CN100405183C - Manufacturing method of elliptical polarizing plate and image display use same - Google Patents
Manufacturing method of elliptical polarizing plate and image display use same Download PDFInfo
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- CN100405183C CN100405183C CNB200610057732XA CN200610057732A CN100405183C CN 100405183 C CN100405183 C CN 100405183C CN B200610057732X A CNB200610057732X A CN B200610057732XA CN 200610057732 A CN200610057732 A CN 200610057732A CN 100405183 C CN100405183 C CN 100405183C
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Abstract
The present invention provides a method of producing an elliptically polarizing plate including the steps of: forming a first birefringent layer on a surface of a transparent protective film; laminating a polarizer on a surface of the transparent protective film; forming a second birefringent layer on a surface of the first birefringent layer; and forming a third birefringent layer on a surface of the second birefringent layer. The first birefringent layer is arranged on the opposite side against the polarizer with respect to the transparent protective film. The step of forming the first birefringent layer includes the steps of: applying a liquid crystal material onto a substrate subjected to an alignment treatment; treating the applied liquid crystal material, so as to form the first birefringent layer on the substrate; and transferring the first birefringent layer onto a surface of the transparent protective film.
Description
The application is based on federal code the 35th chapter the 119th joint, requires the right of priority of the Japanese patent application submitted on February 25th, 2005 2005-51348 number, is hereby incorporated by.
Technical field
The present invention relates to a kind of method of making elliptical polarization plate, and relate to the image display that uses this elliptical polarization plate.More particularly, the present invention relates to a kind ofly have excellent oblique optical property and between adjacent film (layer), have the fusible broadband of excellence and the method for the elliptical polarization plate at wide visual angle with very high efficient manufacturing, relate to a kind of elliptical polarization plate that obtains by this method, and relate to the image display that uses this elliptical polarization plate.
Background technology
Various bloomings with light polarizing film and polarizer (retardation plate) combination are generally used for various image displays, LCD and electroluminescence (EL) display for example, thus obtain optical compensation.
Usually, circular Polarizer is a kind of in the blooming, can by with light polarizing film and quarter wave plate (λ/4 plates hereinafter referred to as) in conjunction with forming.But λ/4 plates have the characteristic that bigger phase difference value is provided with short wavelength, promptly so-called " positive wavelength dispersion characteristics ", and λ/4 plates have high positive wavelength dispersion characteristics usually.Therefore, the problem of λ/4 plates is that it can not demonstrate desired optical (for example function of λ/4 plates) in wide wavelength coverage.For fear of this problem, recommend a kind of polarizer recently, it has the wavelength dispersion characteristics that bigger phase difference value is provided with long wavelength, promptly so-called " inverse loose characteristic ", for example polynorbornene basement membrane or modified polycarbonate basement membrane.But such film exists the problem of cost.
At present, λ/4 plates that will have a positive wavelength dispersion characteristics combine with polarizer or half-wave plate (λ/2 plates hereinafter referred to as) that bigger phase difference value is provided with long wavelength, thereby correct the wavelength dispersion characteristics (for example, referring to JP 3174367B) of λ/4 plates.
Under harden the situation of closing in light polarizing film, λ/4 plates and λ/2 as mentioned above, the angle of optic axis separately, promptly the angle between the slow axis of the absorption axes of light polarizing film and each polarizer must be adjusted.But each optic axis by stretch film formed light polarizing film and polarizer changes according to draw direction usually.Each film must cut and lamination according to the direction of optic axis separately, thereby makes rete long-pending so that absorption axes and slow axis are in desired angle.More particularly, the absorption axes of light polarizing film is parallel with its draw direction usually, and the slow axis of polarizer is also parallel with its draw direction.Therefore, be that angle between absorption axes and the slow axis is 45 ° for example in order to make light polarizing film and polarizer lamination, a kind of in this film must be cut with 45 ° of directions with respect to vertical (draw direction) of film.As mentioned above under the situation that film cuts and adheres to subsequently, for example, angle between the optic axis can change with respect to every kind of film that cut, and this may cause about the problem of the mass discrepancy of every kind of product and production cost is high and the problem of length consuming time.Further problem comprises waste product increase that causes owing to the cutting film and the difficulty of making large-scale film.
As the countermeasure of these problems, proposed a kind of by waiting the method (for example, referring to JP2003-195037A) of regulating draw direction in oblique extension light polarizing film or polarizer.But the problem of this method is that this regulative mode has difficulties.
In addition, the circular Polarizer that comprises the combination of light polarizing film, λ/4 plates and λ/2 plates has another problem.Particularly, triacetyl cellulose (TAC) is used as the protective seam of light polarizing film usually.In many cases and since the TAC film the phase differential of intrinsic thickness direction, can not be in the gratifying circular polarisation function of oblique acquisition.
Summary of the invention
Carry out the present invention in order to solve aforesaid traditional problem, therefore an object of the present invention is to provide: a kind of have excellent oblique optical property and have the method for the elliptical polarization plate at excellent fusible broadband, wide visual angle between adjacent film (layer) with very high efficient manufacturing; A kind of elliptical polarization plate that obtains by this method; And the image display that uses this elliptical polarization plate.
The present inventor has carried out deep research to the character of elliptical polarization plate, find that above-mentioned purpose can be by reaching the birefringent layers lamination with special optical performance beyond λ/4 plates and λ/2 plates, wherein λ/2 plates are to form on base material and shift subsequently by ad hoc approach, thereby have finished the present invention.
Method according to the manufacturing elliptical polarization plate of an embodiment of the invention may further comprise the steps: the surface at transparent protective film (T) forms first birefringent layers; With the surface of polarizer lamination to transparent protective film (T); With the surface of polymer film lamination, thereby form second birefringent layers to first birefringent layers; And to form index distribution on the surface of second birefringent layers be the 3rd birefringent layers of nz＞nx=ny, wherein first birefringent layers is configured in the opposite side with respect to the polarizer of transparent protective film (T), and the step that wherein forms first birefringent layers may further comprise the steps: the coating liquid that will contain liquid crystal material is coated to through orientation to be handled on the base material of (alignmenttreatment); Under the temperature of liquid crystal material demonstration liquid crystal phase, handle the liquid crystal material of this coating, thereby on base material, form first birefringent layers; And first birefringent layers that will form on base material is transferred to the surface of transparent protective film (T).
In an embodiment of the invention, polarizer, transparent protective film (T), first birefringent layers that forms on base material and the polymer film that forms second birefringent layers all contain long film; Polarizer, transparent protective film (T) with formed first birefringent layers on the base material separately vertically according to identical direction configuration in adhere to each other continuously, thereby form the laminate that has polarizer, transparent protective film (T), first birefringent layers and base material successively; Base material is peeled off from laminate; And the polymer film that will peel off the laminate of base material and form second birefringent layers separately vertically according to identical direction configuration in adhere to each other continuously.
The method of manufacturing elliptical polarization plate according to another implementation of the invention may further comprise the steps: forming index distribution on the surface of transparent protective film (T) is the 3rd birefringent layers of nz＞nx=ny; With the surface of polarizer lamination to transparent protective film (T); Form first birefringent layers on the 3rd birefringent layers surface; And with the surface of polymer film lamination, thereby form second birefringent layers to first birefringent layers; And wherein the 3rd birefringent layers is configured in opposite side with respect to the polarizer of transparent protective film (T), and the step that wherein forms first birefringent layers may further comprise the steps: the coating liquid that will contain liquid crystal material is coated on the base material of handling through orientation; Under the temperature of liquid crystal material demonstration liquid crystal phase, handle the liquid crystal material that applies, thereby on base material, form first birefringent layers; And will be on base material formed first birefringent layers transfer to the surface of the 3rd birefringent layers.
In an embodiment of the invention, polarizer, transparent protective film (T), the 3rd birefringent layers, first birefringent layers that forms on base material and the polymer film that forms second birefringent layers all contain long film; The laminate that has polarizer, transparent protective film (T) and the 3rd birefringent layers successively, with first birefringent layers that forms on the base material separately vertically according to identical direction configuration in adhere to each other continuously, thereby form the laminate that has polarizer, transparent protective film (T), the 3rd birefringent layers, first birefringent layers and base material successively; Base material is peeled off from laminate; And the polymer film that will peel off the laminate of base material and form second birefringent layers separately vertically according to identical direction configuration in adhere to each other continuously.
In yet another embodiment of the present invention, liquid crystal material contains at least a in liquid crystal monomer and the liquid crystal polymer.
In another embodiment of the present invention, first birefringent layers contains λ/2 plates.
In another embodiment of the present invention, second birefringent layers contains λ/4 plates.
In another embodiment of the present invention, base material contains the polyethylene terephthalate film.
In another embodiment of the present invention, polymer film contains stretched film.
In another embodiment of the present invention, the absorption axes of polarizer is vertical substantially each other with the slow axis of second birefringent layers.
In another embodiment of the present invention, the slow axis of first birefringent layers is defined as with respect to the absorption axes of a polarizer angle for+8 ° to+38 ° and-8 ° to-38 °.
In another embodiment of the present invention, transparent protective film (T) contains by the film of triacetyl cellulose as principal ingredient and forms.
According to another aspect of the present invention, provide a kind of elliptical polarization plate.This elliptical polarization plate is by above-mentioned manufacture method manufacturing.
According to a further aspect of the invention, provide a kind of image display.This image display comprises above-mentioned elliptical polarization plate.In an embodiment of the invention, elliptical polarization plate is configured in and watches side.
According to the present invention, the slow axis that can play first birefringent layers of λ/2 plate effects can be arranged in any desired direction, therefore can use the long light polarizing film (polarizer) (that is the film of absorption axes in longitudinal direction) in the longitudinal direction in-draw.In other words; through with respect to its longitudinally predetermined angular carry out first birefringent layers of the length that forms on the long substrate that orientation handles, long transparent protective film and long light polarizing film (polarizer), separately vertically according to equidirectional configuration (by so-called reel-to-reel (roll to roll)) in can adhere to each other continuously.Perhaps, through with respect to its longitudinally the predetermined angular laminate that carries out first birefringent layers of the length that forms on the long substrate that orientation handles and have long light polarizing film (polarizer) and a long transparent protective film can adhere to each other continuously by reel-to-reel.Thereby elliptical polarization plate can obtain with very high production efficiency.The method according to this invention, the transparent protective film or the polarizer that are used for lamination needn't carry out about its vertically oblique cutting of (draw direction).As a result, the angle of optic axis can not change with respect to the film of every cutting, thereby obtains elliptical polarization plate that each product quality is changed.And, do not produce waste material by the cutting film yet, can obtain elliptical polarization plate with low cost, and promote the manufacturing of large-scale Polarizer.And according to an embodiment of the invention, second birefringent layers is easy to by the surface of polymer film lamination to first birefringent layers formed.The long limit of the polymer film and first birefringent layers can adhere to each other continuously, thereby obtains second birefringent layers on first birefringent layers.Thereby elliptical polarization plate can obtain with very high production efficiency.Because elliptical polarization plate can obtain by the adhesion of using so-called reel-to-reel, the cohesive between the adjacent layer (film) can be very excellent.In addition, according to the present invention, index distribution is that the 3rd birefringent layers of nz＞nx=ny and λ/4 plates and λ/2 plates are used in combination.Therefore, also have the elliptical polarization plate at the broadband and the wide visual angle of excellent properties and the image display that uses this elliptical polarization plate obliquely even can obtain.
Description of drawings
In the accompanying drawings:
Fig. 1 is the schematic cross-section according to the elliptical polarization plate of preferred implementation of the present invention;
Fig. 2 is the decomposition diagram according to the elliptical polarization plate of preferred implementation of the present invention;
Fig. 3 is the skeleton view that shows a step in the example of method of elliptical polarization plate constructed in accordance;
Fig. 4 is the skeleton view that shows another step in the example of method of elliptical polarization plate constructed in accordance;
Fig. 5 is the synoptic diagram that shows another step in the example of method of elliptical polarization plate constructed in accordance;
Fig. 6 is the synoptic diagram that shows another step in the example of method of elliptical polarization plate constructed in accordance;
Fig. 7 is the synoptic diagram that shows another step in the example of method of elliptical polarization plate constructed in accordance;
Fig. 8 is the synoptic diagram that shows another step in the example of method of elliptical polarization plate constructed in accordance; And
Fig. 9 is the schematic cross-section according to the liquid crystal panel that is used for LCD of preferred implementation of the present invention.
Embodiment
A. elliptical polarization plate
A-1. the general structure of elliptical polarization plate
Elliptical polarization plate according to the embodiment of the present invention comprises polarizer, protective seam, first birefringent layers, second birefringent layers and the 3rd birefringent layers.As long as can obtain effect of the present invention, can use the order that is fit to arbitrarily to come each layer of lamination.For example, shown in Figure 1A, elliptical polarization plate 10 is furnished with polarizer 11, protective seam (transparent protective film) 12, first birefringent layers 13, second birefringent layers 14 and the 3rd birefringent layers 15 according to given order.Such structure makes because from the skew of the optic axis of each layer of watching obliquely or because the different polarization state that phase differential caused of protective seam obtains favourable compensation, thereby guarantees the function of Polarizer in the wide visual angle.Perhaps, shown in Figure 1B, the 3rd birefringent layers 15 is configurable between the protective seam 12 and first birefringent layers 13.In such structure, the phase differential of protective seam is offseted by the phase differential of the 3rd birefringent layers, thereby recovers the linear polarization performance of the light that Polarizer sent, and guarantees the function of Polarizer in wide visual angle.In actual use, elliptical polarization plate according to the embodiment of the present invention can not have a side of configuration protection layer 12 to be furnished with second protective seam 16 at polarizer.
First birefringent layers 13 can be used as so-called λ/2 plates.In instructions of the present invention, λ/2 plates refer to a kind of plate that the linearly polarized photon that will the certain vibration direction be arranged changes the perpendicular linearly polarized photon of direction of vibration into or right-circularly polarized light changed into the function of left circularly polarized light (or change left circularly polarized light into right-circularly polarized light) that has.
Second birefringent layers 14 can be used as so-called λ/4 plates.In instructions of the present invention, λ/4 plates refer to a kind of plate that the linearly polarized photon that will specific wavelength be arranged changes the function of circularly polarized light (or change circularly polarized light into linearly polarized photon) into that has.
The index distribution of the 3rd birefringent layers 15 is nz＞nx=ny.The absolute value Rth of preferred the 3rd birefringent layers 15 thickness direction phase differential
3Ratio R th with the absolute value Rthp of protective seam 12 thickness direction phase differential
3/ Rthp is 1.1 to 4.0, more preferably 1.5 to 3.0.This relation of the thickness direction phase differential of protective seam 12 and the 3rd birefringent layers 15 makes the phase differential of protective seam can access favourable compensation, thereby the oblique performance of excellence is provided for elliptical polarization plate.
Here, nx representative provides the direction of refractive index in the largest face (that is) refractive index, slow-axis direction, the ny representative is perpendicular to refractive index in the face of the direction of slow axis, the refractive index of nz representative thickness direction.In addition, expression formula " nx=ny " not only comprises nx and the identical situation of ny, also comprises the essentially identical situation of nx and ny.In instructions of the present invention, phrase " basic identical " comprises nx but situation that in actual applications not the overall polarization property of elliptical polarization plate exerted an influence different with ny.Phase differential Rth (the Rth of thickness direction
3, Rthp etc.) calculate (d (nm) represents the thickness of film (layer)) herein according to equation Rth={ (nx+ny)/2-nz} * d.
Fig. 2 explains the decomposition diagram (among Fig. 2, for clarity sake, omitted second protective seam 16) of formation according to the optic axis of each layer of elliptical polarization plate of preferred implementation of the present invention.Disposing first birefringent layers 13 makes its slow axis B be limited to predetermined angle [alpha] with respect to the absorption axes A of polarizer 11.Angle [alpha] is preferably+and 8 ° to+38 ° or-8 ° to-38 °, more preferably+13 ° to+33 ° or-13 ° to-33 °, preferred especially+19 ° to+29 ° or-19 ° to-29 °, especially preferred+21 ° to+27 ° or-21 ° to-27 °, most preferably+23 ° arrive+24 ° or-23 ° to-24 °.First birefringent layers and polarizer dispose with above-mentioned angle [alpha], thereby the Polarizer with excellent circular polarization performance is provided.As shown in Figure 2, disposing second birefringent layers 14 makes its slow axis C be basically perpendicular to the absorption axes A of polarizer 11.In instructions of the present invention, phrase " vertical substantially " comprises that angle is 90 ° ± 2.0 °, preferred 90 ° ± 1.0 °, and more preferably 90 ° ± 0.5 ° situation.
The gross thickness of elliptical polarization plate of the present invention is preferably 80 to 250 μ m, more preferably 110 to 220 μ m, most preferably 140 to 190 μ m.Elliptical polarization plate of the present invention can greatly help to reduce the thickness of image display device.Hereinafter, will each layer that constitute elliptical polarization plate of the present invention be described in detail.
A-2. first birefringent layers
As mentioned above, first birefringent layers 13 can be used as so-called λ/2 plates.First birefringent layers is as λ/2 plates, thereby suitably regulates phase differential as the wavelength dispersion characteristics of second birefringent layers of the λ/4 plates wavelength coverage of the phase differential that deviates from λ/4 (especially).Phase differential (Δ nd) is preferably 180 to 300nm in the face of first birefringent layers when wavelength is 590nm, more preferably 210 arrives 280nm, most preferably 230 arrives 240nm.Phase differential (Δ nd) obtains according to equation Δ nd=(nx-ny) * d in the face.Herein, nx represents the refractive index of slow-axis direction, and ny represents the refractive index of the quick shaft direction direction of slow axis (in the identical faces perpendicular to), and d represents the thickness of first birefringent layers.The index distribution of first birefringent layers 13 is preferably nx＞ny=nz.The refractive index of nz representative thickness direction.In instructions of the present invention, equation " ny=nz " not only comprises ny and the identical situation of nz, also comprises the essentially identical situation of ny and nz.
The thickness of setting first birefringent layers makes it be suitable as λ/2 plates most.In other words, its thickness setting is phase differential in the face that expectation can be provided.More particularly, thickness is preferably 0.5 to 5 μ m, more preferably 1 to 4 μ m, most preferably 1.5 to 3 μ m.
As long as above-mentioned characteristic can be provided, the material that is fit to can be as the material that forms first birefringent layers arbitrarily.Preferred liquid crystal material more preferably has the liquid crystal material (nematic crystal) of nematic phase as liquid crystal phase.The example of liquid crystal material comprises liquid crystal polymer and liquid crystal monomer.The liquid crystal liquid crystal property of liquid crystal material can obtain by molten mechanism or the thermic mechanism that causes.Further, the orientation state of liquid crystal is preferably even orientation.
For example, the liquid crystal monomer as liquid crystal material is preferably polymerisable monomer and/or crosslinkable monomers.As described below, this is because the orientation state of liquid crystal monomer polymerization that can be by liquid crystal monomer or crosslinked and fixing.For example, the orientation state of liquid crystal monomer can be by the orientation liquid crystal monomer, then polymerization or crosslinked liquid crystal monomer and fix.Polymkeric substance forms by polymerization, and tridimensional network is by being cross-linked to form.Polymkeric substance and tridimensional network are not liquid crystal.Therefore, formed first birefringent layers can not become liquid crystal phase, glassy phase or crystallization phase to the specific temperature of liquid-crystal compounds mutually by changing.As a result, first birefringent layers is the birefringent layers that has excellent stability and not influenced by temperature change.
The liquid crystal monomer that is fit to can be used as liquid crystal monomer arbitrarily.For example, use polymerizable internal compensation (mesogenic) compound described in JP2002-533742A (WO 00/37585), EP 358208 (US 5211877), EP 66137 (US 4388453), WO 93/22397, EP 0261712, DE 19504224, DE 4408171, the GB 2280445 etc. etc.The object lesson of polymerizable meso compound comprises: buy from the LC242 of BSAF Aktiengesellschaft (trade name); Purchase is from Merck﹠amp; Co.Inc. E7 (trade name); Purchase is from the LC-Silicone-CC 3767 of Wacker-Chemie GmbH (trade name).
For example, the nematic crystal monomer is preferably as liquid crystal monomer, the monomer of structural formula (1) representative shown in its object lesson comprises hereinafter.Liquid crystal monomer can use separately, and perhaps two or more are used in combination.
In said structure formula (1), A
1And A
2Represent polymerizable groups separately, and each other can be identical or different.A
1And A
2In one can represent hydrogen.Each X represent independently singly-bound ,-O-,-S-,-C=N-,-O-CO-,-CO-O-,-O-CO-O-,-CO-NR-,-NR-CO-,-NR-,-O-CO-NR-,-NR-CO-O-,-CH
2-O-or-NR-CO-NR-.R represents hydrogen or has the alkyl of 1 to 4 carbon atom.M represents mesogenic group group.
In said structure formula (1), Xs each other can be identical or different, but preferably identical.
In the monomer of said structure formula (1) representative, preferred each A
2Be configured in respect to A
1The ortho position.
Preferred A
1And A
2Structural formula (2) representative shown in using hereinafter independently of one another, preferred A
1And A
2Represent identical group.
Z-X-(Sp)
n …(2)
In said structure formula (2), Z represents crosslinkable groups, and X is identical with the definition in the said structure formula (1).The Sp representative is by straight chain or the interval base that alkyl constituted side chain, that have 1 to 30 carbon atom that replace or non-replacement.N represents 0 or 1.Carbochain among the Sp can be by sulphur, non-conterminous imino group in the oxygen in the ether functional group, the thioether functional group, the blocking-up such as alkyl imino of 1 to 4 carbon atom are arranged.
In said structure formula (2), any one in the functional group of the structural formula representative shown in Z preferably represents hereinafter.In the structural formula hereinafter, the example of R comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group.
H
2C＝CH-，HC≡C-，
-N＝C＝O，-N＝C＝S，-O-C≡N，
In said structure formula (2), any one of the structural unit of the structural formula representative shown in Sp preferably represents hereinafter.In the structural formula hereinafter, preferred m represents 1 to 3, and preferred p represents 1 to 12.
-(CH
2)
p-，-(CH
2CH
2O)
mCH
2CH
2-，-CH
2CH
2SCH
2CH
2-，-CH
2CH
2NHCH
2CH
2-，
In said structure formula (1), structural formula (3) representative shown in M preferably uses hereinafter.In the structural formula hereinafter (3), defined identical in X and the said structure formula (1).For example, the Q representative replaces or the alkyl or the aryl radical of the straight or branched of non-replacement.For example, Q can represent alkylidene straight or branched, that have 1 to 12 carbon atom of replacement or non-replacement.
Represent under the situation of aryl radical any one aryl radical of the structural formula representative shown in the preferred Q representative hereinafter or the analog of its replacement at Q.
The replacement analog of the aryl radical of said structure formula representative can have 1 to 4 substituting group on each comfortable each aromatic rings, perhaps has 1 to 2 substituting group on each aromatic rings or the group.Substituting group each other can be identical or inequality.Substituent example comprises: the alkyl with 1 to 4 carbon atom; Nitro; Halogeno-group is fluorine, chlorine, bromine or iodine for example; Phenyl; With alkoxy with 1 to 4 carbon atom.
The object lesson of liquid crystal monomer comprises with the monomer of following structural (4) to (19) representative.
The temperature range that liquid crystal monomer demonstrates liquid crystal liquid crystal property changes according to the type of liquid crystal monomer.More particularly, temperature range is preferably 40 to 120 ℃, and more preferably 50 to 100 ℃, most preferably 60 to 90 ℃.
A-3. second birefringent layers
As mentioned above, second birefringent layers 14 can be used as so-called λ/4 plates.According to the present invention, revise by optical characteristics as the wavelength dispersion characteristics of second birefringent layers of λ/4 plates, thereby in wide wavelength coverage, demonstrate gratifying circular polarization function as first birefringent layers of λ/2 plates.Phase differential (Δ nd) is preferably 90 to 180nm in the face of second birefringent layers when wavelength is 550nm, more preferably 90 arrives 150nm, most preferably 105 arrives 135nm.The Nz coefficient of second birefringent layers (=(nx-nz)/(nx-ny)) is preferably 1.0 to 2.2, and more preferably 1.2 to 2.0, most preferably 1.4 to 1.8.Further, the index distribution of second birefringent layers 14 is preferably nx＞ny＞nz.
The thickness of setting second birefringent layers makes it be suitable as λ/4 plates most.In other words, thus setting its thickness provides phase differential in the face of expection.More particularly, thickness is preferably 10 to 100 μ m, more preferably 20 to 80 μ m, most preferably 40 to 70 μ m.
Second birefringent layers forms by polymer film is carried out stretch processing usually.Second birefringent layers with desired optical properties (for example phase differential, thickness direction phase differential and Nz coefficient in index distribution, the face) can obtain by suitable selective polymer type, stretching condition, drawing process etc.
The polymkeric substance that is fit to can be as the polymkeric substance that constitutes polymer film arbitrarily.The object lesson of polymkeric substance comprises for example polymkeric substance of polycarbonate based polyalcohol, norborene based polyalcohol, cellulose-based polymer, polyvinyl alcohol (PVA) based polyalcohol and polysulfones based polyalcohol and so on.
Perhaps, second birefringent layers can be made up of the film that the resin combination that contains polymerisable liquid crystal and chiral reagent forms.Polymerisable liquid crystal and chiral reagent are described in JP 2003-287623A to some extent, are hereby incorporated by.For example, above-mentioned resin combination is coated on the base material that is fit to arbitrarily, and integral body is heated to the temperature that this polymerisable liquid crystal presents mesomorphic state.Therefore polymerisable liquid crystal becomes twisted state (more particularly, by forming cholesteric structure) by the chiral reagent orientation.Polymerisable liquid crystal is with this behavior aggregate, thereby obtains having the fixedly film of cholesteric structure.The content of regulating chiral reagent in the composition allows to change the torsion resistance of cholesteric structure.As a result, can control the slow-axis direction of second birefringent layers of gained.Very preferably such film is because slow-axis direction can be set with 0 ° (parallel) or 90 ° of (vertically) angles in addition with the absorption axes with respect to polarizer.
A-4. the 3rd birefringent layers
As mentioned above, the index distribution of the 3rd birefringent layers 15 is nz＞nx=ny, and it can be used as so-called positive C plate (positive C plate).Preferably, the absolute value Rth of the 3rd thickness of birefringence layer direction phase differential
3Absolute value Rthp with respect to protective layer thickness direction phase differential is specific ratio.The 3rd birefringent layers with this optical property is provided, thereby makes the phase differential of protective layer thickness direction obtain favourable compensation.As a result, even obtained the elliptical polarization plate that also has excellent properties oblique.
As mentioned above, the absolute value Rth of the 3rd thickness of birefringence layer direction phase differential
3Can be optimized according to the absolute value Rthp of protective layer thickness direction phase differential.For example, the absolute value Rth of the 3rd thickness of birefringence layer direction phase differential
3Be preferably 50 to 200nm, more preferably 75 arrive 150nm, most preferably 90 arrive 120nm.Provide the thickness of the 3rd birefringent layers of this absolute value to change according to material that will use etc.For example, the thickness of the 3rd birefringent layers is preferably 0.5 to 10 μ m, more preferably 0.5 to 8 μ m, most preferably 0.5 to 5 μ m.
Preferably the film of fixing liquid crystal material forms the 3rd birefringent layers by containing vertical orientation.But the liquid crystal material of vertical orientation (liquid-crystal compounds) can be liquid crystal monomer or liquid crystal polymer.The exemplary of liquid-crystal compounds is a nematic liquid crystal compound.Summary for the alignment technique of this liquid-crystal compounds is described in for example " Kagaku Sousetsu 44 " (Hyomen NoKaishitsu, Chemical Society of Japan writes the 156-163 page or leaf) to some extent, is hereby incorporated by.
The example that can form the liquid crystal material of vertical orientation is the side chain liquid crystalline polymer that contains following material: the monomeric unit (a) that contains liquid crystal segment side chain; And the monomeric unit (b) that contains non-liquid crystal segment side chain.Such side chain liquid crystalline polymer can be realized vertical orientation under the situation of not using vertical orientation agent (aligner, aligning agent) or vertical orientation film.Side chain liquid crystalline polymer also contains the monomeric unit (b) that contains non-liquid crystal segment side chain with alkyl chain etc. except containing the monomeric unit that contains liquid crystal segment side chain (a) that is included in the normal side chain liquid crystalline polymer.Under the situation of not using vertical orientation agent or vertical orientation film, for example by thermal treatment, the effect that contains the monomeric unit (b) of non-liquid crystal segment side chain estimates to make mesomorphic state (for example nematic crystal phase) to develop, thereby realizes vertical orientation.
Monomeric unit (a) has the side chain that shows nematic crystal, and its example is the monomeric unit with general formula (a) representative.
In general formula (a): R
1Represent hydrogen atom or methyl; A represents 1 to 6 positive integer; X
1Representative-CO
2-group or-the OCO-group; R
2Represent cyano group, have alkoxy, the fluoro base of 1 to 6 carbon atom or have the alkyl of 1 to 6 carbon atom; B and c represent integer 1 or 2.
Monomeric unit (b) has straight side chain, and its example is the monomeric unit with general formula (b) representative.
In general formula (b): R
3Represent hydrogen atom or methyl; R
4Representative has the group of the alkyl of 1 to 22 carbon atom, the fluoroalkyl with 1 to 22 carbon atom or general formula (b1) representative.
In general formula (b1), d represents 1 to 6 positive integer, and R
5Representative has the alkyl of 1 to 6 carbon atom.
Can suitably set the ratio of monomeric unit (a) and monomeric unit (b) according to the kind of purpose and monomeric unit.(b)/{ (a)+(b) } be preferably 0.01 to 0.8 (mol ratio), more preferably 0.1 to 0.5 (mol ratio) is because the ratio of big monomeric unit (b) provides the side chain liquid crystalline polymer that does not represent liquid crystal single domain orientation characteristic usually.
Another example that can form the liquid crystal material of vertical orientation is the side chain liquid crystalline polymer that contains following material: the monomeric unit (a) that contains liquid crystal segment side chain; The monomeric unit (c) that contains crystal segment side chain with alicyclic structure.Such side chain liquid crystalline polymer also can be realized vertical orientation under the situation of not using vertical orientation agent or vertical orientation film.Side chain liquid crystalline polymer also contains the monomeric unit (c) of the crystal segment side chain with alicyclic structure except containing the monomeric unit that contains liquid crystal segment side chain (a) that is included in the normal side chain liquid crystalline polymer.Under the situation of not using the vertical orientation film, for example by thermal treatment, the effect of monomeric unit (c) estimates to make mesomorphic state (for example nematic crystal phase) to develop, thereby realizes vertical orientation.
Monomeric unit (c) has the side chain that shows nematic crystal, and its example is the monomeric unit of general formula (c) representative.
In general formula (c): R
6Represent hydrogen atom or methyl; H represents 1 to 6 positive integer; X
2Representative-CO
2-group or-the OCO-group; E and g represent integer 1 or 2; F represents integer 0 to 2; R
7Represent cyano group or have the alkyl of 1 to 12 carbon atom.
Can suitably set the ratio of monomeric unit (a) and monomeric unit (c) according to the kind of purpose and monomeric unit.(c)/{ (a)+(c) } be preferably 0.01 to 0.8 (mol ratio), more preferably 0.1 to 0.6 (mol ratio) is because the ratio of big monomeric unit (c) provides the side chain liquid crystalline polymer that does not represent liquid crystal single domain orientation characteristic usually.
Above-mentioned monomeric unit only is an example, and the liquid crystal polymer that can form vertical orientation obviously is not limited to contain those of this monomeric unit.Monomeric unit as an example can appropriate combination.
The weight-average molecular weight of side chain liquid crystalline polymer is preferably 2,000 to 100,000.Weight-average molecular weight is adjusted in side chain liquid crystalline polymer in the above-mentioned scope can bring into play effect as liquid crystal polymer effectively.Weight-average molecular weight more preferably 2,500 to 50,000.Weight-average molecular weight is in the above-mentioned scope can provide excellent film forming characteristics and even orientation state for the gained layer.
The top side chain liquid crystalline polymer that exemplifies can by the monomeric unit (a) and (b) or (c) copolymerization of corresponding acrylic monomers or methacrylic acid monomer prepare.Monomeric unit (a) and (b) or (c) corresponding monomer can be synthetic by the method that is fit to arbitrarily.The preparation of multipolymer can be carried out according to the polymerization (for example free radical polymerisation process, cationic polymerization process or anionic polymerisation process) of the acrylic monomers that is fit to arbitrarily etc.In free radical polymerisation process, can use various polymerization initiators.The example of preferred polymerization initiator comprises azoisobutyronitrile and benzoyl peroxide, and they can decompose down in suitable temperature (not high not low), thereby with suitable mechanism and speed initiated polymerization.
Vertical orientation also can form from the liquid-crystal composition that contains side chain liquid crystalline polymer.Such liquid-crystal composition can also contain phtotpolymerizable liquid-crystal compounds except containing side chain liquid crystalline polymer.Phtotpolymerizable liquid-crystal compounds is the liquid-crystal compounds with at least one phtotpolymerizable functional group (group with unsaturated double-bond of acryloyl group for example or methacrylyl), and preferably can show nematic crystal.The object lesson of phtotpolymerizable liquid-crystal compounds comprises the acrylate and the methacrylate that also can be used as monomeric unit (a).Preferred phtotpolymerizable liquid-crystal compounds has the two or more phtotpolymerizable functional group of the permanance that is used to improve the film (the 3rd birefringent layers) that will obtain.The example of phtotpolymerizable liquid-crystal compounds like this is the cross-linking type nematic crystal monomer of following general formula representative.The further example of phtotpolymerizable liquid-crystal compounds comprises: by replace the end group " H in the following general formula with vinyl ether or epoxy radicals
2C=CR-CO
2-" and the compound of acquisition; By using " (CH
2)
3-C
*H (CH
3)-(CH
2)
2-" or " (CH
2)
2-C
*H (CH
3)-(CH
2)
3-" replace the " (CH in the following general formula
2)
m-" and/or " (CH
2)
n-" and the compound of acquisition.
H
2C＝CR
8-CO
2-(CH
2)
m-O-A-Y-B-Y-D-O-(CH
2)
n-O
2C-CR
8＝CH
2
In general formula: R
8Represent hydrogen atom or methyl; A and D represent 1 independently of one another, 4-phenylene or 1,4-cyclohexylidene; Each Y represents independently-the COO-group ,-the OCO-group or-the O-group; B represents 1,4-phenylene, 1,4-cyclohexylidene, 4,4 '-biphenylene or 4,4 '-two cyclohexylidenes; M and n represent 2 to 6 integer independently of one another.
Phtotpolymerizable liquid-crystal compounds can be with side chain liquid crystalline polymer, develops the mesomorphic state of nematic crystal phase for example and vertical orientation by thermal treatment.Then, phtotpolymerizable liquid-crystal compounds can polymerization or crosslinked and fixed vertical orientation, thereby further improves the permanance of the liquid crystal film of vertical orientation.
According to permanance of the liquid crystal film of the kind of purpose, the side chain liquid crystalline polymer that will use and phtotpolymerizable liquid-crystal compounds, the vertical orientation that will obtain etc., can suitably set the ratio of liquid-crystal compounds and side chain liquid crystalline polymer phtotpolymerizable in the liquid-crystal composition.Specifically, phtotpolymerizable liquid-crystal compounds: side chain liquid crystalline polymer (weight ratio) is preferably about 0.1: 1 to 30: 1, and more preferably 0.5: 1 to 20: 1, most preferably 1: 1 to 10: 1.
Liquid-crystal composition can further contain Photoepolymerizationinitiater initiater.The Photoepolymerizationinitiater initiater that is fit to can be used as Photoepolymerizationinitiater initiater arbitrarily.Its concrete example comprises IRGACURE 907, IRGACURE 184, IRGACURE 651 and IRGACURE 369 (trade name is bought from Ciba Specialty Chemicals).Consider the kind of phtotpolymerizable liquid-crystal compounds, the blending ratio of liquid-crystal composition etc., the amount of Photoepolymerizationinitiater initiater can be adjusted in the scope of the vertical orientation characteristic that does not influence liquid-crystal composition.Usually, with respect to the phtotpolymerizable liquid-crystal compounds of 100 weight portions, the amount of Photoepolymerizationinitiater initiater is preferably about 0.5 to 30 weight portion, more preferably 0.5 to 10 weight portion.
A-5. polarizer
According to purposes, can use the polarizer that is fit to arbitrarily as polarizer 11.Its example comprises: by on the hydrophilic polymer film of polyvinyl alcohol (PVA) basement membrane for example, the formalized polyvinyl alcohol (PVA) basement membrane of part or partly-hydrolysed ethylene/vinyl acetate copolymer basement membrane and so on, the dichroic substance of adsorbing iodine for example or dichroic dye, and this film carried out uniaxial tension and the film for preparing; And the polyalkenyl alignment films of the dehydration product of polyvinyl alcohol (PVA) basement membrane or dechlorination product of Polyvinylchloride basement membrane and so on for example.Wherein, because high polarization dichromatism, the especially preferred dichroic substance by on the polyvinyl alcohol (PVA) basement membrane, adsorbing iodine for example and this film carried out the polarizer that uniaxial tension prepares.The thickness of polarizer is not particularly limited, but is typically about 1 to 80 μ m.
By absorption iodine on the polyvinyl alcohol (PVA) basement membrane and this film is carried out the polarizer that uniaxial tension prepares followingly to produce, for example: the polyvinyl alcohol (PVA) basement membrane is immersed the aqueous solution of iodine to dye; And this film is stretched to 3 to 7 times of original length.Aqueous solution can contain boric acid, zinc sulfate, zinc chloride etc. as required, and perhaps the polyvinyl alcohol (PVA) basement membrane can immerse in the aqueous solution of potassium iodide etc.And, can before dyeing, the polyvinyl alcohol (PVA) basement membrane be soaked in water and clean as required.
Water cleans the polyvinyl alcohol (PVA) basement membrane not only can remove the dirt or the detackifier on striping surface, can also prevent for example effect of the unevenness of uneven dyeing and so on to provide by the polyvinyl alcohol (PVA) basement membrane is expanded.Among can after the process that film is dyeed with iodine, to film, dyeing or before film being dyeed this film is stretched with iodine.Stretching can be carried out in the aqueous solution of boric acid or potassium iodide or in the water-bath.
A-6. protective seam
The protective seam 12 and second protective seam 16 are all formed by any film suitable, that can be used as the polarizer protective seam.Object lesson as the material of the principal ingredient of film comprises transparent resin, for example cellulose base resin (for example triacetyl cellulose (TAC)), polyester-based resin, polyvinyl alcohol based resins, polycarbonate-base resin, polyamide-based resins, polyimide-based resin, polyethers sulfuryl resin, polysulfones base resin, polystyrene-based resin, polynorbornene based resin, polyolefin resin, acryl resin and acetate groups resin.Its another example comprises acrylic acid, carbamate groups, propenoic methyl carbamate base, epoxy radicals or silicone base thermoset resin or ultraviolet hardening resin.Its another example comprises glassy polymers, for example silica alkyl polymer.Further, also can use the polymer film of describing among the JP 2001-343529A (WO 01/37007).More particularly, film is made of resin combination, and this resin combination contains having on the side chain and replaces or the thermoplastic resin of the imide of non-replacement and having on side chain replaces or the thermoplastic resin of the phenyl of non-replacement.Its object lesson comprises the resin combination that contains isobutylene and N-methyl maleimide alternating copolymer and vinyl cyanide/styrol copolymer.For example, polymer film can be the extruded product of above-mentioned resin combination.Wherein, preferred TAC, polyimide-based resin, polyvinyl alcohol based resins and glassy polymers.Preferred especially TAC.The protective seam of this material can be used in combination with the 3rd birefringent layers, thereby improves the circular polarization performance obliquely significantly.
Protective seam preferably clear or do not have color.More particularly, the phase differential of protective layer thickness direction is preferably-90nm is to+90nm, more preferably-80nm is to+80nm, and most preferably-70nm is to+70nm.
As long as can access the phase differential of preferred thickness direction, protective seam can have the thickness that is fit to arbitrarily.More particularly, the thickness of protective seam is preferably 5mm or littler, more preferably 1mm or littler, preferred especially 1 to 500 μ m, most preferably 5 to 150 μ m.
B. make the method for elliptical polarization plate
Method according to the manufacturing elliptical polarization plate of an embodiment of the invention comprises: the surface at transparent protective film (T) forms first birefringent layers; With the surface of polarizer lamination to transparent protective film (T); With the surface of polymer film lamination, thereby form second birefringent layers to first birefringent layers; And to form index distribution on the surface of second birefringent layers be the 3rd birefringent layers of nz＞nx=ny.First birefringent layers is configured in the opposite side with respect to the polarizer on the transparent protective film (T).The step that forms first birefringent layers comprises: the coating liquid that will contain liquid crystal material is coated on the base material of handling through orientation; Under the temperature of liquid crystal material demonstration liquid crystal phase, handle the liquid crystal material of this coating, thereby on base material, form first birefringent layers; And first birefringent layers that will form on base material is transferred to the surface of transparent protective film (T).The absolute value Rth of the 3rd thickness of birefringence layer direction phase differential
3Ratio R th with the absolute value Rthp of transparent protective film (T) thickness direction phase differential
3/ Rthp is preferably 1.1 to 4.0.For example, according to this manufacture method, can obtain the elliptical polarization plate shown in Figure 1A.
The method of manufacturing elliptical polarization plate according to another implementation of the invention comprises: forming index distribution on the surface of transparent protective film (T) is the 3rd birefringent layers of nz＞nx=ny; With the surface of polarizer lamination to transparent protective film (T); Form first birefringent layers on the 3rd birefringent layers surface; And with the surface of polymer film lamination, thereby form second birefringent layers to first birefringent layers.The 3rd birefringent layers is configured in the opposite side with respect to the polarizer on the transparent protective film (T).The step that forms first birefringent layers comprises: the coating liquid that will contain liquid crystal material is coated on the base material of handling through orientation; Under the temperature of liquid crystal material demonstration liquid crystal phase, handle the liquid crystal material that applies, thereby on base material, form first birefringent layers; And will be on base material formed first birefringent layers transfer to the surface of the 3rd birefringent layers.The absolute value Rth of the 3rd thickness of birefringence layer direction phase differential
3Ratio R th with the absolute value Rthp of transparent protective film (T) thickness direction phase differential
3/ Rthp is preferably 1.1 to 4.0.For example, can obtain elliptical polarization plate shown in Figure 1B according to this manufacture method.
According to the laminated structure of target elliptical polarization plate, order that can this step of appropriate change.For example, the step of lamination polarizer can be carried out after any one deck in formation or the lamination birefringent layers.Each step is hereinafter described.
B-1. form the step of first birefringent layers
First birefringent layers forms on the surface of transparent protective film (T).The detailed step that forms first birefringent layers is as follows.
At first, the coating liquid that will contain liquid crystal material is coated on the base material of handling through orientation.
As long as can obtain being fit to first birefringent layers of the present invention, can use any suitable base material.Its object lesson comprises glass baseplate, metal forming, plastic sheet and plastic foil.On base material, do not need the vertical orientation film.Any suitable plastic foil can be used as plastic foil.Its object lesson comprises that this transparent polymer comprises by the formed film of following transparent polymer: the polyester based polymer of polyethylene terephthalate and PEN for example; The cellulose-based polymer of diacetyl cellulose and triacetyl cellulose for example; The polycarbonate based polyalcohol; The acrylate copolymer of polymethylmethacrylate for example.The further example of plastic foil comprises the film that is formed by following transparent polymer, and this transparent polymer comprises: the styrene-based polymer of polystyrene and vinyl cyanide/styrol copolymer for example; For example tygon, polypropylene, polyolefin and the olefin-based polymer of ethylene/propene copolymer with ring-type or norborene structure; The chlorovinyl polymkeric substance; And the amido polymer of nylon and aromatic polyamides for example.The further example of plastic foil comprises by the formed film of transparent polymer that comprises imide polymkeric substance, sulfuryl polymkeric substance, polyethersulfone based polyalcohol, polyetheretherketone based polyalcohol, polyphenylene sulfide based polyalcohol, vinyl alcohol based polyalcohol, vinylidene chloride based polyalcohol, vinyl butyral based polyalcohol, arylide based polyalcohol, polyoxymethylene based polyalcohol, epoxy-based polymerization thing and product mix thereof.Wherein, preferably use by the formed plastic foil of polyethylene terephthalate (PET).
The thickness of base material is preferably 20 to 100 μ m, more preferably 30 to 90 μ m, most preferably 30 to 80 μ m.Thickness is in can provide in the step of lamination in the above-mentioned scope and has sufficient intensity supporting the base material of the first extremely thin birefringent layers, and can keep for example operating performance of sliding capability and lift-over travelling performance (roll traveling proerty) and so on suitably.
As long as first birefringent layers of the present invention that can obtain being fit to can adopt any suitable orientation to handle as the orientation of base material and handle.The object lesson that orientation is handled comprises that friction treatment, oblique deposition method (oblique deposition method), stretch processing, light orientation processing, magnetic field orientation are handled and the electric field orientation is handled.Preferred friction treatment.
When the lamination polarizer, the alignment direction that orientation is handled is set with the predetermined angular orientation with respect to the absorption axes of polarizer.The alignment direction slow-axis direction with first birefringent layers 12 as mentioned below basically is identical.Therefore, predetermined angle is preferably+and 8 ° to+38 ° or-8 ° to-38 °, more preferably+13 ° to+33 ° or-13 ° to-33 °, preferred especially+19 ° to+29 ° or-19 ° to-29 °, especially preferred+21 ° to+27 ° or-21 ° to-27 °, most preferably+23 ° arrive+24 ° or-23 ° to-24 °.
The coating liquid that will contain the liquid crystal material that forms first birefringent layers is coated on the base material of handling through orientation.Then, with the liquid crystal material orientation in the coating liquid to form first birefringent layers.This liquid crystal material is through the processing under the temperature that shows liquid crystal phase at liquid crystal material and orientation.Can be according to the suitable fixed temperature really of the type of employed liquid crystal material.Processing under this temperature allows liquid crystal material to be in mesomorphic state, and according to the alignment direction of substrate surface with this liquid crystal material orientation.Therefore, birefringence is caused by the layer that forms by coating, thereby forms first birefringent layers.
The coating liquid that contains liquid crystal material prepares by liquid crystal material is dissolved or is dispersed in the appropriate solvent.
Can dissolve or the solvent that is fit to arbitrarily of dispersed liquid crystal material can be used as solvent.Can suitably select the type of solvent that to use according to the type of liquid crystal material etc.The object lesson of solvent comprises: the halogenated hydrocarbons of chloroform, methylene chloride, phenixin, ethylene dichloride, tetrachloroethane, carrene, triclene, zellon, chlorobenzene and o-dichlorobenzene for example; For example phenol, right-chlorophenol, o-chlorophenol ,-phenols of cresols, neighbour-cresols and p-Cresol; For example benzene,toluene,xylene, mesitylene, methoxybenzene and 1, the aromatic hydrocarbon of 2-dimethoxy benzene; The ketone-based solvent of acetone, methyl ethyl ketone (MEK), methylisobutylketone, cyclohexanone, cyclopentanone, 2-Pyrrolidone and N-N-methyl-2-2-pyrrolidone N-for example; The ester group solvent of ethyl acetate, butyl acetate and propyl acetate for example; The for example tert-butyl alcohol, glycerine, ethylene glycol, triethylene glycol, glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol and 2-methyl-2, the alcohol-based solvent of 4-pentanediol; The amide group solvent of dimethyl formamide and dimethyl acetamide for example; The itrile group solvent of acetonitrile and butyronitrile for example; The ether solvent of ether, butyl ether, tetrahydrofuran and dioxane for example; And carbon disulphide, ethyl cellosolve, butyl cellosolve and ethylhexoate cellosolve.Wherein, preferred toluene, dimethylbenzene, mesitylene, MEK, methylisobutylketone, cyclohexanone, ethyl cellosolve, butyl cellosolve, ethyl acetate, butyl acetate, propyl acetate and ethylhexoate cellosolve.Solvent can use separately or wherein two or more are used in combination.
Can suitably determine the content of the liquid crystal material in the liquid-crystal composition (coating liquid) according to the type of liquid crystal material, the thickness of destination layer etc.More particularly, the content of liquid crystal material is preferably 5 to 50wt%, more preferably 10 arrives 40wt%, most preferably 15 arrives 30wt%.
As required, liquid-crystal composition (coating liquid) can further contain the adjuvant that is fit to arbitrarily.The object lesson of adjuvant comprises polymerization initiator and crosslinking chemical.Use adjuvant when being used as liquid crystal material particularly preferably in liquid crystal monomer.The object lesson of polymerization initiator comprises benzoyl peroxide (BPO) and azoisobutyronitrile (AIBN).The object lesson of crosslinking chemical comprises isocyanate based cross-linker, epoxy radicals crosslinking chemical and metallo-chelate crosslinking chemical.This adjuvant can use separately or wherein two or more unite use.The object lesson of other adjuvants comprises antioxidant, modifier, surfactant, dyestuff, pigment, inhibitor and UV absorbing agent fade.These adjuvants also can use separately or wherein two or more unite use.Examples of antioxidants comprises phenylol compound, amine compound, organic sulfur based compound and phosphino-compound.The example of modifier comprises ethylene glycol, silicone and alcohol.For example, surfactant is used to make the surface of blooming (first birefringent layers that promptly will form) to polish.Its object lesson comprises silicone base surfactant, acrylic acid surfactant and fluorine based surfactant.
Can suitably determine the coated weight of coating liquid according to the concentration of coating liquid, the thickness of destination layer etc.The concentration of the liquid crystal material in coating liquid is under the situation of 20wt%, every 100cm
2The coated weight of base material is preferably 0.03 to 0.17ml, more preferably 0.05 arrives 0.15ml, most preferably 0.08 arrives 0.12ml.
Can use any suitable painting method, its object lesson comprises roller coat, spin coating, seal that ingot is coated with (wire bar coating), dip-coating, extrudes, curtain coating (curtain coating) and spraying.
Then, will form the liquid crystal material orientation of first birefringent layers according to the alignment direction of substrate surface.This liquid crystal material is through the processing under the temperature that shows liquid crystal phase at liquid crystal material and orientation.Can be according to the type appropriating setting temp of employed liquid crystal material.Processing under this temperature allows liquid crystal material to be in mesomorphic state, and this liquid crystal material is according to the alignment direction on transparent protective film surface and orientation.Therefore, birefringence is by causing by applying formed layer, thereby forms first birefringent layers.
Treatment temperature can suitably be determined according to the type of liquid crystal material.More particularly, treatment temperature is preferably 40 to 120 ℃, and more preferably 50 to 100 ℃, most preferably 60 to 90 ℃.Processing time is preferably 30 seconds or longer, and more preferably 1 minute or longer, preferred especially 2 minutes or longer, most preferably 4 minutes or longer.Processing time is less than 30 seconds, and the mesomorphic state of the liquid crystal material that is provided may be insufficient.Simultaneously, the processing time is preferably 10 minutes or shorter, and more preferably 8 minutes or shorter, most preferably 7 minutes or shorter.Processing time surpasses 10 minutes, may cause the distillation of adjuvant.
As under the situation of liquid crystal material, preferably carry out aggregation processing or crosslinking Treatment at above-mentioned liquid crystal monomer by applying the layer that forms.Aggregation processing makes liquid crystal monomer polymerization and fixedly become the repetitive of polymer molecule.Crosslinking Treatment makes liquid crystal monomer form tridimensional network and fixedly becomes a cancellated part.As a result, the orientation state of liquid crystal material is fixed.Polymerization by liquid crystal monomer or crosslinked formed polymkeric substance or three-dimensional structure are " non-liquid crystal ".Therefore, can not become liquid crystal phase, glassy phase or crystallization phase mutually by changing first birefringent layers that forms for the specific temperature of liquid crystal molecule.
Can be according to the type of polymerization initiator that will use or crosslinking chemical the specific procedure of suitable selective polymerization processing or crosslinking Treatment.For example, under the situation of using photo-induced polymerization initiator or photocrosslinking agent, can carry out photic irradiation.Under the situation of using UV polymerization initiator or UV crosslinking chemical, can carry out the UV irradiation.The type that the total amount of the time of light or UV-irradiation, the intensity of irradiation, irradiation etc. can be handled according to the type of liquid crystal material, type of substrate, orientation, the desired characteristic of first birefringent layers etc. suitably are provided with.
First birefringent layers that then, will form on base material is transferred to the surface of transparent protective film (T).The method that shifts first birefringent layers has no particular limits.For example, first birefringent layers by substrate support can be bonded together by bonding agent and transparent protective film (T).This transfer method can be provided at the elliptical polarization plate that has excellent adhesiveness between the adjacent film (layer) with very high efficient.
The object lesson of above-mentioned bonding agent comprises cure adhesive.The object lesson of cure adhesive comprises for example Photocurable adhesive, moisture curable adhesive (moistsettingadhesive) or the resinoid of ultraviolet curing adhesive.The object lesson of resinoid comprises for example resinoid of epoxy adhesive, isocyanate resin bonding agent or polyimide resin adhesive.The object lesson of moisture curable adhesive comprises moisture curing isocyanate resin bonding agent.Preferred moisture curable adhesive (especially moisture curing isocyanate resin bonding agent).Can moisture curable adhesive be solidified.Therefore, as long as after coating, no longer carry out any processing moisture curable adhesive is solidified, thereby excellent operability is provided.And then, do not need heating during owing to curing, so when first birefringent layers and transparent protective film (T) are not heated when being attached together.As a result, owing to do not produce thermal shrinkage, so even under the extremely thin situation of first birefringent layers and transparent protective film (T), can prevent the problem such as ftractureing when lamination significantly yet.Incidentally, the isocyanate resin bonding agent is comprise polyisocyanate resin bonding agent and urethane resin bonding agent blanket.
As for cure adhesive, for example can use commercially available bonding agent.Perhaps, cured resin binder solution (or dispersion liquid) can be by with dissolution with solvents or disperse any one above-mentioned cured resin to prepare.During preparation cured resin binder solution (or suspension), the solids content of cured resin is preferably 10 to 80wt%, more preferably 20 arrives 65wt%, more preferably 25 arrives 65wt%, most preferably 30 arrives 50wt%.According to the type of cured resin, any suitable solvent can be used as solvent.The object lesson of solvent comprises: ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene and dimethylbenzene.Solvent can use or unite use separately.
Can suitably determine the use amount of bonding agent according to purpose, for example, for every 1cm
2The use amount of first birefringent layers or transparent protective film is preferably 0.3 to 3ml, more preferably 0.5 arrives 2ml, most preferably 1 arrives 2ml.After using, the solvent in the bonding agent can vapor away by air drying or hot-air drying as required.The thickness of the formed adhesive phase of said process is preferably 0.1 to 20 μ m, more preferably 0.5 to 15 μ m, most preferably 1 to 10 μ m.The indentation hardness of adhesive phase (microhardness) is preferably 0.1 to 0.5GPa, more preferably 0.2 arrives 0.5GPa, most preferably 0.3 arrives 0.4GPa.Indentation hardness can change into Vickers hardness, because known indentation hardness is associated with Vickers hardness.Can load by depth of cup of measuring with film hardness measuring instrument (for example, NEC Corporation makes, trade name: MH4000 or MHA-400) and impression and calculate indentation hardness.
At last, divest base material from first birefringent layers.Like this, finish the laminate of first birefringent layers and transparent protective film.
B-2. the step of lamination polarizer
The polarizer lamination is on the surface of transparent protective film (T).As mentioned above, in manufacture method of the present invention, polarizer is in suitable some lamination in time.For example, polarizer can be in advance transparent protective film (T) go up lamination, can form lamination after first birefringent layers, can form after second birefringent layers lamination or can be after forming the 3rd birefringent layers lamination.
Any suitable lamination method (for example adhering to) can be as the method for lamination transparent protective film (T) and polarizer.Can adhere to by using any suitable bonding or contact adhesive.Can suitably select the type of bonding agent or contact adhesive according to the type of adherend (that is, transparent protective film and polarizer).The object lesson of bonding agent comprises: acrylic acid, ethene alcohol radical, silicone base, polyester-based, polyurethane-base and polyether-based polymer adhesive; The isocyanates based adhesive; And rubber-based adhesive.That the object lesson of contact adhesive comprises is acrylic acid, ethene alcohol radical, silicone base, polyester-based, polyurethane-base, polyether-based, isocyanate group and rubber-based pressure-sensitive adhesive.
The thickness of bonding agent or contact adhesive has no particular limits, but preferred 10 to 200nm, more preferably 30 arrive 180nm, most preferably 50 arrive 150nm.
Manufacturing method according to the invention, the slow axis of first birefringent layers can the direction setting to expect in the orientation of base material is handled.Thereby, can use the long light polarizing film (polarizer) of longitudinal stretching.In other words, can with vertically carried out at a predetermined angle with respect to it first birefringent layers (first birefringent layers that is forming on the base material) of the length that orientation handles, long transparent protective film (T) and long light polarizing film (polarizer) separately vertically according to identical direction configuration in be attached together continuously.Thereby, can obtain elliptical polarization plate in very high manufacturing efficient ground.The method according to this invention, transparent protective film need not carry out oblique cutting with respect to its longitudinal direction (draw direction) during lamination.As a result, the angle of optic axis can not change with respect to each film that cut, and causes the elliptical polarized light film not have mass discrepancy with respect to each product.Further, the cutting by film does not produce waste, and can obtain elliptical polarization plate with low cost, is easy to make big Polarizer.The absorption axes direction of polarizer is basically parallel to the vertical of long film.
B-3. form the step of second birefringent layers
Further, second birefringent layers forms on the surface of first birefringent layers.Usually, by forming second birefringent layers at the above-mentioned polymer film of the surperficial lamination of first birefringent layers.Polymer film is preferably stretched film.The lamination method has no particular limits, and any suitable bonding or contact adhesive (for example above-mentioned bonding agent or contact adhesive) can be used for lamination.
Perhaps, as mentioned above, the resin combination that will contain polymerisable liquid crystal and chiral reagent is applied on any suitable substrates, and integral body is heated to the temperature that polymerisable liquid crystal presents mesomorphic state.Like this, by chiral reagent, be twisted state (more particularly, by forming cholesteric structure) with the polymerisable liquid crystal orientation.Polymerisable liquid crystal polymerization under this state, thus obtain having the fixedly film of cholesteric structure.Film is transferred to the surface of first birefringent layers from base material, thereby form second birefringent layers 13.
B-4. form the step of the 3rd birefringent layers
Further, the 3rd birefringent layers forms on the surface of second birefringent layers.Usually, contain the described film of A-4 joint by lamination on the surface of second birefringent layers and form the 3rd birefringent layers with the fixing liquid crystal material of vertical orientation.Preferably form the film that contains with the fixing liquid crystal material of vertical orientation: A-4 is saved described liquid crystal material (liquid crystal monomer or liquid crystal polymer) and liquid-crystal composition is applied on the base material by following method; Vertical orientation shows each liquid crystal material and the liquid-crystal composition of liquid crystal phase; Keep vertical orientation and fixedly liquid crystal material and liquid-crystal composition.The concrete manufacturing course of film will be described hereinafter.
Any suitable substrates can be used as base material.Its object lesson comprises glass baseplate, metal forming, plastic sheet and plastic foil.The thickness of base material is about 10 to 1,000 μ m usually.On base material, do not need the vertical orientation film.
As long as film does not change under the temperature that is used for the orientation liquid crystal material, can use any suitable plastic film.Its object lesson comprises the film that is formed by following transparent polymer, and this transparent polymer comprises: the polyester based polymer of polyethylene terephthalate and PEN for example; The cellulose-based polymer of diacetyl cellulose and triacetyl cellulose for example; The polycarbonate based polyalcohol; The acrylate copolymer of polymethylmethacrylate for example.The further example of plastic foil comprises the film that is formed by following transparent polymer, and this transparent polymer comprises: the styrene-based polymer of polystyrene and vinyl cyanide/styrol copolymer for example; For example tygon, polypropylene, polyolefin and the olefin-based polymer of ethylene/propene copolymer with ring-type or norborene structure; The chlorovinyl polymkeric substance; And the amido polymer of nylon and aromatic polyamides for example.The further example of plastic foil comprises by the formed film of transparent polymer that comprises imide polymkeric substance, sulfuryl polymkeric substance, polyethersulfone based polyalcohol, polyetheretherketone based polyalcohol, polyphenylene sulfide based polyalcohol, vinyl alcohol based polyalcohol, vinylidene chloride based polyalcohol, vinyl butyral based polyalcohol, arylide based polyalcohol, polyoxymethylene based polyalcohol, epoxy-based polymerization thing and product mix thereof.Wherein, the preferred use by triacetyl cellulose, polycarbonate, norbornene polyolefin or the plastic foil that has high hydrogen bonded performance and form as the analog of blooming.The example of metal forming comprises aluminium foil.
Base material can be furnished with any suitable bonding layer and binding layer sequentially from the base material side.The object lesson that forms the material of adhesive phase comprises coupling agent (for example silane coupling agent, titanium coupling agent or zirconium coupling agent) and organic priming paint.The examples of material that forms binding layer comprises metal alkoxide.Adhesive phase and binding layer can form by any suitable method.
The example that liquid crystal material (liquid crystal monomer or liquid crystal polymer) or liquid-crystal composition is coated to the method on the base material comprises: the solution coating process that relates to the solution that use prepares by dissolving liquid crystal material or liquid-crystal composition in solvent; The melt coating process that relates to the melt that use prepares by fusing liquid crystal material or liquid-crystal composition.Wherein, the preferred solution coating process is because can be accurately and easily realize vertical orientation.
Any suitable solvent that can dissolve liquid crystal material or liquid-crystal composition can be used as the solvent of the solution of preparation solution cladding process.The object lesson of solvent comprises: the halogenated hydrocarbons of chloroform, methylene chloride, ethylene dichloride, tetrachloroethane, triclene, zellon and chlorobenzene for example; The phenols of phenol and right-chlorophenol for example; For example benzene,toluene,xylene, methoxybenzene and 1, the aromatic hydrocarbon of 2-dimethoxy benzene; Other are acetone, ethyl acetate, the tert-butyl alcohol, glycerine, ethylene glycol, triethylene glycol, glycol monoethyl ether, diethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, pyridine, triethylamine, tetrahydrofuran, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, acetonitrile, butyronitrile, carbon disulphide and cyclohexanone for example.The concentration of solution can change according to the kind (solubleness) of the liquid crystal material that will use etc., the thickness of expection etc.Specifically, the concentration of preferred solution is 3 to 50wt%.More preferably 7 arrive 30wt%.
Go up to use at base material (binding layer) that the example of the method for solution comprises that roller coat, gravure formula are coated with, spin coating and rod be coated with (bar coating).Wherein, preferred gravure formula is coated with rod and is coated with because they can be on large tracts of land the coating of uniformity.After using solution, remove solvent, thereby on base material, form liquid crystal material layer or liquid-crystal composition layer.The condition of removing solvent has no particular limits, as long as solvent can be removed substantially and liquid crystal material layer or liquid-crystal composition layer fluidisation or flow away from base material not.Usually, by at room temperature dry, at the drying oven inner drying, method such as on heating plate, heat and remove solvent.
Then, liquid crystal material layer that will form on base material or liquid-crystal composition layer are transformed into liquid crystal state and vertical orientation.For example heat-treat and make liquid crystal material or liquid-crystal composition demonstrate liquid crystal state, and mesomorphic liquid crystal material layer or liquid-crystal composition layer vertical orientation.Thermal treatment can be carried out in the mode identical with above-mentioned drying means.Heat treated temperature can change according to the kind of liquid crystal material that will use or liquid-crystal composition and the kind of base material.Specifically, heat treated temperature is preferably 60 to 300 ℃, and more preferably 70 to 200 ℃, most preferably 80 to 150 ℃.Heat treatment time also can change according to the kind of liquid crystal material that will use or liquid-crystal composition and the kind of base material.Specifically, heat treatment period is preferably 10 seconds to 2 hours, and more preferably 20 seconds to 30 minutes, most preferably 30 seconds to 10 minutes.Heat treatment time is shorter than the abundant formation that will hinder vertical orientation in 10 seconds.Heat treatment time is longer than the further formation that will suppress vertical orientation in 2 hours usually, therefore considers not preferred from processibility and throughput rate invention.
After thermal treatment is finished, carry out cooling down operation.By being placed to room temperature, the hot-air of liquid crystal film from heat treatment operation that is subjected to heat treated vertical orientation carry out cooling down operation.Further, cooling down operation can comprise for example air cooling and water-cooled pressure cooling.The liquid crystal film of vertical orientation is cooled to the glass transition temperature that is equal to or less than liquid crystal material, thereby is fixed in the vertical orientation.
Under the situation of using liquid-crystal composition, the liquid crystal film of the vertical orientation of said fixing can be subjected to photic irradiation or UV-irradiation is used for polymerization or crosslinked phtotpolymerizable liquid-crystal compounds, thereby fix phtotpolymerizable liquid-crystal compounds, thereby further improve the permanance of film.For example, the UV-irradiation condition optimization comprises the inert atmosphere that is used for fully quickening polyreaction or cross-linking reaction.Usually, illuminance is about 80 to 160mW/cm
2The high-pressure mercury UV-lamp as the UV-irradiation means.Further, can use for example other lamp of metal halide uviol lamp and incandescent lamp.During UV-irradiation, preferably regulate temperature and make the surface temperature of liquid crystal layer remain on liquid crystal layer to show in the mesomorphic temperature range.The example of regulating method of temperature comprises: use cold mirror; For example water-cooled cooling processing; With the increase linear speed.
Like this, form and fixed the film of liquid crystal material or liquid-crystal composition, and its vertical orientation is maintained, thereby obtains the liquid crystal film of vertical orientation.By bonding agent or contact adhesive with the surface of this film (last, the 3rd birefringent layers) lamination to second birefringent layers, thereby obtain elliptical polarization plate of the present invention.
B-5. on the surface except protective seam (transparent protective film) surface, form the situation of first birefringent layers
For example, described with reference to Figure 1B, first birefringent layers can form (in Figure 1B, first birefringent layers forms on the surface of the 3rd birefringent layers) on the surface except protective seam (transparent protective film) surface.
B-6. concrete manufacturing course
The example of the specific procedure of manufacture method of the present invention is described with reference to Fig. 3 to 8.In Fig. 3 to 8, reference number 111,111 ', 112,112 ', 113,114,115,116,117,118,118 ', 119 and 119 ' is represented separately and is used to roll the film of each layer of formation and/or the roller of laminate.
At first, the long polymer film of preparation is as the raw material of polarizer as mentioned above, and it is carried out painted, stretching etc.Long polymer film is continued longitudinal stretching.Like this, as shown in the skeleton view of Fig. 3, obtain having vertically (draw direction: the direction of the arrow A) polarizer 11 of the length of absorption axes.
Simultaneously, shown in the skeleton view of Fig. 4 A, the base material 17 that preparation is long, and friction treatment is carried out by using friction roller 120 in the surface of film.Obtain having vertically (draw direction: the direction of the arrow A) polarizer 11 of the length of absorption axes.At this moment, frictional direction is with for example+8 ° to the direction of the predetermined angular of+38 ° or-8 ° to-38 ° with respect to the longitudinal direction of transparent protective film 12.Then, shown in the skeleton view of Fig. 4 B, first birefringent layers 13 forms on the surface of the base material 17 of the above-mentioned friction treatment of process.First birefringent layers 13 has along the liquid crystal material of frictional direction orientation, and the direction of its slow axis frictional direction basic and base material 17 is same direction (direction of arrow B).
Next; shown in the synoptic diagram of Fig. 5 A; polarizer 11, transparent protective film (protective seam) 12 and first birefringent layers 13 transmit with the direction of arrow with the laminate 121 of base material 17, and by adhering to each other with (not shown)s such as bonding agents, and separately vertically be configured in same direction.In Fig. 5 A, reference number 122 representative is used for guide roller (using too at Fig. 6 to 8) that film is adhered to each other.Preferably, second transparent protective film (protective seam) 16 can be attached to the opposite side with respect to the polarizer 11 on the transparent protective film (protective seam) 12, thereby obtains laminate 123 '.
Then; shown in Fig. 5 B; divest base material 17 from (second transparent protective film (protective seam) 16, polarizer 11, transparent protective film (protective seam) 12, first birefringent layers 13 and base material 17) laminate 123 ', thereby obtain (second transparent protective film (protective seam) 16, polarizer 11, transparent protective film (protective seam) 12 and first birefringent layers 13) laminate 123.
Shown in the synoptic diagram of Fig. 6; second birefringent layers 14 that preparation is long; and the second long birefringent layers 14 transmits with the direction of arrow with (second transparent protective film (protective seam) 16, polarizer 11, transparent protective film (protective seam) 12 and first birefringent layers 13) laminate 123; and by adhering to each other with (not shown)s such as bonding agents, and separately vertically be configured in same direction.Second birefringent layers can be formed by the polymer film of above-mentioned stretching, and its slow axis can suitably be determined according to drawing process (draw direction etc.).In the present invention, the slow-axis direction of first birefringent layers can be handled and optionally be provided with by the orientation of above-mentioned transparent protective film.Therefore, for example, process can be used as second birefringent layers perpendicular to the general stretching polymer film of cross directional stretch longitudinally, thereby is convenient to handle.
Shown in the synoptic diagram of Fig. 7 A, preparation laminate 125 (forming) by on base material 26, using the 3rd birefringent layers 15.Laminate 125 and (second transparent protective film (protective seam) 16, polarizer 11, transparent protective film (protective seam) 12, first birefringent layers 13 and second birefringent layers 14) laminate 124 transmit with the direction of arrow; and by adhering to each other with (not shown)s such as bonding agents, and separately vertically be configured in same direction.At last, shown in Fig. 7 B, divest base material 26 from the laminate that adheres to.
As mentioned above, obtain elliptical polarization plate 10 of the present invention.
Another example of the specific procedure of manufacture method of the present invention hereinafter will be described.
As mentioned above, shown in the skeleton view of Fig. 3, obtain long polarizer 11.And then, shown in the skeleton view of Fig. 4 A and 4B, obtain the laminate 121 of first birefringent layers 13 and base material 17.
Then; shown in the synoptic diagram of Fig. 8 A; polarizer 11, transparent protective film (protective seam) 12 and second transparent protective film (protective seam) 16 transmit with the direction of arrow, and by adhering to each other with (not shown)s such as bonding agents, and separately vertically be configured in same direction.Obtain the laminate 126 of second transparent protective film (protective seam) 16, polarizer 11 and transparent protective film (protective seam) 12 thus.
Next; shown in the synoptic diagram of Fig. 8 B; (second transparent protective film (protective seam) 16, polarizer 11 and transparent protective film (protective seam) 12) laminate 126 and (first birefringent layers 13 and base material 17) laminate 121 transmit with the direction of arrow; and by adhering to each other with (not shown)s such as bonding agents, and separately vertically be configured in same direction.Obtain the laminate 123 ' of second transparent protective film (protective seam) 16, polarizer 11, transparent protective film (protective seam) 12, first birefringent layers 13 and base material 17 thus.
Next, shown in Fig. 5 B, divest base material 17, thereby obtain (second transparent protective film (protective seam) 16, polarizer 11, transparent protective film (protective seam) 12 and first birefringent layers 13) laminate 123 from laminate 123 '.
In addition, shown in the synoptic diagram of Fig. 6, second birefringent layers 14 that preparation is long, and the second long birefringent layers 14 transmits with the direction of arrow with laminate 123, and by adhering to each other with (not shown)s such as bonding agents, and separately vertically be configured in same direction.
Then, shown in the synoptic diagram of Fig. 7 A, preparation laminate 125 (forming) by on base material 26, using the 3rd birefringent layers 15.Laminate 125 and (second transparent protective film (protective seam) 16, polarizer 11, transparent protective film (protective seam) 12, first birefringent layers 13 and second birefringent layers 14) laminate 124 transmit with the direction of arrow; and by adhering to each other with (not shown)s such as bonding agents, and separately vertically be configured in same direction.At last, shown in Fig. 7 B, divest base material 26 from the laminate that adheres to.
As mentioned above, obtain elliptical polarization plate 10 of the present invention.
B-7. other components of elliptical polarization plate
Elliptical polarization plate of the present invention may further include another optical layers.According to the type of purpose or image display, any suitable optical layers can be used as other optical layers.The object lesson of other optical layers comprises birefringent layers (phase retardation film), liquid crystal film, light-diffusing films and diffraction film.
As mentioned above, elliptical polarization plate of the present invention can be included in polarizer 11 lip-deep second transparent protective films (protective seam) 16 and not form transparent protective film (protective seam) 12 thereon.Any suitable transparent protective film (protective seam) can be used as second transparent protective film (protective seam).For example, A-6 saves described film and can be used as second protective seam.Second transparent protective film (protective seam) 16 each other can be consistent or inequality with transparent protective film (protective seam) 12.As required, second transparent protective film (protective seam) 16 can stand dura mater processing, anti-reflex treated, release treatment and non-glare treated etc.
Elliptical polarization plate of the present invention can comprise that further adhesive layer is as outermost layer at least one side.Comprise that adhesive layer helps the lamination of elliptical polarization plate and miscellaneous part (for example liquid crystal cell) as outermost layer, thereby prevent that elliptical polarization plate from stripping down from miscellaneous part.Any suitable material can be as the material of adhesive layer.The object lesson of this material comprise B-2 joint described those.Because the foaming that the degeneration of the moisture absorption, optical property causes or peel off, and because the preferred material with good humidity resistance and thermal resistance that uses is considered in the aspects such as distortion of the liquid crystal cell that the difference of thermal expansion causes from prevention.
For practical purpose, the surface coverage of adhesive layer has suitable spacer, till this elliptical polarization plate of certain use, thereby prevents to pollute.Spacer can provide release coat to form on any suitable film by for example using silicone base, chain alkyl, fluorine-based or molybdenum sulfide separant.
Each layer of elliptical polarization plate of the present invention can be handled by the ultraviolet absorbers such as complex salt based compound with for example salicylate (salt) based compound, benzophenone based compound, benzotriazole based compound, alpha-cyanoacrylate ester group compound or nickel, or similar processing, and uv absorption property is provided.
C. the use of elliptical polarization plate
Elliptical polarization plate of the present invention is applicable to various image displays (for example LCD and self luminous display).Can use the object lesson of the image display of elliptical polarization plate to comprise LCD, EL display, plasma scope (PD) and field-emitter display (FFD).For example, the elliptical polarization plate of the present invention that is used for LCD is of value to viewing angle compensation.Elliptical polarization plate of the present invention is useful to the LCD of circular polarisation mode, and to switch (IPS) LCD in the TN LCD of vertical orientation, the plate and vertical orientation (VA) LCD particularly useful.For example, the present invention is used for the elliptical polarization plate of EL display for preventing the electrode reflection effectively.
D. image display
LCD will be described as the example of image display of the present invention.Here, the liquid crystal panel that is used for LCD will be described.According to purpose, any appropriate structures can be used as the structure of the LCD except that liquid crystal panel.Fig. 9 is the schematic cross-section according to the liquid crystal panel of preferred implementation of the present invention.Liquid crystal panel 100 comprises: liquid crystal cell 20, be configured in the polarizer 30 and 30 ' of liquid crystal cell 20 both sides; Be configured in the Polarizer 10 and 10 ' in each polarizer outside.According to the alignment mode of purpose and liquid crystal cell, any suitable polarizer can be used as polarizer 30 and 30 '.According to the alignment mode of purpose and liquid crystal cell, at least one in the polarizer 30 and 30 ' can be omitted.Polarizer 10 uses aforesaid elliptical polarization plate of the present invention.Configuration Polarizer (elliptical polarization plate) 10 makes birefringent layers 13,14 and 15 between polarizer 11 and liquid crystal cell 20.Polarizer 10 ' uses any suitable Polarizer.Common configuration Polarizer 10 and 10 ' makes separately, and the absorption axes of polarizer is perpendicular to one another.As shown in Figure 9, elliptical polarization plate 10 preferred disposition of the present invention in LCD of the present invention (liquid crystal panel) watch side (above).Liquid crystal cell 20 comprises: a pair of substrate (typically being glass substrate) 21 and 21 '; Be configured in the liquid crystal layer 22 between the substrate as display medium.A substrate (active-matrix substrate (active matrix substrate)) 21 ' is furnished with: the on-off element (being generally TFT) that is used to control the electro-optical properties of liquid crystal; And be used to on-off element that the sweep trace of gate signal is provided and be used to its signal wire that source signal is provided (this element and line do not show); Another substrate (colour filtering chip basic board) 21 is furnished with the color filter (not shown).Color filter also can be provided in active-matrix substrate 21 ' in.Substrate 21 and 21 ' between distance (cell gap) control by the spacer (not shown).For example will be provided in by the both alignment layers (not shown) that polyimide forms each substrate 21 and 21 ' with liquid crystal layer 22 contacted sides on.
Hereinafter, will the present invention more specifically be described by embodiment.But, the invention is not restricted to these examples.The method of measurement characteristics is described below in example.
(1) measurement of phase differential
With refractive index n x, ny and the nz of automatic birefringence analyser (the automatic birefringence analyser KOBRA-31PR that Oji Scientific Instruments makes) measurement sample film, and interior phase difference nd of calculating face and thickness direction phase differential Rth.Measuring temperature is 23 ℃, and the measurement wavelength is 590nm.
(2) measurement of thickness
Interfere thickness measure (interference thickness measurement) to measure the thickness of first birefringent layers by the MCPD-2000 that uses Otsuka Elcetronics Co.Ltd. to make.The thickness of other various films is all measured with dial gauge.
(3) measurement of transmissivity
Same elliptical polarization plate adheres to each other and forms the elliptical polarization plate of embodiment 1.The elliptical polarization plate that adheres to A series makes each the 3rd birefringent layers toward each other.The elliptical polarization plate that adheres to B series makes each second birefringent layers toward each other.For elliptical polarization plate is adhered to each other, the configuration elliptical polarization plate makes the slow axis of each second birefringent layers be 90 ° (making that the absorption axes of each polarizer is 90 °).Use " DOT-3 " (trade name, Murakami ColorResearch Laboratory makes) to measure the transmissivity that each adheres to sample.The laminated structure of elliptical polarization plate is described below.
Elliptical polarization plate A01 is to A18: polarizer/protective seam/first birefringent layers/second birefringent layers/the 3rd birefringent layers
Elliptical polarization plate B01 is to B18: polarizer/protective seam/the 3rd birefringent layers/first birefringent layers/second birefringent layers
(4) measurement of contrast
Same elliptical polarization plate and use backlight illumination superposes.Display white image (absorption axes of polarizer is parallel to each other) and black image (absorption axes of polarizer is perpendicular to one another), watching side to scan from-60 ° to 60 ° by using " EZ Contrast 160D " (trade name, ELDIM SA makes) with respect to 45 ° of-135 ° of directions of absorption axes of polarizer with respect to normal direction.Calculate oblique contrast " YW/YB " from the Y value (YW) of white image and the Y value (YB) of black image.
[embodiment 1]
I. the manufacturing of the elliptical polarization plate shown in Figure 1A
I-a. (preparation orientation base material) handled in the orientation of base material
The substrate passed orientation is handled, thereby makes the orientation base material.
Base material (1) to (6): the surface of polyethylene terephthalate (PET) film (thickness 50 μ m) carry out friction treatment by using friction cloth with the rubbing angle shown in the table 1, thereby form each orientation base material.
Table 1
| Base material | Rubbing angle (angle [alpha]) |
| (1) | 13° |
| (2) | -13° |
| (3) | 23° |
| (4) | -23° |
| (5) | 33° |
| (6) | -33° |
I-b. the manufacturing of first birefringent layers
The polymerisable liquid crystal (Paliocolor LC242, the trade name that 10g are shown the nematic crystal phase; Derive from BASF Aktiengesellschaft), and 3g is used for the Photoepolymerizationinitiater initiater of polymerisable liquid crystal compound, and (IRGACURE 907, trade name; Derive from Ciba Specialty Chemicals) be dissolved in 40g toluene, thus preparation liquid-crystal composition (coating liquid).This liquid-crystal composition arrives on (6) by the orientation base material (1) that uses spreading rod to be coated to above-mentioned preparation, and integral body is heated and dry 2 minutes at 90 ℃, thereby makes LCD alignment.The liquid crystal layer of Xing Chenging is by using metal halide lamp 1mJ/cm thus
2Rayed, and with this curable liquid crystal layer, thereby on each base material, form each first birefringent layers.
Regulate the thickness and the phase differential of each first birefringent layers by the coated weight that changes coating liquid.Table 2 shows the thickness (μ m) and the interior phase differential (nm) of face of formed each first birefringent layers.
Table 2
| Base material+first birefringent layers | Base material | Rubbing angle (angle [alpha]) | The thickness of first birefringent layers (μ m) | Phase differential (nm) in the face of first birefringent layers |
| (1a) | (1) | 13° | 2.4 | 240 |
| (2a) | (2) | -13° | 2.4 | 240 |
| (3a) | (3) | 23° | 2.2 | 180 |
| (3b) | (3) | 23° | 2.4 | 240 |
| (3c) | (3) | 23° | 2.6 | 300 |
| (4a) | (4) | -23° | 2.2 | 180 |
| (4b) | (4) | -23° | 2.4 | 240 |
| (4c) | (4) | -23° | 2.6 | 300 |
| (5a) | (5) | 33° | 2.4 | 240 |
| (5b) | (6) | -33° | 2.4 | 240 |
I-c. the manufacturing of second birefringent layers
Uniaxial tension polycarbonate membrane under predetermined temperature (thickness 60 μ m) or norborene basement membrane (Arton, trade name; Derive from JSR Corporation; Thickness 60 μ m), thus form each film of second birefringent layers.Table 3 shows type (polycarbonate membrane is represented with PC, and the norborene film is represented with NB), stretching condition (for example draw direction), the orientation angle of employed film and the phase difference value that will obtain.Notice that the orientation angle refers to the angle with respect to the slow axis of the film of longitudinal direction.
Table 3
I-d. the manufacturing of the 3rd birefringent layers
(wherein: numeral 65 and 35 is represented the mol% of monomeric unit respectively with the side chain liquid crystalline polymer of the following chemical formula representative of 20 weight portions; For simplicity polymkeric substance is represented with block polymer; The weight-average molecular weight of polymkeric substance is 5,000), the polymerizable nematic crystal of the demonstration liquid crystal phase of 80 weight portions " Paliocolor LC242 " (trade name, derive from BASFAktiengesellschaft) and Photoepolymerizationinitiater initiater " the IRGACURE 907 " (trade name of 5 weight portions, derive from Ciba Specialty Chemicals) be dissolved in the cyclopentanone of 200 weight portions, thus form the liquid crystal coating liquid.Then, coating liquid is coated on the base material film " ZEONOR " (Zeon Corporation provides for trade name, norborene base resin film) by using spreading rod, whole under 100 ℃ of heating conditions dry 10 minutes, thus make LCD alignment.The liquid crystal layer UV-irradiation, and with this curable liquid crystal layer, thereby the 3rd birefringent layers C1 on the formation base material is to each film of C4.Phase differential is 0 substantially in the face of each film of the 3rd birefringent layers.The phase differential of the thickness direction of the film of table 4 demonstration the 3rd birefringent layers.
Table 4
I-e. the manufacturing of elliptical polarization plate
Polyvinyl alcohol film is painted in containing iodine aqueous solution, and subsequently in borated aqueous solution between the roller of different rates uniaxial tension to 6 double-length degree, thereby obtain polarizer.
Shown in the synoptic diagram of Fig. 5 A; polarizer, protective seam (TAC film; thickness 40 μ m; thickness direction phase differential 60nm) and the laminate of first birefringent layers and base material transmit according to the direction of arrow; and comprise isocyanate " M-631N " (trade name by use; derive from Mitsui Takeda Chemicals, moisture curable adhesive Inc.) adheres to each other, and vertically being configured in the equidirectional separately.The thickness of bonding agent is 5 μ m.
Then, shown in Fig. 5 B, base material is peeled off from (polarizer, protective seam, first birefringent layers and base material) laminate, thereby obtains (polarizer, protective seam and first birefringent layers) laminate.
Further, shown in the synoptic diagram of Fig. 6, prepared long second birefringent layers (a1) to (a7) with (b1) to (b2), and each second long birefringent layers transmits according to the direction of arrow with the laminate that obtains above, and comprise isocyanate " M-631N " (trade name by use, MitsuiTakeda Chemicals, Inc. provides) moisture curable adhesive be bonded together and vertically being configured in the equidirectional separately.
Shown in the synoptic diagram of Fig. 7 A; the 3rd birefringent layers (C1) prepares on long substrate respectively to (C4); the 3rd birefringent layers on the base material transmits according to the direction of arrow with (polarizer, protective seam, first birefringent layers and the second birefringent layers) laminate that obtains above; and comprise isocyanate " M-631N " (trade name by use; Mitsui Takeda Chemicals; Inc. provide) moisture curable adhesive be bonded together and vertically being configured in the equidirectional separately.At last, shown in Fig. 7 B, base material is peeled off from the laminate that adheres to.
As mentioned above, the elliptical polarization plate A01 that obtained as shown in table 5 is to A18.
[embodiment 2]
II. the manufacturing of the elliptical polarization plate shown in Figure 1B
The laminate of same polarizer, protective seam, first birefringent layers and base material, second birefringent layers (a1) to (a7) and (b1) on base material, form respectively to (C4), and the identical bonding agent of use and embodiment 1 to (b2), the 3rd birefringent layers (C1).Polarizer, protective seam, the 3rd birefringent layers, first birefringent layers and second birefringent layers is as shown in table 6 is used in combination, and carry out lamination by reel-to-reel, thus obtain each elliptical polarization plate B01 to B18.In the lamination step, the 3rd birefringent layers is transferred to the surface of protective seam from base material film, and first birefringent layers is transferred to the surface of the 3rd birefringent layers from base material film.Second birefringent layers forms on the surface of first birefringent layers.
[embodiment 3]
Elliptical polarization plate A01 is overlapping to measure contrast.Table 5 shows the Rth of elliptical polarization plate
3/ Rthp is 1.1.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 50 °, and the difference between maximum and the minimum angles is 10 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.Further, 10 ° difference is very little between maximum and the minimum angles, and also is level very preferably in actual use, so this elliptical polarization plate has balanced visual signature.
[embodiment 4]
Elliptical polarization plate A02 is overlapping to measure contrast.Table 5 shows the Rth of elliptical polarization plate
3/ Rthp is 1.1.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 50 °, and the difference between maximum and the minimum angles is 10 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.Further, 10 ° difference is very little between maximum and the minimum angles, and also is level very preferably in actual use, so this elliptical polarization plate has balanced visual signature.
[embodiment 5]
Elliptical polarization plate A03 is overlapping to measure contrast.Table 5 shows the Rth of elliptical polarization plate
3/ Rthp is 1.8.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 60 °, and the difference between maximum and the minimum angles is 20 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[embodiment 6]
Elliptical polarization plate A04 is overlapping to measure contrast.Table 5 shows the Rth of elliptical polarization plate
3/ Rthp is 1.8.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 60 °, and the difference between maximum and the minimum angles is 20 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use
[embodiment 7]
Elliptical polarization plate A05 is overlapping to measure contrast.Table 5 shows the Rth of elliptical polarization plate
3/ Rthp is 2.5.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 70 °, and the difference between maximum and the minimum angles is 30 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[embodiment 8]
Elliptical polarization plate A06 is overlapping to measure contrast.Table 5 shows the Rth of elliptical polarization plate
3/ Rthp is 2.5.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 70 °, and the difference between maximum and the minimum angles is 30 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[embodiment 9]
Elliptical polarization plate A07 is overlapping to measure contrast.Table 5 shows the Rth of elliptical polarization plate
3/ Rthp is 3.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 90 °, and the difference between maximum and the minimum angles is 50 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[embodiment 10]
Elliptical polarization plate A08 is overlapping to measure contrast.Table 5 shows the Rth of elliptical polarization plate
3/ Rthp is 3.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 90 °, and the difference between maximum and the minimum angles is 50 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[comparative example 1]
To except not forming the 3rd birefringent layers, have with each elliptical polarization plate of elliptical polarization plate A01 same structure overlapping to measure contrast.This elliptical polarization plate is 30 ° to the minimum angles of omnirange contrast 10, and maximum angle is 50 °, and the difference between maximum and the minimum angles is 20 °.The minimum angles that realizes omnirange contrast 10 is 30 °, is not suitable level in actual use.
[comparative example 2]
To except not forming the 3rd birefringent layers, have with each elliptical polarization plate of elliptical polarization plate A02 same structure overlapping to measure contrast.This elliptical polarization plate is 30 ° to the minimum angles of omnirange contrast 10, and maximum angle is 50 °, and the difference between maximum and the minimum angles is 20 °.The minimum angles that realizes omnirange contrast 10 is 30 °, is not suitable level in actual use.
[embodiment 11]
Elliptical polarization plate B01 is overlapping to measure contrast.Table 6 shows the Rth of elliptical polarization plate
3/ Rthp is 1.1.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 50 °, and the difference between maximum and the minimum angles is 10 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.Further, 10 ° difference is very little between maximum and the minimum angles, and also is level very preferably in actual use, so this elliptical polarization plate has balanced visual signature.
[embodiment 12]
Elliptical polarization plate B02 is overlapping to measure contrast.Table 6 shows the Rth of elliptical polarization plate
3/ Rthp is 1.1.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 50 °, and the difference between maximum and the minimum angles is 10 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.Further, 10 ° difference is very little between maximum and the minimum angles, and also is level very preferably in actual use, so this elliptical polarization plate has balanced visual signature.
[embodiment 13]
Elliptical polarization plate B03 is overlapping to measure contrast.Table 6 shows the Rth of elliptical polarization plate
3/ Rthp is 1.8.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 60 °, and the difference between maximum and the minimum angles is 20 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[embodiment 14]
Elliptical polarization plate B04 is overlapping to measure contrast.Table 6 shows the Rth of elliptical polarization plate
3/ Rthp is 1.8.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 60 °, and the difference between maximum and the minimum angles is 20 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[embodiment 15]
Elliptical polarization plate B05 is overlapping to measure contrast.Table 6 shows the Rth of elliptical polarization plate
3/ Rthp is 2.5.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 70 °, and difference is 30 ° between maximum and the minimum angles.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[embodiment 16]
Elliptical polarization plate B06 is overlapping to measure contrast.Table 6 shows the Rth of elliptical polarization plate
3/ Rthp is 2.5.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 70 °, and the difference between maximum and the minimum angles is 30 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[embodiment 17]
Elliptical polarization plate B07 is overlapping to measure contrast.Table 6 shows the Rth of elliptical polarization plate
3/ Rthp is 3.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 90 °, and the difference between maximum and the minimum angles is 50 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[embodiment 18]
Elliptical polarization plate B08 is overlapping to measure contrast.Table 6 shows the Rth of elliptical polarization plate
3/ Rthp is 3.This elliptical polarization plate is 40 ° to the minimum angles of omnirange contrast 10, and maximum angle is 90 °, and the difference between maximum and the minimum angles is 50 °.The minimum angles that realizes omnirange contrast 10 is 40 °, is preferred levels in actual use.
[comparative example 3]
To except not forming the 3rd birefringent layers, have with each elliptical polarization plate of elliptical polarization plate B01 same structure overlapping to measure contrast.This elliptical polarization plate is 30 ° to the minimum angles of omnirange contrast 10, and maximum angle is 50 °, and the difference between maximum and the minimum angles is 20 °.The minimum angles that realizes omnirange contrast 10 is 30 °, is not suitable level in actual use.
[comparative example 4]
To except not forming the 3rd birefringent layers, have with each elliptical polarization plate of elliptical polarization plate B02 same structure overlapping to measure contrast.This elliptical polarization plate is 30 ° to the minimum angles of omnirange contrast 10, and maximum angle is 50 °, and the difference between maximum and the minimum angles is 20 °.The minimum angles that realizes omnirange contrast 10 is 30 °, is not suitable level in actual use.
[evaluation]
The result of embodiment and comparative example shows that the elliptical polarization plate of embodiments of the invention all is formed with the 3rd birefringent layers, thereby the minimum angles that realizes omnirange contrast 10 is 40 °, and this has guaranteed preferred levels in actual use.Particularly the maximum of each contrast 10 and the difference between the minimum angles have reduced to 10 ° in embodiment 3,4,11 and 12, and this provides very balanced visual property, and also are very preferred level in actual use.On the contrary, the result of comparative example shows that the minimum angles of omnirange contrast 10 of the elliptical polarization plate of comparative example is 30 °, and this is not suitable level in actual use.
The result of embodiment and comparative example shows, according to the present invention, the slow axis that can play first birefringent layers of λ/2 plate effects can be arranged in the direction of any expection, therefore can use the long light polarizing film (polarizer) (that is the film of absorption axes in longitudinal direction) at longitudinal stretching.In other words, first birefringent layers of the length that on the long substrate that process is handled with respect to its predetermined angular orientation longitudinally, forms, long transparent protective film and long light polarizing film (polarizer); Perhaps at first birefringent layers that passes through the length that forms on the long substrate of handling with respect to its predetermined angular orientation longitudinally and laminate with long light polarizing film (polarizer) and long transparent protective film; They can separately vertically according to the equidirectional configuration in adhere to each other continuously (by so-called reel-to-reel).Thereby elliptical polarization plate obtains with very high production efficiency.The method according to this invention, transparent protective film or polarizer needn't be carried out when lamination with respect to its vertically oblique cutting of (draw direction).As a result, the angle of optic axis can not change with respect to every cutting film, thereby obtains can not making the elliptical polarized light film of each product quality change.And, do not produce waste by the cutting film yet, can obtain elliptical polarization plate with low cost, and promote the manufacturing of large-scale Polarizer.And according to the embodiment of the present invention, second birefringent layers is easy to by the surface of polymer film lamination to first birefringent layers formed.The long limit of the polymer film and first birefringent layers can adhere to each other continuously, thereby obtains second birefringent layers on first birefringent layers.Thereby elliptical polarization plate can obtain with very high production efficiency.Because elliptical polarization plate can obtain by using so-called reel-to-reel to adhere to, the cohesive between the adjacent layer (film) can be very excellent.In addition, according to the present invention, index distribution is that the 3rd birefringent layers of nz＞nx=ny and λ/4 plates and λ/2 plates are used in combination.Therefore, also have the elliptical polarization plate at the broadband and the wide visual angle of excellent properties and the image display that uses this elliptical polarization plate obliquely even obtained.
By the obtainable elliptical polarization plate of method of the present invention applicable to various image displays (for example LCD and self-emitting display).
Under the situation that does not depart from scope and spirit of the present invention, many other changes will be readily apparent to persons skilled in the art and are to implement easily.The scope that therefore it should be understood that claims is not limited by the details of instructions, but will explain widely.
Claims (22)
1. method of making elliptical polarization plate may further comprise the steps:
Form first birefringent layers on the surface of transparent protective film, described first birefringent layers contains λ/2 plates;
With the opposite side surface of polarizer lamination to described transparent protective film;
With the surface of polymer film lamination to described first birefringent layers, thereby form second birefringent layers, described second birefringent layers contains λ/4 plates; And
Forming index distribution on the surface of described second birefringent layers is the 3rd birefringent layers of nz＞nx=ny,
Wherein said first birefringent layers is configured in the opposite side of the above polarizer of transparent protective film, and
The step that wherein forms described first birefringent layers may further comprise the steps: the coating liquid that will contain liquid crystal material is coated on the base material of handling through orientation; Show under the temperature of liquid crystal phase alignment direction according to substrate surface at described liquid crystal material with described liquid crystal material orientation, thereby on described base material, form described first birefringent layers; And described first birefringent layers that will form on described base material is transferred to the surface of described transparent protective film.
2. the method for manufacturing elliptical polarization plate according to claim 1 is characterized in that:
Described polarizer, described transparent protective film, described first birefringent layers that forms on described base material and the described polymer film that forms described second birefringent layers all contain long film;
Described polarizer, described transparent protective film with described first birefringent layers that forms on the described base material separately vertically according to identical direction configuration in adhere to each other continuously, thereby form the laminate that has described polarizer, described transparent protective film, described first birefringent layers and described base material successively;
Described base material is peeled off from described laminate; And
With the laminate of having peeled off described base material and the described polymer film that forms described second birefringent layers separately vertically according to identical direction configuration in adhere to each other continuously.
3. the method for manufacturing elliptical polarization plate according to claim 1 is characterized in that described liquid crystal material contains at least a in liquid crystal monomer and the liquid crystal polymer.
4. the method for manufacturing elliptical polarization plate according to claim 1 is characterized in that described base material contains the polyethylene terephthalate film.
5. the method for manufacturing elliptical polarization plate according to claim 1 is characterized in that described polymer film contains stretched film.
6. the method for manufacturing elliptical polarization plate according to claim 1 is characterized in that the absorption axes of described polarizer is vertical substantially each other with the slow axis of described second birefringent layers.
7. the method for manufacturing elliptical polarization plate according to claim 1, the slow axis that it is characterized in that described first birefringent layers are defined as with respect to the absorption axes of a described polarizer angle for+8 ° to+38 ° and-8 ° to-38 °.
8. the method for manufacturing elliptical polarization plate according to claim 1 is characterized in that described transparent protective film forms by containing the film of triacetyl cellulose as principal ingredient.
9. method of making elliptical polarization plate may further comprise the steps:
Forming index distribution on the surface of transparent protective film is the 3rd birefringent layers of nz＞nx=ny;
With the opposite side surface of polarizer lamination to described transparent protective film;
Form first birefringent layers on the surface of described the 3rd birefringent layers, described first birefringent layers contains λ/2 plates; And
With the surface of polymer film lamination to described first birefringent layers, thereby form second birefringent layers, described second birefringent layers contains λ/4 plates; And
Wherein said the 3rd birefringent layers is configured in the opposite side of the above polarizer of transparent protective film, and
The step that wherein forms described first birefringent layers may further comprise the steps:
The coating liquid that will contain liquid crystal material is coated on the base material of handling through orientation; Show under the temperature of liquid crystal phase alignment direction according to substrate surface at described liquid crystal material with described liquid crystal material orientation, thereby on described base material, form described first birefringent layers; And described first birefringent layers that will form on described base material is transferred to the surface of described the 3rd birefringent layers.
10. the method for manufacturing elliptical polarization plate according to claim 9 is characterized in that
Described polarizer, described transparent protective film, described the 3rd birefringent layers, described first birefringent layers that forms on described base material and the described polymer film that forms described second birefringent layers all contain long film;
Have the laminate of described polarizer, described transparent protective film and described the 3rd birefringent layers and described first birefringent layers that on described base material, forms successively, separately vertically according to identical direction configuration in adhere to each other continuously, thereby form the laminate that has described polarizer, described transparent protective film, described the 3rd birefringent layers, described first birefringent layers and described base material successively;
Described base material is peeled off from described laminate; And
With the laminate of having peeled off described base material and the described polymer film that forms described second birefringent layers separately vertically according to identical direction configuration in adhere to each other continuously.
11. the method for manufacturing elliptical polarization plate according to claim 9 is characterized in that described liquid crystal material contains at least a in liquid crystal monomer and the liquid crystal polymer.
12. the method for manufacturing elliptical polarization plate according to claim 9 is characterized in that described base material contains the polyethylene terephthalate film.
13. the method for manufacturing elliptical polarization plate according to claim 9 is characterized in that described polymer film contains stretched film.
14. the method for manufacturing elliptical polarization plate according to claim 9 is characterized in that the absorption axes of described polarizer is vertical substantially each other with the slow axis of described second birefringent layers.
15. the method for manufacturing elliptical polarization plate according to claim 9, the slow axis that it is characterized in that described first birefringent layers are defined as with respect to the absorption axes of a described polarizer angle for+8 ° to+38 ° and-8 ° to-38 °.。
16. the method for manufacturing elliptical polarization plate according to claim 9 is characterized in that described transparent protective film forms by containing the film of triacetyl cellulose as principal ingredient.
17. an elliptical polarization plate, it is by manufacture method manufacturing according to claim 1.
18. an image display, it contains elliptical polarization plate according to claim 17.
19. image display according to claim 18 is characterized in that described elliptical polarization plate is configured in to watch side.
20. an elliptical polarization plate, it is by manufacture method manufacturing according to claim 9.
21. an image display, it contains elliptical polarization plate according to claim 20.
22. image display according to claim 21 is characterized in that described elliptical polarization plate is configured in to watch side.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106461839A (en) * | 2014-04-30 | 2017-02-22 | 日东电工株式会社 | Circular polarizer for organic el display device, and organic EL display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101525998B1 (en) * | 2011-12-12 | 2015-06-04 | 제일모직주식회사 | Polarized film for organic light emitting diodes and display device comprising the same |
| US9921351B2 (en) | 2012-05-10 | 2018-03-20 | Samsung Electronics Co., Ltd. | Multilayered optical film, manufacturing method thereof, and display device |
| US10216041B2 (en) * | 2015-09-16 | 2019-02-26 | Samsung Electronics Co., Ltd. | Optical film, manufacturing method thereof and display device |
| KR102435573B1 (en) * | 2018-06-20 | 2022-08-23 | 삼성에스디아이 주식회사 | Optical film, polarizing plate comprising the same and display apparatus comprising the same |
| CN112740304A (en) * | 2018-09-28 | 2021-04-30 | 东洋纺株式会社 | Image display device with fingerprint verification sensor |
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| CN106461839A (en) * | 2014-04-30 | 2017-02-22 | 日东电工株式会社 | Circular polarizer for organic el display device, and organic EL display device |
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| CN106461839B (en) * | 2014-04-30 | 2020-11-03 | 日东电工株式会社 | Circular polarizing plate for organic EL display device and organic EL display device |
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