer and various optical functions that can with good grounds birefringence.For example aftermentioned is used the TAC (cellulose triacetate) that plays negative C plate effect as macromolecule membrane like that, is molecular structure that bar-shaped liquid crystal material is when using as the refractive index anisotropic material, because the effect as negative C plate has been strengthened in described phase differential strengthening region, phase-contrast film therefore of the present invention has been changed as negative the with better function of C plate.

Phase-contrast film of the present invention is as describing in detail in " manufacture method of B, phase-contrast film " hurdle, for example only by dissolving or disperseed the phase differential strengthening region of described refractive index anisotropic material to form to be coated with coating liquid, the refractive index anisotropic material is soaked into from the surface of macromolecule membrane and be filled in the macromolecule membrane, just can easily form the phase differential strengthening region, therefore when short run need have the compensating plate etc. of multiple lagged value, also can be easily and obtain phase-contrast film at low cost, have such advantage.

As mentioned above, phase-contrast film of the present invention is different with the existing film that has formed phase separation layer on matrix material, owing to being forms the phase differential strengthening region and the unfilled matrix material zone of having filled the refractive index anisotropic material to constitute in phase-contrast film, therefore the problem that does not have the existing phase separation layer that becomes problem to peel off, reliability such as thermotolerance and water tolerance height can be stablized use.And because alkali resistance improves for example to patience being arranged with the fashionable basification of polarized light laminating.And because workability (usability repeatedly) is good again, so yield rate height in the operation is favourable.

When being filled in the macromolecule membrane in that the refractive index anisotropic material is soaked into from the surface of macromolecule membrane, usually described to have the concentration gradient of the anisotropic material of refractive index on the macromolecule membrane thickness direction be continually varying.At this moment particularly owing to the stress of specific interface in the layer concentrated disappear, so the peel strength grow, the reliability of thermotolerance and water tolerance (repeatedly cold and hot under environment for use or when contacting with water to the permanance of interface peel) etc. uprises.

Below this phase-contrast film of the present invention is described in detail by each each structure.

1, macromolecule membrane

There is no particular limitation for macromolecule membrane used in the present invention, but can use resin by the light that sees through the visible region to form usually rightly.At this light that sees through the visible region, be meant that average light transmitance among the 380～780nm of visible region more than 50%, is more preferably more than 70%, further be well the situation more than 85%.The mensuration of light transmission rate is to use ultraviolet-visible pectrophotometer (for example UV-3100PC of (strain) Shimadzu Seisakusho Ltd. system), the value of measuring in room temperature, atmosphere.

As macromolecule membrane used in the present invention preferably refractive index have regular.Promptly preferably have in the face and lag behind and/or thickness direction lags behind as macromolecule membrane used in the present invention.Why phase-contrast film of the present invention obtains bigger lagged value and as optically functional films such as optical compensation plates and bring into play function, though indeterminately can infer it is following reason.Promptly the chances are when being filled into the refractive index anisotropic material in the macromolecule membrane, the refractive index anisotropic material that is filled has more been strengthened the regularity of the original refractive indexes such as birefringence that have of macromolecule membrane, can obtain having the phase-contrast film of various characteristics like this.Therefore, as macromolecule membrane used in the present invention, can use rightly to have some refractive index regularity.

So-called refractive index regularity for example can be enumerated (1) macromolecule membrane and has negative C plate, the characteristic etc. of C plate, A plate or biaxiality plate just as work macromolecule membrane that (2) stretch of negative C plate among the present invention.

The thickness direction of macromolecule membrane used in the present invention lags behind (Rth) preferably in the scope of 20nm～100nm, particularly in the scope of 25nm～80nm for well, especially be better in the scope of 30nm～60nm.

In addition, lag behind (Re) in the face preferably in the scope of 0nm～300nm, particularly in the scope of 0nm～150nm for well, especially be better in the scope of 0nm～125nm.

At this, the lagged value of direction for example is to use automatic double refraction detection device (prince's instrumentation machine Co., Ltd. system for example in described thickness direction and the face, trade name: KOBRA-21ADH), under 23 ℃, the environment of 55%RH, carry out three-dimensional detecting refractive index with wavelength 589nm, just can obtain by obtaining refractive index n x, ny, nz.

The present invention is as describing in detail in aftermentioned " manufacture method of B, the phase-contrast film " hurdle, be dissolving in the solvent or having disperseed the phase differential strengthening region formation of described refractive index anisotropic material to be coated on the surface of macromolecule membrane with coating liquid, utilize solvent to make its swelling and described refractive index anisotropic material is soaked in macromolecule membrane and be filled in the macromolecule membrane, therefore preferably high for the specified solvent swellbility.Macromolecule membrane swelling when preferably being immersed in macromolecule membrane in the specified solvent specifically.This phenomenon can judge that with range estimation (film thickness: number μ m), the solvent that drips just can be confirmed the swellability for solvent by the situation of soaking into of observing solvent for example to form macromolecule membrane thereon.

Macromolecule membrane used in the present invention can be to have flexible flexible material, or also can be not have flexible rigid material, but preferably uses flexible material.This is owing to by using flexible material just can make phase-contrast film of the present invention manufacturing process become the process of volume-volume (roll to roll), can obtain the cause of the phase-contrast film of highly productive.

As the material that constitutes described flexible material, can example illustrate: celluosic resin, norbornene-based polymer, cyclic olefine polymkeric substance, polymethylmethacrylate, polyvinyl alcohol (PVA), poly-imines, polyarylate, polyethylene terephthalate, polysulfones, polyethersulfone, amorphous polyolefin, modified acroleic acid based polymer, polystyrene, epoxy resin, polycarbonate, polyesters etc., the present invention can use celluosic resin and norbornene-based polymer rightly.

Can enumerate cyclic olefin polymer (COP) or cyclic olefine copolymer (COC) as described norbornene-based polymer, but the present invention preferably uses cyclic olefin polymer.This is because the water absorption and the permeability of cyclic olefin polymer is low, therefore by macromolecule membrane used in the present invention is made of cyclic olefin polymer, just can make phase-contrast film of the present invention good cause on the aging stability of optical characteristics.

The concrete example of the described cyclic olefin polymer that uses as the present invention for example can be enumerated JSR Corp.'s system, trade name ARTON.

Preferably use cellulose esters as described celluosic resin, and in cellulose esters, preferably use the cellulose acylate class.Because the cellulose acylate class is widely used industrial, so on this aspect of purchase property easily, be favourable.

As the described cellulose acylate class low-grade fatty acid ester of carbon number 2～4 preferably.As low-grade fatty acid ester for example can be that cellulose acetate so only contains single low-grade fatty acid ester, or for example also can be that cellulose acetate-butyrate or cellulose-acetate propionate contain many fatty acid ester like this.

Among the present invention, in described low-grade fatty acid ester, can use cellulose acetate especially suitably.As optimal average acetoxylation degree 57.5～62.5% (degree of exchange: cellulose triacetate 2.6～3.0) that is to use of cellulose acetate.Be meant the cellulosic acetate binding capacity of per unit mass at this acetoxylation degree.The acetoxylation degree can be obtained by the mensuration and the calculating of degree of acetylation among the ASTM:D-817-91 (test methods of cellulose acetate etc.).

The macromolecule membrane that the present invention uses also can be implemented stretch processing.This is because by implement stretch processing, the cause that described refractive index anisotropic material is soaked into easily in macromolecule membrane.There is no particular limitation as this stretch processing, just can according to the arbitrary decisions such as material that constitute macromolecule membrane.Can illustration unilateral stretching processing and two-way stretch processing as stretch processing.

It is that layer institute by single constituted that the structure of the macromolecule membrane that the present invention uses is not limited to, and also can be multiple-layer laminated structure.It is laminated when having multiple-layer laminated structure can be that the layer of same composition carries out, and also can be to have the different multilayers of forming to carry out laminated.

There is no particular limitation for the film thickness of the macromolecule membrane that the present invention uses, and just can as long as suitably select.Therefore, it is the film of so-called narrow sense that the said film of the present invention is not limited to, but also comprises so-called sheet, plate zone film thickness.But many usually things that uses film., particularly can appropriately use in 20 μ m～100 mu m ranges normally in the scope of 10 μ m～200 μ m as film thickness.

When use stretching the macromolecule membrane that forms, after carrying out laminated grade, add to have man-hour and produce the tendency of contraction (reinstatement of stretching) by added heat to the polarization photosphere.At this moment follow the situation of shrinking and having lagged value to change.In order to prevent this point, preferably in advance macromolecule membrane is carried out heat treated (annealing), discharge or relax shrink resulting residual stress by macromolecule membrane.As the temperature conditions of this heat treated, usually preferably from the glass temperature of macromolecule membrane to the temperature the temperature of fusion (or fusing point).

The deviation that thickness direction described later lags behind also depends on employed macromolecule membrane, therefore, in order to dwindle deviation, measure the institute's macromolecule membrane thickness direction that the used hysteresis (Rth) obtain deviation in the pellicular front direction with wavelength 550nm, preferably with the mean value of Rth as benchmark in the scope of ± 5nm.

2, refractive index anisotropic material

The following describes the refractive index anisotropic material that the present invention uses.The refractive index anisotropic material that uses as the present invention, so long as can be filled in the macromolecule membrane and be have a birefringence material just can and there is no particular limitation.

The present invention is to be fit to use the molecular weight ratio materials with smaller according to the easy degree of filling in macromolecule membrane.Be exactly be fit to use molecular weight in 200～1200 scopes specifically, material in 400～800 scopes particularly.This said molecular weight for have polymerizable functional groups described later group, in macromolecule membrane polymerisable refractive index anisotropic material, expression be molecular weight before the polymerization.

The refractive index anisotropic material that uses as the present invention preferably molecular structure is bar-shaped material.If this is owing to bar-shaped material, then than the cause that is easier to enter into the macromolecule membrane internal clearance.

In addition, the refractive index anisotropic material that uses as the present invention material (liquid crystal liquid crystal property molecule) that preferably has liquid crystal liquid crystal property.This is because the refractive index anisotropic material is that liquid crystal liquid crystal property is divided the period of the day from 11 p.m. to 1 a.m, when being filled, the refractive index anisotropic material might in macromolecule membrane, become mesomorphic state in macromolecule membrane, the cause that can more effectively in phase-contrast film, reflect the birefringence of refractive index anisotropic material.

Can use as the refractive index anisotropic material among the present invention: nematic crystal molecular material, cholesteric crystal molecular material, Chinrally nematic (chiral nematic) liquid crystal liquid crystal property molecular material, saucer-like configuration liquid crystal liquid crystal property molecular material, discoid liquid crystal liquid crystal property molecular material, wherein refractive index anisotropic material nematic crystal molecular material preferably.If this is because during the nematic crystal molecular material, the number～hundreds of nematic crystal molecules that then entered into the macromolecule membrane internal clearance are orientated in macromolecule membrane, therefore the cause that the refractive index anisotropy is occurred more reliably.Particularly described nematic crystal molecule preferably has the molecule of base at interval at the mesogen two ends.This is that the nematic crystal molecule of base has flexibility owing to have at interval at the mesogen two ends, so can prevent to produce when entering in the gap in macromolecule membrane the cause of gonorrhoea.

The refractive index anisotropic material that the present invention uses is fit to use and has polymerizable functional groups group in the molecule, especially it is desirable to have can be 3 D cross-linked polymerizable functional groups group.This is because if having polymerizable functional groups group, the then effect of the atomic group that the irradiation of back by light produces from Photoepolymerizationinitiater initiater in being filled into macromolecule membrane or the effect by electron ray etc., and the refractive index anisotropic material can carry out producing high-molecular (crosslinked) in macromolecule membrane, the unfavorable condition that therefore can prevent that after becoming phase-contrast film refractive index anisotropic material from oozing out etc. can obtain stablizing the cause of the phase-contrast film of use.

" 3 D cross-linked " is to instigate the mutual 3 dimension polymerizations and become the network structure state of liquid crystal liquid crystal property molecule.

Do not limit as this polymerizable functional groups group is special, can use the effect of ionizing radiations such as passing through ultraviolet ray, electron ray or hot effect and the various polymerizable functional groups group of polymerization.Typical example as these polymerizable functional groups groups can be enumerated: free-radical polymerised functional group or cationic polymerization functional group etc.And the typical example as free-radical polymerised functional group can be enumerated: have the functional group of the unsaturated dual key of ethene of at least one energy addition polymerization, can enumerate as concrete example: have or do not have substituent vinyl, acrylate-based (general name that comprises acryloyl group, methacryl, acryloxy, methacryloxy) etc.Concrete example as the cationic polymerization functional group can be enumerated epoxy radicals etc.Polymerizable functional groups group as other for example can enumerate: isocyanate group, unsaturated triple bond etc.See the suitable functional group that uses from the point of handling in the middle of them with ethene unsaturated double-bond.

Wherein being particularly suitable for using molecular structure among the present invention is bar-shaped liquid crystal liquid crystal property molecule, and terminal has an above-mentioned polymerizable functional groups group.This is because for example if use the nematic crystal molecule that has polymerizable functional groups group at two ends, then can mutual 3 dimension polymerization and become the network structure state, can make the cause of more firm macromolecule membrane.

Be exactly to be fit to use the terminal acrylate-based liquid crystal liquid crystal property molecule that has specifically.The concrete example that end has acrylate-based nematic crystal molecule is indicated in following chemical formula (1)～(6).

[Chemical formula 1]

At this, the liquid crystal liquid crystal property molecular energy shown in chemical formula (1), (2), (5) and (6) is according to D.J.BroerMakromol Chem.190,3201-3215 (1989) or D.J.Broer MakromolChem.190,2255～2268 (1989) disclosed methods or modulate similarly with it.Being modulated among the DE195,04,224 of liquid crystal liquid crystal property molecule is disclosed shown in chemical formula (3) and (4).

The concrete example that has an acrylate-based nematic crystal molecule as end can be enumerated in below chemical formula (7)～(17) represented.

[Chemical formula 2]

Also can use two or more refractive index anisotropic materials among the present invention.

For example the refractive index anisotropic material contain molecular structure be bar-shaped and at two ends to have the liquid crystal liquid crystal property molecule of an above polymerizable functional groups group and molecular structure be bar-shaped and divide under the subcase in the liquid crystal liquid crystal property that an end has an above polymerizable functional groups group, just can suitably adjust polymerization density (cross-linking density) and phase difference function by the proportioning of adjusting both, it is desirable putting from this.

This is because the rod shaped liquid crystal molecule that has an above polymerizable functional groups group at an end soaks in macromolecule membrane easily, and/or in macromolecule membrane orientation easily, therefore the cause of easier reinforcement phase difference function tendency is arranged.On the other hand, this is because the rod shaped liquid crystal molecular energy that has an above polymerizable functional groups group at two ends improves polymerization density, therefore can pay and prevent that molecule is exudative, the cause of permanance such as solvent resistance and thermotolerance.

Refractive index anisotropic material as the present invention's use, consider that from the aspect of strengthening phase difference function more and improving the film reliability preferably to use molecular structure be bar-shaped and have the liquid crystal liquid crystal property molecule of described polymerizable functional groups group and molecular structure is bar-shaped and does not have the liquid crystal liquid crystal property molecule of described polymerizable functional groups group.Particularly preferably use: molecular structure is bar-shaped and is bar-shaped and is bar-shaped and does not have the liquid crystal liquid crystal property molecule of described polymerizable functional groups group at two ends at liquid crystal liquid crystal property molecule, molecular structure that an end has a described polymerizable functional groups group at liquid crystal liquid crystal property molecule, molecular structure that two ends have a described polymerizable functional groups group.This is owing to the rod shaped liquid crystal molecule that does not have polymerizable functional groups group soaks in macromolecule membrane easily, and/or is orientated easily in macromolecule membrane, therefore the cause of easier reinforcement phase difference function.On the other hand, this is the polymerization that can carry out owing to mix the rod shaped liquid crystal molecule with polymerizable functional groups group between the molecule, can pay like this and prevent that molecule is exudative, the cause of permanance such as solvent resistance and thermotolerance.

3, concentration gradient

The anisotropic material of refractive index described in the present invention has concentration gradient on the thickness direction of described macromolecule membrane.

Have a concentration gradient among the present invention, so long as thickness direction any 2 locate the concentration difference just can, there is no particular limitation.The form that the present invention is desirable can be described as: the concentration gradient of refractive index anisotropic material is a high concentration in a face side of macromolecule membrane, and just become the concentration gradient form (first form) of low concentration towards another face side, and the concentration gradient of refractive index anisotropic material is high concentration in two face side of macromolecule membrane, and just becomes these two forms of concentration gradient form (second form) of low concentration towards central portion.But also can be that face side is a low concentration, and have the form of area with high mercury in the inside of macromolecule membrane.Below two desirable forms are described by each each form.

(1) first form

First form of the present invention is that the refractive index anisotropic material is high concentration in the concentration gradient of macromolecule membrane thickness direction in a face side of macromolecule membrane, and just becomes the concentration gradient form of low concentration towards another face side.This first form is schematically shown at Fig. 1.As shown in Figure 1, a face side 3 at macromolecule membrane 1 in this form is formed with the phase differential strengthening region 2 of containing the refractive index anisotropic material, is formed with matrix material zone 5 in the face side 4 of opposition side.

This phase differential strengthening region is to contain or soak into the refractive index anisotropic material to form in macromolecule membrane.The state of the molecule of the molecule of macromolecule membrane and refractive index anisotropic material still fails fully to understand in the phase differential strengthening region, but the refractive index anisotropic material that is made of the rodlike molecule that has electric dipole moment at its long axis direction is soaked into when making, can infer it roughly is following state.

Be that wire macromolecule in the macromolecule membrane is arranged on average in roughly parallel with the pros and cons of the macromolecule membrane face and (distributes but form mixed and disorderly direction in this parallel surface).In addition, the molecule of the bar-shaped refractive index anisotropic material that soaks into from the macromolecule membrane surface on average is arranged in (but being that mixed and disorderly direction distributes) in the face parallel with the pros and cons of macromolecule membrane according to the arrangement of this macromolecule membrane in this parallel surface by aligning direction forcibly.

Like this, electric dipole moment vector owing to the refractive index anisotropic material in the phase differential strengthening region is arranged in the face parallel with the pros and cons of macromolecule membrane fifty-fifty, so the refractive index of the normal direction of the face quadrature parallel with the macromolecule membrane pros and cons relatively is lower than the refractive index of direction in this face.Therefore the characteristic that negative C plate occurs.

In addition, each molecule at this refractive index anisotropic material has polymerizable functional groups group, they carry out polymerizing curable and when forming the refractive index anisotropic material, in the phase differential strengthening region the crosslinked body of 3 of refractive index anisotropic material molecule dimensions with regard to envelope the strand of macromolecule membrane, the strand that becomes macromolecule membrane is inserted in the state in the network of the crosslinked body of refractive index anisotropic material molecule 3 dimensions.And the molecular energy of the molecule of macromolecule membrane and refractive index anisotropic material carries out under the chemically combined situation mutually, and the molecule of the molecule of macromolecule membrane and refractive index anisotropic material just becomes the crosslinked composite high-molecular state of 3 dimensions.

By above state, oozing out of refractive index anisotropic material is prevented from, and stable refractive index anisotropy occurs.

First form is characterized in that as described above, is formed in a face side of macromolecule membrane in the phase differential strengthening region of containing the refractive index anisotropic material.In this phase differential strengthening region the concentration gradient of refractive index anisotropic material normally the face side of macromolecule membrane become high concentration, the central side of macromolecule membrane thickness direction becomes low concentration.And it is the matrix material zone that another face side of macromolecule membrane is formed with the zone of not containing the refractive index anisotropic material.

This form is owing to formed the phase differential strengthening region in a face side of macromolecule membrane like this, so have following advantage.

Promptly because described matrix material area side does not contain the refractive index anisotropic material, so the character that macromolecule membrane had is intactly remaining.Because having the zone of not containing the refractive index anisotropic material is the matrix material zone, so for example when the good situation of the cementability of macromolecule membrane self is inferior, just can easily make polarized light film etc. by the polarization photosphere being bonded in described matrix material area side etc., have such advantage.And intensity is low sometimes to contain the phase differential strengthening region of refractive index anisotropic material, but just can keep as the intensity of phase-contrast film etc. by having above-mentioned matrix material zone, has such advantage.

The thickness of phase differential of the present invention strengthening region particularly is desirable in the scope of 1 μ m～4 μ m normally in the scope of 0.5 μ m～8 μ m.This is owing to hour then can not obtain enough lagged values than above-mentioned scope, makes thickness than the big then difficult cause of above-mentioned scope.

Whether the concentration gradient of judging the refractive index anisotropic material becomes this form like this, just can judge by the composition analysis in phase differential strengthening region and matrix material zone.

Method as composition analysis can be enumerated: by GSP (accurate inclined cutting method) phase-contrast film is cut off the section that exposes thickness direction, measure the method that the thickness direction concentration of material distributes by this section being carried out flight time type secondary ion mass spectrometry (TOF-SISM).

As flight time type secondary ion mass spectrometry (TOF-SISM), for example use TFS-2000 as the Physical Electronics society system of flight time type secondary ion mass spectrometry meter, for example the primary ions kind being set at is Ga ⁺, the primary ions energy settings for be 25kV, back segment is quickened to be set at is 5kV, measure phase-contrast film thickness direction section just and/or negative secondary ion carry out.At this moment the CONCENTRATION DISTRIBUTION of refractive index anisotropic material thickness direction can be by obtaining the curve of making for thickness direction from the secondary ion intensity of refractive index anisotropic material.As if the curve of making similarly for thickness direction, can see then that the relative concentration of refractive index anisotropic material and matrix material film changes for the secondary ion intensity that comes from matrix material.From the secondary ion of refractive index anisotropic material, can use for example by section tem observation etc. other analytical approach and can infer the surface or the position of having filled the refractive index anisotropic material, the summation of the secondary ion that observes doughtily etc. relatively.From the secondary ion of matrix material film, can use for example by section tem observation etc. other analytical approach and can infer the surface or the position of not filling the refractive index anisotropic material, the summation of the secondary ion that observes doughtily etc. relatively.

In first form, preferably a surface is different with another surface for the contact angle of pure water for described phase-contrast film.This is because by this structure, for example directly pasting with PVA on this phase-contrast film is that the polarization photosphere is when making polarized light film as the hydrophilic resin of matrix material, if being sticked on, the polarization photosphere has on the surface of lower contact angle, even then use the water system bonding agent especially, also cementability can be do not hindered, the cause of polarized light film can be obtained.

Among the present invention phase-contrast film for a surface of pure water contact angle and another surperficial difference preferably twice more than, be more preferably more than four degree, particularly five degree are above is ideal.

In addition, the example of Fig. 1 is that a face side 3 at macromolecule membrane 1 is formed with phase differential strengthening region 2, be formed with the form in matrix material zone 5 in the face side 4 of opposition side, but first form also comprises the refractive index anisotropic material and contains with high concentration in a face side of macromolecule membrane, the form that the refractive index anisotropic material contains with low concentration in another face side of macromolecule membrane.For the cementability on surface and intensity etc., the low concentration side also has the advantage than the nearly macromolecule membrane self property of high concentration side joint in this case.This low concentration side surface of other course when bonding, the cementability that the concentration of refractive index anisotropic material preferably self is not had for macromolecule membrane brings the concentration in the obstacle scope, for example phase-contrast film for the difference of the high concentration side surface of pure water contact angle and low concentration side surface be twice more than, be more preferably more than four degree, particularly the above such concentration of five degree.

(2) second forms

Second form of the present invention is that the refractive index anisotropic material is high concentration in the concentration gradient of macromolecule membrane thickness direction in two face side of macromolecule membrane, and is the concentration gradient form of low concentration towards central portion.This second form is schematically shown at Fig. 2.As shown in Figure 2, this form is formed with the phase differential strengthening region 2 of containing the refractive index anisotropic material in two face side of macromolecule membrane 1, is formed with matrix material zone 5 at central portion.

This form is characterised in that, the phase differential strengthening region of containing the refractive index anisotropic material is formed on two face side of macromolecule membrane.In this phase differential strengthening region the concentration gradient of refractive index anisotropic material normally the face side of macromolecule membrane be high concentration, the central side of macromolecule membrane thickness direction is a low concentration.And being formed with the zone of not containing the refractive index anisotropic material at the central part of the thickness direction of macromolecule membrane is the matrix material zone.

At this moment so the film thickness of phase differential strengthening region and the first above-mentioned homomorphosis are in this description will be omitted.

This form is owing to formed the phase differential strengthening region in two face side of macromolecule membrane like this, so have following advantage.

Be this form owing to have the phase differential strengthening region, so the anticipation of the lagged value of phase differential strengthening region is the twice of described first form in two face side.Therefore under the situation of the first form lag value deficiency, the situation of lagged value is beneficial significantly for further needs.

And the phase differential strengthening region of containing the refractive index anisotropic material reduces as the intensity of phase-contrast film sometimes, but owing to have the zone of not containing the refractive index anisotropic material at central portion is the matrix material zone, so can keep intensity as phase-contrast film etc., have such advantage.

In addition, the example of Fig. 2 is that two face side at macromolecule membrane 1 are formed with the phase differential strengthening region 2 of containing the refractive index anisotropic material, be formed with the form in matrix material zone 5 at central portion, but second form also comprises the refractive index anisotropic material and contains the form that the refractive index anisotropic material contains with low concentration at central portion with high concentration in two face side of macromolecule membrane.For intensity etc., low concentration region also has the advantage than the nearly macromolecule membrane self property of high concentration side joint in this case.

Whether the concentration gradient of judging the refractive index anisotropic material becomes this form like this, has been to use and the identical method of the above-mentioned first form situation, just can judge by the composition analysis in phase differential strengthening region and matrix material zone.

Above-mentioned all forms preferably all are that the concentration gradient with described macromolecule membrane thickness direction of the anisotropic material of described refractive index is a continually varying among the present invention.This be since this situation with compare in the situation of the discontinuous variation of certain thickness concentration, stress to specific interface in the layer is concentrated disappearance, so the peel strength grow, reliability such as thermotolerance and water tolerance (repeatedly cold and hot under environment for use or when contacting to the permanance of interface peel) and alkali resistance and the cause that uprises of workability again with water.

This so-called concentration gradient change continuously be meant for example such as Fig. 3 (a)～(e) shown in, the longitudinal axis is got into concentration, when transverse axis is got into thickness direction, the concentration change of thickness direction is continuous.

Preferably have among the present invention: described to have the anisotropic concentration of material gradient of refractive index be mild zone and described to have the anisotropic concentration of material gradient of refractive index be steep anxious zone.This be since in this case the regional centralized of high concentration and mild concentration gradient the having the anisotropic material of refractive index of q.s and guaranteed enough lagged values at this, in the zone of steeper anxious concentration gradient, between area with high mercury and low concentration region, concentration is connected continuously and can prevents that stress specific interface in layer from concentrating, therefore have the cause that can improve reliability when wishing phase differential.

Mild and steep anxious being meant of concentration gradient has the relativeness that the anisotropic material of refractive index distributes in the thickness direction concentration gradient among the present invention.The steep anxious zone of zone that concentration gradient is mild and concentration gradient is relatively the zone that connects with the little value of concentration gradient to be divided with the regional macroscopic view that is connected with big value.At this moment include the certain zone of concentration gradient in the zone that concentration gradient is mild.The zone that concentration gradient is mild among the present invention can be enumerated as the zone (A) of the zone of Fig. 3 (a) (A), Fig. 3 (b), the concentration of refractive index anisotropic material is high relatively, and the refractive index anisotropic material is to be filled in situation in the macromolecule membrane etc. near saturated concentration.It is such that the zone (B) of zone (B) as Fig. 3 (a), Fig. 3 (b) can be enumerated in the steep anxious zone of concentration gradient among the present invention, from the zone of containing the refractive index anisotropic material with high relatively concentration to the zone of the regional transition of the matrix material that does not contain the refractive index anisotropic material etc.Requiring under the situation of high lagged value, Fig. 3 (a), the such concentration gradient of Fig. 3 (b) generally are desirable.But when the high lagged value of special requirement not, then also can be as Fig. 3 (c), nearby concentration has been filled form that the concentration gradient mild zone of refractive index anisotropic material be connected to the steep anxious zone of the concentration gradient of low concentration transition and portion's side in the central with low concentration from high concentration towards central portion on the macromolecule membrane surface of having filled the refractive index anisotropic material with high concentration.

In above-mentioned first form, about comprising described situation with zone of mild zone of the anisotropic concentration of material gradient of refractive index and the steep urgency of concentration gradient, can enumerate as Fig. 4 schematically shows: a face side 3 at macromolecule membrane 1 is formed with the phase differential strengthening region 2 of containing the refractive index anisotropic material, face side 4 at opposition side is formed with matrix material zone 5, in phase differential strengthening region 2,, be formed with from contain the situation of the mild zone of refractive index anisotropic material and concentration gradient with high relatively concentration to the steep anxious zone line 9 of the concentration gradient of the matrix material zone transition that does not contain the refractive index anisotropic material with the borderline region place in matrix material zone 5.

In above-mentioned second form, about comprising described situation with zone of mild zone of the anisotropic concentration of material gradient of refractive index and the steep urgency of concentration gradient, can enumerate as Fig. 5 schematically shows: two face side at macromolecule membrane 1 are formed with the phase differential strengthening region 2 of containing the refractive index anisotropic material, be formed with matrix material zone 5 at central portion, in phase differential strengthening region 2,, be formed with from contain the situation of the mild zone of refractive index anisotropic material and concentration gradient with high relatively concentration to the steep anxious zone line 9 of the concentration gradient of the matrix material zone transition that does not contain the refractive index anisotropic material with the borderline region place in matrix material zone 5.

In addition, concentration gradient with described macromolecule membrane thickness direction of described refractive index anisotropic material changes, has the mild zone of the anisotropic concentration of material gradient of described refractive index continuously and has the steep anxious zone of the anisotropic concentration of material gradient of described refractive index, and this CONCENTRATION DISTRIBUTION analysis that can carry out flight time type secondary ion mass spectrometry (TOF-SISM) etc. by the section to the phase-contrast film thickness direction of above-mentioned explanation is judged.

4, phase-contrast film

The phase-contrast film of the present invention preferably visible region lagged value of phase-contrast film is that short wavelength side is greater than long wavelength side.This be since in general the lagged value of the employed liquid crystal material of liquid crystal indicator liquid crystal layer visible region to be short wavelength side than long wavelength side big.Therefore when phase-contrast film of the present invention for example being used as optical compensation plate, the cause of the advantage that all wavelengths of pair visible region can both compensate is arranged.

For the visible region lagged value that makes phase-contrast film becomes short wavelength side greater than long wavelength side, the visible region lagged value of preferably selecting macromolecule membrane and refractive index anisotropic material is that short wavelength side is greater than long wavelength side.But the employed TAC film of protective film of polarization photosphere (for example polyvinyl alcohol (PVA) (PVA)) does not have such lagged value, so the refractive index anisotropic material preferably selects to have above-mentioned lagged value.

On the other hand, the lagged value in the visible region of phase-contrast film described in the present invention also can be long wavelength side greater than short wavelength side.This is when using as polaroid because phase-contrast film of the present invention for example fitted with polarized light film, and the point with advantage good on light leak compensates sees it is desirable.

Phase-contrast film of the present invention is when measuring with wavelength 550nm, and described phase-contrast film thickness direction lags behind (Rth) in the deviation of pellicular front direction, preferably with the mean value of Rth as benchmark in the scope of ± 5nm.Therefore phase-contrast film of the present invention mainly is to come the control lag value by soaking into the refractive index anisotropic material, for example compares with the phase-contrast film of the negative C plate of making by two-way stretch, can reduction face in and the deviation of thickness direction lagged value.If only when stretch the control lag value, then to obtain uniform phase differential be unusual difficulty in whole zone in face, in general can not use the end.When phase-contrast film of the present invention for example was useful in this phase-contrast film in the display device as optical compensating film because the hysteresis deviation is little, the interior quilt of display frame is optical compensation equably, can obtain the good display device of display quality such as field angle.

At this, the hysteresis of thickness direction, in pellicular front the hysteresis of direction axially (pellicular front in the direction direction of refractive index maximum) refractive index be set at nx, leading axial (in the pellicular front in the direction direction of refractive index minimum) refractive index in the pellicular front be set at ny, when the refractive index of film thickness direction is set at nz, then can be expressed as Rth[nm]=(nx+ny)/2-nz} * d (d: thickness), hysteresis can be expressed as Re[nm in the face]=(nx-ny) * d (d: thickness).

Thickness direction lags behind and for example can followingly estimate in the deviation of pellicular front direction.Whole zone in pellicular front is measured thickness direction by every predetermined distance and is lagged behind.Calculate mean value from measured value, deduct mean value from each measured value of each predetermined distance and then can calculate change.At film is under the situation of long size film, make and create conditions when not changing in time, owing to can suppose that in the longitudinal direction it is certain that thickness direction lags behind, therefore also can measure thickness direction by every predetermined distance to the Width vertical with length direction lags behind, calculate mean value from measured value, deduct mean value from each measured value of each predetermined distance and calculate change.

In addition, the described thickness direction of the phase-contrast film of the present invention preferably 70～300nm that lags behind.This is owing to for example can improve the cause that field angle is improved effect in this case.

The lagged value of direction for example is to use automatic double refraction detection device (prince's instrumentation machine Co., Ltd. system for example in described thickness direction and the face, trade name: KOBRA-21ADH), under 23 ℃, the environment of 55%RH, carry out 3 dimension detecting refractive indexes with wavelength 589nm, just can obtain by obtaining refractive index n x, ny, nz.

According to the present invention, be to change the amount and the concentration of described coating liquid and use the method for phase differential strengthening region to come the control lag value.And during by stretching control lag value, in general if increase stretching ratio, then phase-contrast film thicken unclear, turbidity value uprises, depolarization uprises, promptly there is polarized light state disorderly and can not control the problem of polarized light, but the lagged value that the present invention can obtain wishing and depolarization is become considerably less when improving field angle and improve effect.

Be phase-contrast film of the present invention being that the turbidity value of benchmark when measuring can reach below 1% with JIS-K7105, further can reach below 0.8%.

Phase-contrast film of the present invention contains described refractive index anisotropic material at least and forms in macromolecule membrane, but only otherwise damage effect of the present invention, then also can contain other composition.For example also can contain remaining solvent, photopolymerization begins agent, polymerization inhibitor, levelling agent, chirality agent, silane coupling agent etc.

Phase-contrast film of the present invention also can be further directly laminated and form with other layer.For example as phase-contrast film and lagged value also can be further directly laminated with other phase separation layer when not enough.And as described later also can for example the polarization photosphere be directly laminated with other optical functional layer.

In the phase-contrast film of the present invention, by dissolving in the solvent or disperseed the phase differential strengthening region of described refractive index anisotropic material to form to be coated on the surface of macromolecule membrane with coating liquid, described refractive index anisotropic material is soaked in macromolecule membrane and when forming, comprise that also described refractive index anisotropic material is soaked into the lip-deep form of side macromolecule membrane with membranaceous remaining in.

Phase-contrast film described in the present invention preferably can be wound into the reel of minimum diameter below 6 inches.This be since phase-contrast film for improve its make, keeping, circulation and after add the batch process in man-hour and production efficiency and band-like film (also the being called thin bar) form of preferred fabrication growth size, make, check and after when adding keeping beyond man-hour, carrying and processing standby, preferably make the cause of the reel form that is wound on the cylinder.As the diameter of the pipe of the volume core that becomes this reel, below 6 inches, it according to circumstances is 3 inches normally.Therefore, go up favourable drum in order to be wound into to handle, phase-contrast film preferably can be wound into minimum diameter below 6 inches, is more preferably can be wound into below 3 inches.

On the other hand, have the anisotropic material of refractive index and generally have hard, crisp tendency.Its tendency is strong when particularly having carried out polymerization for immobilization.Therefore, the existing phase-contrast film that constitutes for the phase separation layer of other layers in macromolecule membrane matrix material upper strata cooperation, because hard, crisp phase separation layer, so then produce the problem that crackle or phase separation layer are peeled off from matrix material appears on the phase separation layer when the diameter that is wound into below 6 inches.In order to prevent that this crackle just need be provided with protective seam again on phase separation layer.In addition, if phase-contrast film for example with the such sheet state of the square square sheets of 30cm make, during keeping, then this problem can solve, but production efficiency and batch process property are bad.On the contrary, the phase-contrast film that the present invention obtains is to contain described refractive index anisotropic material and form the phase differential strengthening region in macromolecule membrane, therefore phase separation layer (phase differential strengthening region) wraps in macromolecule membrane inside in being, but also has the zone of not containing phase separation layer (even or contain, its amount is also few).Even therefore protective seam etc. is not set, when being wound into the roller shape, also be difficult to produce and concentrate caused crackle by stress, can manufacture the drum form rightly.

Phase-contrast film of the present invention also can be fitted as required and use with laminated form more than two except the individual layer specification of a slice only.Can enumerate as laminated two concrete example: direction (optically anisotropic direction) the alignment laminated form two slice or more of same phase-contrast film by principal refractive index, same phase-contrast film is made the mutual differently laminated form more than two of direction of principal refractive index, the different mutually phase-contrast film of optical anisotropy is pressed the laminated form more than two of direction (optically anisotropic direction) alignment of principal refractive index, or mutual different phase-contrast films direction (optically anisotropic direction) the differently laminated form more than two mutually that makes principal refractive index of optical anisotropy.These situations can realize a slice only can not realize the optical anisotropy value of size like that, maybe can realize the only irrealizable complicated optical anisotropy of a slice.

In addition, the applying between the phase-contrast film, laminated for example press from both sides to fit every suitable transparent adhesive layer implement.

5 purposes

As the purposes of phase-contrast film of the present invention, can in various uses, use as optical functional film.Specifically can enumerate: optical compensation plate (for example viewing angle compensation plate), ellipsoidal polarizing plate, raising brightness plate etc.

Among the present invention particularly the purposes as optical compensation plate be suitable.Be that bar-shaped liquid crystal compounds just can use in the purposes as negative C plate by using the TAC film as macromolecule membrane, using molecular structure exactly specifically as the refractive index anisotropic material.

In addition, phase-contrast film of the present invention can use as the various optical functional films that use in the liquid crystal indicator.Be phase-contrast film of the present invention optical compensation plate when using as negative C plate as described above for example, can be rightly in VA signal or OCB signal etc. has the liquid crystal indicator of liquid crystal layer, use.

The manufacture method of B, phase-contrast film

The manufacture method of phase-contrast film of the present invention comprises: painting process, and the phase differential strengthening region that dissolving or dispersion refractive index anisotropic material form in its solvent forms and is coated at least one surface of macromolecule membrane with coating liquid; Soak into operation, it makes the described phase differential strengthening region formation by described painting process coating be impregnated in the described macromolecule membrane with the described refractive index anisotropic material in the coating liquid; Drying process, it forms with the described solvent seasoning in the coating liquid the described phase differential strengthening region by described painting process coating.

Use accompanying drawing to specify the manufacture method of this phase-contrast film of the present invention.Fig. 6 is the process chart of expression phase-contrast film manufacture method one example of the present invention.Shown in Fig. 6 (a), at first carry out the coating phase differential strengthening region formation painting process that applies liquid 6 on macromolecule membrane 1.Shown in Fig. 6 (b), the phase differential strengthening region is formed with the described refractive index anisotropic material that applies in the liquid be impregnated into soaking into operation and the described phase differential strengthening region by described painting process coating is formed with the drying process that applies the described solvent seasoning in the liquid in the described macromolecule membrane then.Like this, described phase differential strengthening region forms with the refractive index anisotropic material in the coating liquid to be soaked into from the surface of macromolecule membrane, contains the phase differential strengthening region 2 of refractive index anisotropic material in the face side formation of macromolecule membrane.Like this, the phase differential strengthening region 2 of containing the refractive index anisotropic material and the matrix material zone 5 of not containing the refractive index anisotropic material in macromolecule membrane, have just been formed.Last shown in Fig. 6 (c), the curing process by make the refractive index anisotropic material that is included in the macromolecule membrane carry out polymerization from described phase differential strengthening region 2 side irradiation ultraviolet radiations 7 has so just formed phase-contrast film 8.

Manufacture method according to this phase-contrast film of the present invention, form with coating liquid and just can easily form phase-contrast film by being coated with described phase differential strengthening region, and only form the lagged value that just can change the phase-contrast film that obtains with the coating weight that applies liquid etc. by changing described phase differential strengthening region.Therefore according to the present invention, also can be had the advantage of the phase-contrast film of any lagged value easily even have few quantity.

Also can carry out each operation more than twice respectively.For example also can at first carry out the coating first phase differential strengthening region formation painting process that applies liquid on macromolecule membrane, the first phase differential strengthening region be formed with the first refractive index anisotropic material in the coating liquid be impregnated into soaking into operation and making the described first phase differential strengthening region formation drying process of the solvent seasoning in the coating liquid in the macromolecule membrane.Form and be coated with the second phase differential strengthening region again on the face with coating liquid one side and form being coated with the first phase differential strengthening region then with the painting process that applies liquid, the second phase differential strengthening region is formed with what the second refractive index anisotropic material in the coating liquid soaked into soak into operation and the described second phase differential strengthening region is formed with the solvent in the coating liquid and carry out dry drying process, and by carrying out the immobilization operation with a side that applies liquid and form phase-contrast film from being coated with the formation of the second phase differential strengthening region.If at this moment for example use and do not have easy rod shaped liquid crystal molecule to the polymerizable functional groups group that macromolecule membrane soaks into as the first refractive index anisotropic material, use rod shaped liquid crystal molecule with polymerizable functional groups group as the second refractive index anisotropic material, like this, macromolecule membrane just forms the zone of the rod shaped liquid crystal molecule that contains the polymerizable functional groups group with easier hardening constituent potential difference and contains the zone coexistence of the rod shaped liquid crystal molecule with polymerizable functional groups group in more close face side, can obtain having the phase differential of more strengthening, the macromolecule membrane surface is aggregated and the effect of stabilization by the immobilization operation simultaneously.Even use polymerizable functional groups group rod shaped liquid crystal molecule still less as the first refractive index anisotropic material, use polymerizable functional groups to roll into a ball more rod shaped liquid crystal molecule as the second refractive index anisotropic material, also can obtain and above-mentioned same effect.

The present invention coating phase differential strengthening region form with the described painting process of coating liquid and described soak into operation and described drying process after, also can have: dissolving in the solvent or disperse not to be the refractive index anisotropic material but to have operation, the operation that makes this coating liquid drying that coating liquid that the material of polymerizable functional groups group forms is coated with once more, the operation that the polymerizable functional groups reunion is closed.At this moment, do not have polymerizable functional groups group even for example be contained in the formation of phase differential strengthening region with the refractive index anisotropic material in the coating liquid, also carry out polymerization and curing and can prevent oozing out of refractive index anisotropic material, can pay film permanance and stability by the polymerizable functional groups group material that has that is present in the more close face side of macromolecule membrane.

Below press the manufacture method of every specification phase-contrast film of the present invention.

1, painting process

Painting process of the present invention is dissolving or disperse the phase differential strengthening region formation coating liquid that the refractive index anisotropic material forms in the solvent, being coated at least one lip-deep operation of macromolecule membrane.

The present invention utilizes the coating weight that the phase differential strengthening region forms with coating liquid in the painting process just can change the lagged value of the phase-contrast film that obtains.

Phase differential used in the present invention strengthening region forms with applying liquid to be contained solvent and dissolving at least or is dispersed in refractive index anisotropic material in the described solvent, is added other adjuvant as required.The Shi Zeneng that is light-cured type at employed refractive index anisotropic material particularly as this adjuvant enumerates Photoepolymerizationinitiater initiater etc.Enumerating of other: polymerization inhibitor, levelling agent, chirality agent, silane coupling agent etc.

As forming the refractive index anisotropic material that uses in the liquid with applying in described phase differential strengthening region, with in above-mentioned " A, phase-contrast film " hurdle, put down in writing identical, so in this description will be omitted.In addition, the refractive index anisotropic material is the material with polymerizable functional groups group, when in the manufacturing process of phase-contrast film, carrying out immobilization operation described later (make the polymerization of refractive index anisotropic material and form high molecular operation), the refractive index anisotropic material that is contained in the phase-contrast film carries out polymerization with the degree of polymerization of regulation, and therefore strict saying forms different with what use in the coating liquid with the phase differential strengthening region.

In addition, as the solvent of described phase differential strengthening region formation with the use of coating liquid, so long as can make the abundant swelling of macromolecule membrane, and the solvent of described refractive index anisotropic material dissolving or dispersion just is not particularly limited.Be exactly specifically macromolecule membrane be that TAC, refractive index anisotropic material are ends when having the nematic crystal of acrylate, be fit to use cyclohexanone.

The concentration that forms with refractive index anisotropic material in the coating liquid solvent as phase differential of the present invention strengthening region is not particularly limited, but normally in the scope of 5 quality %～40 quality %, is best in the scope of 15 quality %～30 quality % particularly.

As the coating weight on macromolecule membrane, different and different with the desired lagged value of the phase-contrast film that obtains, but the dried coating weight of refractive index anisotropic material is at 0.8g/m ²～8g/m ²Scope in, particularly at 1.6g/m ²～5g/m ²Scope in be best.

As long as the coating process of this operation is can form the phase differential strengthening region with applying liquid be coated on the lip-deep method of macromolecule membrane equably and just be not particularly limited, can use: rod is coated with method, scraper plate and is coated with that method, spin-coating method, mould are coated with method, slit is coated with methods such as method, rolling method, dip coating, ink-jet method, microgrid plate method.Especially preferably use scraper plate to be coated with that method, mould are coated with method, slit is coated with method and rolling method among the present invention.

2, soak into operation and drying process

The present invention carries out behind described painting process: soak into operation, it makes the described phase differential strengthening region formation by described painting process coating be impregnated in the described macromolecule membrane with the described refractive index anisotropic material in the coating liquid; Drying process, it forms with the described solvent seasoning in the coating liquid the described phase differential strengthening region by described painting process coating.

The described operation of soaking into is the operation of placing coating back macromolecule membrane for the refractive index anisotropic material fully is impregnated in the macromolecule membrane, but also can carry out simultaneously with drying process according to the use solvent types.

The described operation of soaking into preferably makes the formation of described phase differential strengthening region have more than 90% weight with the described refractive index anisotropic material in the coating liquid, is more preferably more than 95% weight, it is desirable to 100% weight especially and is impregnated in the macromolecule membrane all.This is owing to if described refractive index anisotropic material is not impregnated into to be remained in the macromolecule membrane on the macromolecule membrane surface for a long time, and then film surface thickens unclear and cause that light transmission rate film reduces sometimes.

Therefore, soak into drying process after macromolecule membrane, with JIS-K7105 be the surface of soaking into side the turbidity value of benchmark when measuring preferably below 10%, especially below 2%, particularly 1% below be ideal.

Described drying process is the phase differential strengthening region to be formed with the solvent in the coating liquid carry out dry operation, with the use solvent types with whether with soak into that operation is carried out simultaneously and temperature and time has significantly different.For example use cyclohexanone as solvent, and with soak into operation when carrying out simultaneously, normally with the temperature in room temperature～120 ℃, preferably 70 ℃～100 ℃ scopes, carry out drying process with the time about 30 seconds～10 minutes, preferably 1 minute～5 minutes.

3, immobilization operation

When employed refractive index anisotropic material has polymerizable functional groups group, then carry out the immobilization operation in order to make refractive index anisotropic material polymerization producing high-molecular.Can prevent to enter into the refractive index anisotropic material in the macromolecule membrane by this immobilization operation and ooze out, improve the stability of the phase-contrast film that obtains.

Immobilization operation of the present invention can make according to employed refractive index anisotropic material and in all sorts of ways.For example make it contain Photoepolymerizationinitiater initiater when the refractive index anisotropic material is cross-linked compound, irradiation ultraviolet radiation or irradiation electron ray are if heat-curable compounds then is to heat.

C, optical functional film

The following describes optical functional film of the present invention.Optical functional film of the present invention is to form by directly paste phase-contrast film optical functional layer in addition on the phase-contrast film that illustrates in above-mentioned " A, phase-contrast film " hurdle.

Optical functional layer of the present invention so long as in using the various uses of phase-contrast film of the present invention with phase-contrast film synergy of the present invention the comprehensive optical function of wishing realized, just there is no particular limitation.For example can enumerate for optical functional layer of the present invention: prevent reflection horizon, UV-absorbing layer, infrared ray absorbing layer etc.

Therefore, optical functional film of the present invention is to have the function of the phase-contrast film that illustrates in above-mentioned " A, phase-contrast film " hurdle and the film of above-mentioned each optical function layer function simultaneously.Optical functional film of the present invention is not because with other functions that just have the function that phase-contrast film of the present invention was had such as optical compensation for example simultaneously and for example prevent to reflect etc., therefore having needs indivedual settings to have the advantage of each function film.

As preventing that there is no particular limitation in the reflection horizon, but for example can enumerate: on the transparent base material film, form by the low-index layer that constitutes than this transparent base material low-refraction material, or the low-index layer that constitutes the high refractive index layer that constitutes by material with by material on the transparent base material film than this transparent base material low-refraction than this transparent base material high index of refraction by this sequence alternate ground each more than laminated one deck etc.These high refractive index layers and low-index layer are according to forming in the long-pending represented optical thickness of geometric thickness of layer and refractive index 1/4 mode for the light wavelength that should prevent to reflect by vacuum evaporation, coating etc.Constituent material as high refractive index layer can use titanium dioxide, zinc sulphide etc., can use magnesium fluoride, cryolite etc. as the constituent material of low-index layer.

There is no particular limitation as UV-absorbing layer, but for example can enumerate: add the ultraviolet light absorber that is made of benzotriazole based compound, benzophenone based compound, salicylate based compound etc. and carry out film forming in films such as vibrin, acrylic resin.

There is no particular limitation as the infrared ray absorbing layer, but for example can enumerate: form by coating infrared ray absorbing layer on film matrix materials such as vibrin.For example can use the infrared absorbent of formations such as two imido (diimmonium) based compound, phthalocyanine based compound added to as the infrared ray absorbing layer and carry out film forming in the adhesive resin that constitutes by acrylic resin, vibrin etc.

First form of phase-contrast film described in the present invention, the concentration gradient that is the refractive index anisotropic material is that a face side at macromolecule membrane is a high concentration and just become the concentration gradient of low concentration towards another face side, and another face side is that such phase-contrast film of matrix material regional morphology is used by suitable.Though this is because also according to the kind of the employed macromolecule membrane of phase-contrast film and difference, mostly the face that does not have refractive index anisotropic material one side is the cause good with the cementability of optical functional layer.

D, polarized light film

The following describes polarized light film of the present invention.Polarized light film of the present invention is by being the polarization photosphere that bonding agent is directly pasted and formed with polyvinyl alcohol (PVA) (PVA) on the phase-contrast film that illustrates in above-mentioned " A, phase-contrast film " hurdle.

Polarized light film is formed with the protective seam on polarization photosphere and its two surface usually, and the present invention is an above-mentioned phase-contrast film and can for example manufacture the polarized light film with optical compensation function by the protective seam of one side is made for example.

There is no particular limitation as the polarization photosphere, but for example can use: iodine is that the dyestuff of polarization photosphere, use dichroic dye is that polarization photosphere and polyenoid are polarization photosphere etc.Iodine is that polarization photosphere and dyestuff are that the polarization photosphere generally is to use the polyvinyl alcohol (PVA) manufacturing.

Suitable first form of using described phase-contrast film among the present invention, the concentration gradient that is the refractive index anisotropic material is a high concentration for a face side at macromolecule membrane, and just becomes the phase-contrast film of the concentration gradient form of low concentration towards another face side.The polarization photosphere is many by the situation that polyvinyl alcohol (PVA) (PVA) constitutes usually, though this is owing in this case also according to the kind of the employed macromolecule membrane of phase-contrast film and different, do not have the good cause of cementability of the face of refractive index anisotropic material one side.

D, display device

Display device of the present invention is described at last.For example can enumerate as display device of the present invention: liquid crystal indicator, organic EL display etc.

First form of display device of the present invention is characterised in that, the phase-contrast film of the invention described above is configured on the light path.Display device of the present invention problem such as is not peeled off by configuration and is had the phase-contrast film of suitable hysteresis and the reliability height, and display quality is good.

Fig. 7 is the stereographic map of liquid crystal indicator one example in the expression display device of the present invention.As shown in Figure 7, liquid crystal indicator 20 of the present invention has the side of injecting polaroid 102A, emitting side polaroid 102B and liquid crystal cells 104. Polaroid 102A and 102B constitute and only make the rectilinearly polarized light selective permeation with regulation direction of vibration vibration plane, make separately direction of vibration be in right-angle relationship ground and dispose relatively with the crossed nicols state.Liquid crystal cells 104 is the liquid crystal cells that comprise a plurality of unit corresponding with pixel, is configured between polaroid 102A and the 102B.

At this, liquid crystal cells 104 adopts sealed VA (Vertical Alignment) mode of nematic crystal with negative induced anisotropy in the liquid crystal indicator 20, when having seen through the cell mesh of the rectilinearly polarized light of injecting side polaroid 102A non-driven state in seeing through liquid crystal cells 104, do not carry out phase-shifts ground and see through and interdicted by emitting side polaroid 102B.Relatively in seeing through liquid crystal cells 104 during the cell mesh of driving condition, rectilinearly polarized light carries out phase-shifts, with the light transmission emitting side polaroid 102B of this phase-shifts amount respective amount and penetrate.Like this, just can show the image of wishing by driving voltage in emitting side polaroid 102B side to the suitable control in each each unit liquid crystal cells 104.

The light path configuration described of the present invention phase-contrast film 10 of the liquid crystal indicator 20 of this structure between liquid crystal cells 104 and emitting side polaroid 102B (seeing through the polarisation of light sheet of the regulation polarized light state that penetrates from liquid crystal cells 104 selectively), by phase-contrast film 10 can compensate from the light of the regulation polarized light state of liquid crystal cells 104 ejaculations to the polarisation of light light state of the normal slope direction ejaculation of liquid crystal cells 104.

As above, liquid crystal indicator 20 according to said structure, owing between the liquid crystal cells 104 of liquid crystal indicator 20 and emitting side polaroid 102B, disposed the high phase-contrast film 10 of the invention described above reliability, compensated the polarisation of light light state that from the light that liquid crystal cells 104 penetrates, penetrates to normal slope direction with liquid crystal cells 104, so can improve the view angle dependency problem of liquid crystal indicator 20 effectively, display quality is good and reliability is high.

Liquid crystal indicator 20 shown in Figure 7 is infiltration types that light is seen through from a side direction opposite side of thickness direction, but the example of display device of the present invention is not limited thereto, and the phase-contrast film 10 of the invention described above similarly also can be assembled in the reflection-type liquid-crystal display device and use.And similarly also can be assembled in the light path of other display device as described above and use.

Liquid crystal indicator 20 shown in Figure 7 is that the phase-contrast film 10 of the invention described above is configured between liquid crystal cells 104 and the emitting side polaroid 102B, but also can be configured in liquid crystal cells 104 to phase-contrast film 10 and inject between the side polaroid 102A according to the form of optical compensation.And also can phase-contrast film 10 be configured in liquid crystal cells 104 both sides (liquid crystal cells 104 and inject between the side polaroid 102A and liquid crystal cells 104 and emitting side polaroid 102B between).In addition, be configured in liquid crystal cells 104 and inject between the side polaroid 102A or be configured in liquid crystal cells 104 and emitting side polaroid 102B between phase-contrast film to be not limited to be one, but also can dispose a plurality of.And also can be configured in other optical functional films on the light path.

Second form of display device of the present invention is characterised in that, the optical functional film of the invention described above is configured on the light path.So just do not need setting in addition to have the above-mentioned phase-contrast film optical function plate of function in addition, can obtain the good display device of reliability height and display quality.

Fig. 8 is the stereographic map of liquid crystal indicator one example in the expression display device of the present invention.As shown in Figure 8, liquid crystal indicator 30 of the present invention has the side of injecting polaroid 102A, emitting side polaroid 102B and liquid crystal cells 104. Polaroid 102A, 102B and liquid crystal cells 104 can use with above-mentioned Fig. 7 same, are the configurations same with Fig. 7.

The liquid crystal indicator 30 of this structure disposes described optical functional film of the present invention 40 on the light path between liquid crystal cells 104 and the emitting side polaroid 102B, there is no particular limitation for the function that this optical functional film had in the lump, but in optical compensation function, have in the lump when absorbing ultraviolet function, can compensate the polarisation of light light state that penetrates to normal slope direction the light of the regulation polarized light state that penetrates from liquid crystal cells 104 with liquid crystal cells 104 by optical functional film 40, and can absorb the ultraviolet ray that originally just has the daylight in liquid crystal indicator, injected from the outside etc., can improve the photostability of liquid crystal indicator.

As above, liquid crystal indicator 30 according to said structure, because liquid crystal indicator 30 has disposed the high optical functional film 40 of the invention described above reliability between liquid crystal cells 104 and emitting side polaroid 102B, compensated the polarisation of light light state that from the light that liquid crystal cells 104 penetrates, penetrates to normal slope direction with liquid crystal cells 104, so can improve the view angle dependency problem of liquid crystal indicator 30 effectively, and for example can improve photostability by absorbing ultraviolet function, display quality is good.

The example of display device of the present invention is not limited thereto, and the optical functional film 40 of the invention described above similarly also can be assembled in the reflection-type liquid-crystal display device and use.And similarly also can be assembled in the light path of other display device as described above and use.

Liquid crystal indicator 30 shown in Figure 8 is that the optical functional film 40 of the invention described above is configured between liquid crystal cells 104 and the emitting side polaroid 102B, but according to optical compensation and have function in the lump form also can be configured in liquid crystal cells 104 to optical functional film 40 and inject between the side polaroid 102A.And also can optical functional film 40 be configured in liquid crystal cells 104 both sides (liquid crystal cells 104 and inject between the side polaroid 102A and liquid crystal cells 104 and emitting side polaroid 102B between).Also optical functional film 40 can be configured in the outside (face side) of emitting side polaroid 102B.In addition, be configured in liquid crystal cells 104 and inject between the side polaroid 102A or be configured in liquid crystal cells 104 and emitting side polaroid 102B between or the film that is configured in the emitting side polaroid 102B outside to be not limited to be one, but also can dispose a plurality of.

The 3rd form of display device of the present invention is characterised in that, the polarized light film of the invention described above is configured on the light path.So just do not need to be provided with in addition optical compensation plate, can obtain the good display device of reliability height and display quality.

Fig. 9 is the stereographic map of liquid crystal indicator one example in the expression display device of the present invention.As shown in Figure 9, liquid crystal indicator 50 of the present invention has polarized light film of the present invention 60 and the liquid crystal cells 104 of injecting side polaroid 102A, emitting side.Polaroid 102A and polarized light film of the present invention 60 constitute, and the rectilinearly polarized light with regulation direction of vibration vibration plane is seen through, and make separately direction of vibration be in right-angle relationship ground and dispose relatively with the crossed nicols state.In addition, liquid crystal cells 104 can use identical with Fig. 7, is configured between polaroid 102A and the polarized light film of the present invention 60.

Liquid crystal indicator 50 according to said structure, owing between the liquid crystal cells 104 of liquid crystal indicator 50 and emitting side, disposed the high polarized light film 60 of the invention described above reliability, compensated the polarisation of light light state that from the light that liquid crystal cells 104 penetrates, penetrates to normal slope direction with liquid crystal cells 104, so can improve the view angle dependency problem of liquid crystal indicator 50 effectively, display quality is good and reliability is high.

The example of display device of the present invention is not limited thereto, and the polarized light film 60 of the invention described above similarly also can be assembled in the reflection-type liquid-crystal display device and use.And similarly also can be assembled in the light path of other display device as described above and use.

In addition, liquid crystal indicator 50 shown in Figure 9 is that the polarized light film 60 of the invention described above is configured between liquid crystal cells 104 and the emitting side, but also can be the side of injecting that is configured in liquid crystal cells 104 according to the form of optical compensation.And also can be polarized light film 60 and 60 ' the be configured in both sides of liquid crystal cells 104.In addition, at liquid crystal cells 104 and inject between the side polaroid 102A or also configuration phase difference film or other optical functional films in addition between liquid crystal cells 104 and the emitting side polarized light film 60.

Below only be that example is illustrated with the liquid crystal indicator, but above-mentioned phase-contrast film of the present invention and polarized light film also can use in other display device, for example can also enumerate having above-mentioned phase-contrast film of the present invention of circular polarizing disk function or polarized light film to be configured in organic EL display on the light path.

The present invention is not limited to above-mentioned embodiment, and above-mentioned embodiment is an illustration, has same structure in fact with the technological thought of patent claimed range of the present invention record and the same purpose effect is arranged, and also is included in the technical scope of the present invention.

Embodiment

Below show embodiment and specify the present invention.

(embodiment 1)

As the refractive index anisotropic material optical polymerism liquid-crystal compounds (following compound (1)) is dissolved in the cyclohexanone with 20% quality, utilizing rod to be coated with method is coated in by TAC film (Fuji Photo Film Co., Ltd.'s system, trade name TF80UL) on the matrix material film surface of Gou Chenging, making dried coating weight is 2.5g/m ²Solvent seasoning was removed in 4 minutes with 90 ℃ of heating then, this optical polymerism liquid-crystal compounds is soaked in this TAC film.Further, by make the immobilization of described optical polymerism liquid-crystal compounds to the coated face irradiation ultraviolet radiation, produce phase-contrast film.The phase-contrast film that obtains is carried out the evaluation of following project as sample.

[chemical formula 3]

1, optical characteristics

By automatic double refraction detection device (prince's instrumentation machine Co., Ltd. system, trade name: KOBRA-21ADH) measured the phase differential of sample.Make that to measure light vertical or tilt to inject to sample surfaces, according to its optical phase difference with measure the chart that light is injected angle, the anisotropy of having confirmed to make the phase differential of matrix material film to increase.And utilize with determinator and measured 3 dimension refractive indexes.Be nx, ny consequently setting with the refractive index of the surperficial parallel in-plane of matrix material film, when the setting of the refractive index of thickness direction is nz, nz＜nx=ny sets up like that shown in following table 1, owing to become negative C plate, so work as contrast with top measuring difference of phases result, then think: the direction of orientation of liquid crystal molecule is have liquid crystal molecule in the face parallel with the matrix material film surface, and the direction of orientation in this face to be even (homogeneous) orientation at random.

Table 1

N X	1.6
		N Y	1.6
N Z	1.5

2, the SEM section is observed

Embeding resin is coated on the liquid crystal applicator surface of sample and on thickness direction, cuts off, by the section of SEM observation sample.The result is illustrated in Figure 10.As recognizing from Figure 10, between sample surfaces and embeding resin, do not have layer, with top measuring difference of phases result contrast, then judge and in macromolecule membrane, soaked into liquid-crystal compounds.

3, the TEM section is observed

The liquid crystal applicator surface of sample is carried out the surface protection of metal oxide, carry out being bonded on the low temperature brace table after the epoxy resin embedding.Carry out deburring/surperficial centering by cryogenic system with the ultra micro microtome that diamond tool is installed then, implement the steam dyeing of metal oxide, carrying out carrying out tem observation after ultra-thin section is made.The result is illustrated in Figure 11.As recognizing from Figure 11, the refractive index anisotropic material of having known sample soaks into side and is divided into three layers (zone line in the area with high mercury in the phase differential strengthening region, the phase differential strengthening region and matrix material zones).

4, turbidity

In order to investigate the transparency of sample, using nephelometer (Japanese electric look Industrial Co., Ltd system, trade name NDH2000) is that benchmark has been measured turbidity value with JIS-K7105.Consequently 0.35%, good.

5, being adjacent to property test

Carried out disbonded test in order to investigate being adjacent to property.As disbonded test is the square slit of 1mm of marking the go plate-like on the sample that obtains, and splicing tape (ニ チ バ Application Co., Ltd. system, glass paper tape (login trade mark)) is sticked on the liquid crystal face, then band is peeled off, and uses visualization.Consequently degree of being adjacent to 100%.

Degree of being adjacent to (%)=(part of not being stripped from/pasted the zone of band) * 100

6, hot resistance test-1

Sample was immersed in 90 ℃ the hot water 60 minutes, and measured optical characteristics and being adjacent to property by said method.Optical characteristics does not have change with being adjacent to property before and after consequently the test of discovery.

7, hot resistance test-2

Sample was left standstill 24 hours under 80 ℃, the environment of humidity 95%, measure optical characteristics and being adjacent to property by said method.Optical characteristics does not have change with being adjacent to property before and after consequently the test of discovery.And even oozing out of refractive index anisotropic material arranged after test, do not find gonorrhoea yet.

8, water resistant test

Sample was immersed under room temperature (23.5 ℃) in the pure water one day, measures optical characteristics and being adjacent to property by said method.Optical characteristics does not have change with being adjacent to property before and after consequently the test of discovery.

9, alkaline resistance test

Sample was immersed under 55 ℃ in the aqueous alkali (sodium hydrate aqueous solution of 1.5N) 3 minutes, and wash, drying, measure optical characteristics and being adjacent to property by said method.Optical characteristics does not have change with being adjacent to property before and after consequently the test of discovery.And yet and do not find to be colored.

10, the material concentration measure of spread of thickness direction

By GSP (accurate inclined cutting method) phase-contrast film is cut off the section that exposes thickness direction, use flight time type secondary ion mass spectrometry meter (TOF-SISM) (device: the TFS-2000 of PhysicalElectronics society system) measure face of tool thickness direction concentration of material and distribute.Condition determination is: secondary ion polarity is that positive and negative, mass range (M/Z) are 0～1000, raster size is that 180 μ m, minute are that 3 minutes, noenergy filtrator, contrast diaphragm (constrast diaphragm) are that to quicken be 5kV, measure vacuum tightness is 4 * 10 for 0#, back segment ^-7Pa (3 * 10 ^-9Torr), the primary ions kind is Ga ⁺, the primary ions energy be 25kV, sample current potential be+3.2kV, pulsed frequency are that 8.3kHz, pulse width are 12ns, do not have pack, are that charged neutralization, temporal resolution (time resolution) they are 1.1ns/ch.

As measurement result, in positive secondary ion spectrum, the coated face at the refractive index anisotropic material be measured to strongly 27,55,104,121,275amu is as the peak value from the refractive index anisotropic material, be measured to strongly at the reverse side that does not have coating 15,43,327amu is as the peak value from the TAC film, these peak strengths separately and carried out normalized value as the longitudinal axis with total secondary ion intensity, the coated face of refractive index anisotropic material as zero thickness direction as transverse axis, distribution curve is illustrated in Figure 12.But because 27,55amu also observes from the TAC film and obtaining, so in the part contribution that also comprises the TAC film as the positive secondary ion place from the peak value of refractive index anisotropic material.

In addition, similarly in negative secondary ion spectrum, the coated face at the refractive index anisotropic material be measured to strongly 13,26,118,217amu is as the peak value that comes from the refractive index anisotropic material, be measured to strongly at the reverse side that does not have coating 16,59amu is as the peak value that comes from the TAC film, these peak strengths separately and carried out normalized value as the longitudinal axis with total secondary ion intensity, the coated face of refractive index anisotropic material as zero thickness direction as transverse axis, distribution curve is illustrated in Figure 13.But obtain, so also comprise the part contribution of TAC film from the positive secondary ion place of the peak value of refractive index anisotropic material in conduct owing to 13amu also observes from the TAC film.

In the thickness direction distribution plan result of positive secondary ion spectrum and negative secondary ion spectrum, recognize: from coated face near the 1.5 μ m all being the zone that concentration ratio is higher and concentration gradient is mild of refractive index anisotropic material, 1.5 near the μ m～3 μ m near refractive index have the concentration decay of anisotropic material and the steep anxious zone of concentration gradient, and from there being the matrix material zone that contains the refractive index anisotropic material hardly near the 3 μ m.This soaks into the section observations by TEM that side is divided into three layers (zone line in the area with high mercury in the phase differential strengthening region, the phase differential strengthening region and matrix material zones) with the refractive index anisotropic material is consistent.

(embodiment 2)

Identical with embodiment 1 except the mixed solvent (ratio of solvent 7:1) that the solvent among the embodiment 1 is become cyclohexanone and butanone (MEK), make phase-contrast film.The phase-contrast film that obtains is carried out optical characteristics, being adjacent to property, hot resistance test and water resistant test similarly to Example 1, and the result has obtained the result identical with embodiment 1.

(embodiment 3)

Except the mixed solvent (ratio of solvent 7:1) that the solvent among the embodiment 1 become cyclohexanone and MEK, coating process become mould be coated with the method identically with embodiment 1, make phase-contrast film.The phase-contrast film that obtains is estimated similarly to Example 1, and the result has obtained the result identical with embodiment 1.

(embodiment 4)

The surface, phase differential strengthening region of the phase-contrast film that obtains from embodiment 1 and the contact angle of matrix material region surface are measured.Just be to use contact angle determination device (consonance interface science Co., Ltd. system, CA-Z type) to measure surface, phase differential strengthening region and matrix material region surface (TAC face) contact angle specifically for pure water.Contact angle is that the pure water of 0.1ml is measured after the mensuration face dripped 30 seconds.Consequently surface, phase differential strengthening region is 62.6 °, and the matrix material region surface is 57.3 °, and surface, phase differential strengthening region is high value, is not the result of the surperficial possess hydrophilic property of phase differential strengthening region.

(embodiment 5)

In embodiment 1, dried coating weight become 2.0,2.6,3.2,3.8g/m ²Make sample, carry out same evaluation.Consequently obtain same result.And (in the lagged value with 30 ° of goniometries of relative normal direction: 30 ° of Re) linear relationship is as shown in Figure 14 arranged, it is poor to recognize with coating weight energy control phase to find coating weight and phase differential.

(embodiment 6)

Be dissolved in optical polymerism liquid-crystal compounds (following compound (1)) in the mixed solvent (ratio of solvent 9:1) of cyclohexanone and n-propanol with 20% quality as the refractive index anisotropic material, utilizing rod to be coated with method is coated in by TAC film (Fuji Photo Film Co., Ltd.'s system, trade name TF80UL) on the matrix material film surface of Gou Chenging, making dried single face coating weight is 1g/m ², carry out two sided coatings.Solvent seasoning was removed in 4 minutes with 70 ℃ of heating then, this optical polymerism liquid-crystal compounds is soaked in this TAC film.In addition, by make the immobilization of described optical polymerism liquid-crystal compounds to the coated face irradiation ultraviolet radiation.

By automatic double refraction detection device (prince's instrumentation machine Co., Ltd. system, trade name: KOBRA-21ADH) measured the phase differential of sample.Make that to measure light vertical or tilt to inject to sample surfaces, the anisotropy of having confirmed to make the phase differential of matrix material film to increase according to its optical phase difference and the chart of injecting angle of measuring light.What Figure 15 represented is phase differential angle dependence.

In addition, measured turbidity value similarly to Example 1, the result is 0.7%.

(embodiment 7)

Except dried coating weight is become single face 3g/m ², identical with embodiment 6 beyond the single face of matrix material film is coated with, be made into phase-contrast film.

By automatic double refraction detection device (prince's instrumentation machine Co., Ltd. system, trade name: KOBRA-21ADH) measured the phase differential of sample.Figure 15 has represented phase differential angle dependence in the lump.

In addition, measured turbidity value similarly to Example 1, the result is 0.5%.

Embodiment 6 and embodiment 7 are compared then as shown in Figure 15 as can be known, under situation about obtaining with the degree phase differential, when the phase differential strengthening region being set to two sided coatings and on the two sides than only to single face coating and when single face is provided with the phase differential strengthening region, have the advantage of total coating weight that can reduce the refractive index anisotropic material.

(embodiment 8)

Be dissolved in the cyclohexanone with 20% quality as refractive index anisotropic material handle and embodiment 1 identical optical polymerism liquid-crystal compounds (following compound (1)), be coated in the long size of width 650mm, length 30m by TAC film (Fuji Photo Film Co., Ltd.'s system, trade name TF80UL) on the matrix material film surface of Gou Chenging, making each dried coating weight is 3g/m ²Solvent seasoning was removed in 4 minutes with 90 ℃ of heating then, this optical polymerism liquid-crystal compounds is soaked in this TAC film.In addition, by make the immobilization of described optical polymerism liquid-crystal compounds to the coated face irradiation ultraviolet radiation, make phase-contrast film of the present invention.The long size phase-contrast film that is cut into 3m as the form that is wound into minimum diameter 31mm drum, was preserved one month down at 23 ℃.There is change on the surface of consequently not finding phase-contrast film before and after preserving, do not crack, and does not also paste between the wound film.

(embodiment 9)

As the refractive index anisotropic material optical polymerism liquid-crystal compounds (following compound (1)) is dissolved in the cyclohexanone with 20% quality, utilize rod to be coated with method and be coated in unilateral stretching COP (cyclic olefin polymer) film (JSR Corp.'s system, trade name ARTON) on, coating weight is 3g/m ²Removed in 2 minutes with 50 ℃ of heating then and desolvate.In addition,, residual solvent was removed in 2 minutes, produced phase-contrast film with 90 ℃ of heating by make the immobilization of described optical polymerism liquid-crystal compounds to the coated face irradiation ultraviolet radiation.The phase-contrast film that obtains is carried out the evaluation of following project as sample.

1, optical characteristics

By automatic double refraction detection device (prince's instrumentation machine Co., Ltd. system, trade name: KOBRA-21ADH) measured the phase differential of sample.Make that to measure light vertical or tilt to inject to sample surfaces, the anisotropy of having confirmed to make the phase differential of matrix material film to increase according to its optical phase difference and the chart of injecting angle of measuring light.And utilize with determinator and measured 3 dimension refractive indexes.Its result is indicated on table 2.

Table 2

N X	1.59
		N Y	1.56
N z	1.53

2, observe by the section of SEM

Result by SEM observation sample section is illustrated in Figure 16.As recognizing from Figure 16, there is not the border of phase differential strengthening region and macromolecule membrane in the sample, with top measuring difference of phases result contrast, then judge and in macromolecule membrane, soaked into liquid-crystal compounds.

3, turbidity

In order to investigate the transparency of sample, measured turbidity value by method similarly to Example 1.Consequently below 0.3%, good.

4, being adjacent to property test

In order to investigate being adjacent to property, carried out disbonded test by method similarly to Example 1.Consequently degree of being adjacent to 100%.

5, hot resistance test

By having carried out hot resistance test with the same method of the hot resistance test-1 of embodiment 1.Optical characteristics does not have change with being adjacent to property before and after consequently the test of discovery.

6, water resistant test

Carried out water resistant test by method similarly to Example 1.Optical characteristics does not have change with being adjacent to property before and after consequently the test of discovery.

(embodiment 10)

Upward make phase-contrast film by method similarly to Example 9 at the COP film that do not stretch (JSR Corp.'s system, trade name ARTON).Carry out evaluation similarly to Example 9, the result is except optical characteristics (3 dimension refractive index) becomes the result shown in the table 3, has obtained result similarly to Example 9.

Table 3

N X	1.56
		N Y	1.56
N z	1.55

Phase-contrast film of the present invention for example can utilize on optical functional film purposes such as optical compensation plate (for example viewing angle compensation plate), ellipsoidal polarizing plate, brightness raising plate.

Claims (23)

1. phase-contrast film, be to contain at macromolecule membrane to have the phase-contrast film that the anisotropic material of refractive index forms, it is characterized in that, it is described that to have the anisotropic material of refractive index be the material with polymerizable functional groups group, and this has the anisotropic material of refractive index and have concentration gradient on the thickness direction of described macromolecule membrane

It is described that to have the anisotropic material of refractive index be the material that had liquid crystal liquid crystal property before carrying out polymerization between the described polymerizable functional groups group.

2. phase-contrast film, be to contain at macromolecule membrane to have the phase-contrast film that the anisotropic material of refractive index forms, it is characterized in that, it is described that to have the anisotropic material of refractive index be the material with polymerizable functional groups group, and this has the anisotropic material of refractive index and have concentration gradient on the thickness direction of described macromolecule membrane, and this concentration gradient changes continuously

It is described that to have the anisotropic material of refractive index be the material that had liquid crystal liquid crystal property before carrying out polymerization between the described polymerizable functional groups group.

3. phase-contrast film as claimed in claim 1 or 2 is characterized in that described macromolecule membrane has regularity on refractive index.

4. phase-contrast film as claimed in claim 1 or 2 is characterized in that, described molecular structure with the anisotropic material of refractive index is bar-shaped.

5. phase-contrast film as claimed in claim 1 or 2 is characterized in that, described polymerizable functional groups group be can be 3 D cross-linked polymerizable functional groups group.

6. phase-contrast film as claimed in claim 1 or 2 is characterized in that, described to have the anisotropic material of refractive index be that molecular structure is bar-shaped and has the material of polymerizable functional groups group endways.

7. phase-contrast film as claimed in claim 1 or 2, it is characterized in that, described have the concentration gradient of the anisotropic material of refractive index on described macromolecule membrane thickness direction, be that a face side at described macromolecule membrane is a high concentration, and just become the concentration gradient of low concentration towards another face side.

8. phase-contrast film as claimed in claim 7 is characterized in that, described phase-contrast film is that a surface is different with another surface for the contact angle of pure water.

9. phase-contrast film as claimed in claim 1 or 2, it is characterized in that, described have the concentration gradient of the anisotropic material of refractive index on described macromolecule membrane thickness direction, be that two face side at described macromolecule membrane are high concentrations, and just become the concentration gradient of low concentration towards central portion.

10. phase-contrast film as claimed in claim 1 or 2 is characterized in that, it has described have mild zone of the anisotropic concentration of material gradient of refractive index and described zone with the steep urgency of the anisotropic concentration of material gradient of refractive index.

11. phase-contrast film as claimed in claim 1 or 2 is characterized in that, it has and does not contain described zone with the anisotropic material of refractive index.

12. phase-contrast film as claimed in claim 1 or 2, it is characterized in that, if the hysteresis longitudinal refractive index of the interior direction of the face of described film is set at nx, the leading longitudinal refractive index of direction in the face of film is set at ny, the refractive index of the thickness direction of film is set at nz, is thickness setting d, using Rth[nm]=(nx+ny)/and it is thickness direction when lagging behind that Rth that 2-nz} * d represents is set at, it is 70～300nm that described thickness direction lags behind.

13. phase-contrast film as claimed in claim 1 or 2 is characterized in that, is that the turbidity value of benchmark when measuring is below 1% with JIS-K7105.

14. phase-contrast film as claimed in claim 1 or 2 is characterized in that, the lagged value of described phase-contrast film in the visible region be short wavelength side greater than long wavelength side.

15. phase-contrast film as claimed in claim 1 or 2 is characterized in that, the lagged value of described phase-contrast film in the visible region be long wavelength side greater than short wavelength side.

16. phase-contrast film as claimed in claim 1 or 2, it is characterized in that, if the hysteresis longitudinal refractive index of direction in the face of described phase-contrast film is set at nx, the leading longitudinal refractive index of direction in the face of film is set at ny, the refractive index of the thickness direction of film is set at nz, is thickness setting d, using Rth[nm]=(nx+ny)/it is that thickness direction is when lagging behind that Rth that 2-nz} * d represents is set at, the thickness direction of measuring the described phase-contrast film obtain with wavelength 550nm lags behind in the deviation of pellicular front direction, with the mean value of Rth as benchmark in the scope of ± 5nm.

17. phase-contrast film as claimed in claim 1 or 2 is characterized in that, it can be wound into the drum of minimum diameter below 6 inches.

18. a phase-contrast film is characterized in that, its claim 1 or 2 described individual layer phase-contrast films are fitted mutually and are formed more than two.

19. an optical functional film is characterized in that, the optical functional layer beyond its claim 1 or 2 described phase-contrast films and the phase-contrast film is directly fitted and is formed.

20. a polarized light film is characterized in that, its claim 1 or 2 described phase-contrast films and polarization photosphere are directly fitted and are formed.

21. a display device is characterized in that, its claim 1 or 2 described phase-contrast films are configured on the light path.

22. a display device is characterized in that, the described optical functional film of its claim 19 is configured on the light path.

23. a display device is characterized in that, the described polarized light film of its claim 20 is configured on the light path.

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