CN101887143A - Polarization element diaphragm, Polarizer and liquid crystal display cells - Google Patents
Polarization element diaphragm, Polarizer and liquid crystal display cells Download PDFInfo
- Publication number
- CN101887143A CN101887143A CN201010180638XA CN201010180638A CN101887143A CN 101887143 A CN101887143 A CN 101887143A CN 201010180638X A CN201010180638X A CN 201010180638XA CN 201010180638 A CN201010180638 A CN 201010180638A CN 101887143 A CN101887143 A CN 101887143A
- Authority
- CN
- China
- Prior art keywords
- polarization element
- substrate layer
- diaphragm
- element diaphragm
- polarizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
Abstract
The invention relates to a kind of polarization element diaphragm, Polarizer and liquid crystal display cells, its purpose is to provide a kind of and has implemented at the easily then cellulose esters system polarization element diaphragm of the novelty of shape and have the Polarizer and the liquid crystal display cells of this polarization element diaphragm by polarization element that polyvinyl alcohol (PVA) constituted.This polarization element diaphragm of the present invention has cellulose esters system transparent substrate layer, and has the micro concavo-convex shape that is formed on described substrate layer inner face, and the alignment diagram surface roughness (Ra) of substrate layer inner face is below the above 10 μ m of 1 μ m.The mean roughness (Rz) at ten places of described substrate layer inner face is preferably below the above 60 μ m of 2 μ m, and the mean roughness (Rz) at ten places of substrate layer inner face is preferably more than 1 below 15 with respect to the roughness ratio (Rz/Ra) of arithmetic average roughness (Ra).
Description
Technical field
The liquid crystal display cells that the present invention relates to a kind of polarization element diaphragm, has the Polarizer of polarization element diaphragm and have Polarizer.
Background technology
In recent years, (liquid crystal display be that slim, light weight and power consumption are little LCD), so (cathode ray tube CRT) is extensive use of can to replace cathode-ray tube (CRT) because liquid crystal indicator.The use field of liquid crystal indicator, be from small-sized product such as in the past counter or clock expand to automobile with instrument, (personal computer is PC) in the large-scale product such as display, TV for computer.
As shown in Figure 5, the common liquid crystal display cells 21 that is configured on the liquid crystal indicator has: liquid crystal cells 25, and it is to be formed by the transparent dielectric layer 26 of two faces (for example glass) clamping liquid crystal layer 27; Polarizer 22, its be have polarisation can two faces of polarization element 24 applying polarization element diaphragm 23 forms via solid; And has the structure that forms from holding liquid crystal unit 25 up and down by Polarizer 22 via adhesion agent layer 28.As mentioned above, improve intensity certainly and become easy viewpoint consideration, protect polarization element 24 by polarization element diaphragm 23 with making operation.
The material of polarization element uses the polyvinyl alcohol (PVA) (polyvinylalcohol as hydrophilic resin usually, PVA), by with behind the PVA film uniaxial extension, dye with iodine or dichroic dye, perhaps after dyeing, extend, then carry out crosslinked with boron compound and the formation polarization element.In addition, the polarization element diaphragm require to have on the optics transparent and birefringence is little, with characteristics such as then property excellence by the polarization element that PVA constituted, therefore use usually triacetyl cellulose (triacetylcellulose, TAC).After with alkali triacetyl cellulose being carried out saponification and handles (ester group is replaced to hydroxyl as hydrophilic radical), via water-soluble solid then on by the polarization element that polyvinyl alcohol (PVA) constituted as hydrophilic resin.
Tri acetyl cellulose membrane utilizes solution film casting method manufacturing usually.So-called solution film casting method is meant the mix solution of (dope) of the what is called that triacetyl cellulose is dissolved in form in the halogen series solvent equal solvent, and the stream casting is on as the endless belt of the rotation of supporter or drum and the method for making of film forming.After stream casting, the part of solvent is in addition dry on supporter, peel off the film that solidifies and obtain from supporter, remaining solvent seasoning is obtained tri acetyl cellulose membrane.
This method must be removed at the inner remaining solvent of the film that is shaped, so equipment such as the recovery of the solvent of drying line or evaporation and regenerating unit and manufacturing cost become huge.In addition, because use the halogen series solvent, so with regard to the environmental problem aspect, also need to develop substitute material and other manufacture methods.On the other hand, also proposed to utilize extrusion by melting (melt extrusion method) to make the method (for example the Jap.P. spy opens the 2006-63169 communique, the Jap.P. spy opens 2006-306027 communique etc.) of cellulose ester membrane.Yet, according to the cellulose ester membrane that utilizes these methods to obtain, have following problem:, and can't obtain and then property fully owing to form the surface smoothly by polarization element that PVA constituted.
Patent documentation 1: the Jap.P. spy opens the 2006-63169 communique
Patent documentation 2: the Jap.P. spy opens the 2006-306027 communique
Summary of the invention
The objective of the invention is to; overcome the defective that above-mentioned prior art exists; and provide a kind of enforcement to be very suitable for practicality at the easily then cellulose esters system polarization element diaphragm of the novelty of shape and have the Polarizer and the liquid crystal display cells of this polarization element diaphragm by polarization element that polyvinyl alcohol (PVA) constituted.
The object of the invention to solve the technical problems realizes by the following technical solutions.According to a kind of polarization element diaphragm that the present invention proposes, it has cellulose esters system transparent substrate layer, and
Have the micro concavo-convex shape that is formed on described substrate layer inner face,
The alignment diagram surface roughness (Ra) of substrate layer inner face is below the above 10 μ m of 1 μ m.
This polarization element diaphragm becomes with the surfaceness (Ra) of this inner face at the substrate layer inner face that the mode below the 10 μ m has the micro concavo-convex shape more than the 1 μ m.Because this polarization element diaphragm has the micro concavo-convex shape of described size at the whole inner face of substrate layer as mentioned above, so the surface area of substrate layer inner face obviously increases.Therefore, according to this polarization element diaphragm,, thereby follow the property raising because polarization element or adhesion agent layer obviously increase with the area that the substrate layer inner face contacts.In addition, if inner face has the cellulose esters system substrate layer saponification of broad surface area as inciting somebody to action as mentioned above with alkali, so interior face surface produce as the hydroxyl of hydrophilic radical than increasing usually, also can improve effectively thus with by the polarization element that polyvinyl alcohol (PVA) constituted and the then property of adhesion agent layer.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid polarization element diaphragm; the mean roughness (Rz) at ten places of wherein said substrate layer inner face is preferably below the above 60 μ m of 2 μ m, and the mean roughness (Rz) at ten places of substrate layer inner face is preferably more than 1 below 15 with respect to the roughness ratio (Rz/Ra) of arithmetic average roughness (Ra).The mean roughness (Rz) at ten places by making the substrate layer inner face and can further enlarge the surface area of inner face in described scope, and further improves then property.In addition, the micro concavo-convex shape by the substrate layer inner face is in the mode of roughness ratio (Rz/Ra) in described scope, has fixing roughness on the whole and roughly is formed uniformly, and can increase the surface area of substrate layer inner face and can reduce concavo-convex inequality.Therefore, according to this polarization element diaphragm, can improve the homogeneity of following with polarization element, and can reduce the bright spot on the film, can improve quality as the diaphragm of polarization element.
Aforesaid polarization element diaphragm, wherein said cellulose esters is preferably cellulose-acetate propionate.The meltbility of cellulose-acetate propionate, have excellent formability, therefore can be easily and form the concaveconvex shape of substrate layer inner face economically.In addition, easily cellulose-acetate propionate is carried out saponification and handle, can be easily and given play to the water wettability of substrate layer inner face fully by saponification.
Aforesaid polarization element diaphragm, wherein this polarization element diaphragm can have anti-reflecting layer (for example comprise the anti-reflecting layer that be called antiglare layer (anti-glare layer), anti-reflecting layer, low-index layer) or the hard conating of lamination at the substrate layer exterior side.When the polarization element diaphragm with anti-reflecting layer is provided in the display surface side of liquid crystal display cells, in the protection polarization element, can give play to anti-reflection function.In addition, further have hard conating, and can strengthen the defencive function of polarization element by the polarization element diaphragm.
Aforesaid polarization element diaphragm; wherein this polarization element diaphragm preferably utilizes and extrudes the thin slice forming process and form; that is, the roller die of the counter-rotating shape of the cellulose esters that makes molten condition by having described substrate layer inner face around and the bite of other rollers, and the described shape of transfer printing.If by utilizing this so-called embossing of extruding the thin slice forming process to process the concaveconvex shape that forms the substrate layer inner face, so can be easily and exactly to the size of this concaveconvex shape or concrete shape, and the surfaceness of substrate layer inner face etc. set and adjust.In addition, extrude the concaveconvex shape shaping that the thin slice forming process is carried out film shaping and substrate layer inner face simultaneously by utilization, and when the film that is shaped is reeled, because the existence of the concaveconvex shape of substrate layer inner face, and can reduce intermembranous connecting airtight property, therefore can make the film of speciality volume.
The object of the invention to solve the technical problems also realizes by the following technical solutions.A kind of Polarizer according to the present invention's proposition; it possess polarization element with polyvinyl alcohol (PVA), and lamination at a pair of polarization element diaphragm of two face sides of this polarization element; in Polarizer, preferred this polarization element diaphragm of having a micro concavo-convex shape at the substrate layer inner face of using is as the polarization element diaphragm of a slice at least.In this Polarizer; by at least one face side at polarization element; use has this polarization element diaphragm of easily following the substrate layer of shape of having implemented at polyvinyl alcohol (PVA); and can improve the then property of polarization element and this polarization element diaphragm, the permanance of following, but also can improve intensity, the operability of Polarizer.
The object of the invention to solve the technical problems realizes in addition more by the following technical solutions.A kind of liquid crystal display cells according to the present invention's proposition; its have liquid crystal cells, with lamination at a pair of Polarizer of two face sides of this liquid crystal cells; in liquid crystal display cells; the preferred use has the described Polarizer that has the polarization element diaphragm of micro concavo-convex shape at the substrate layer inner face, is used as the Polarizer of a slice at least.In this liquid crystal display cells, the then property of polarization element and polarization element diaphragm, then permanance height, the intensity of Polarizer, operability excellence, so each characteristic that liquid crystal display cells had can bring into play long-term and stably, reliability improves.
In addition, in the present invention, so-called " inner face " is meant in the Polarizer that the clamping polarization element forms between a pair of polarization element diaphragm, the polarization element side at center, and so-called " outside " is meant the opposition side of the polarization element side at this center.In addition, so-called " exterior side " waits certain " face side ", not only refers to the situation of direct lamination at this certain face, and comprises the situation of the lamination via other layers.In addition, " arithmetic average roughness (Ra) " reaches " mean roughness at ten places (Rz) " is according to JIS B0601-1994, is 2.5mm at cutoff value λ c, the value when evaluation length is 12.5mm.
The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme; polarization element diaphragm of the present invention, Polarizer and liquid crystal display cells have following advantage and beneficial effect at least: according to polarization element diaphragm of the present invention; inner face form at by polarization element that polyvinyl alcohol (PVA) constituted easily then shape, be the micro concavo-convex shape, therefore improved by leaps and bounds with the then property that has as the polarization element of the polyvinyl alcohol (PVA) of hydrophilic resin.In addition, owing to have this concaveconvex shape, and can make the film of extruding in the thin slice shaping realize long size.In addition, because Polarizer has this polarization element diaphragm, and the intensity of this Polarizer, operability are improved.In addition, because liquid crystal display cells has this Polarizer, and can bring into play desired characteristic long-term and stably.
In sum; the invention relates to a kind of polarization element diaphragm, Polarizer and liquid crystal display cells, its purpose is to provide a kind of and has implemented at the easily then cellulose esters system polarization element diaphragm of the novelty of shape and have the Polarizer and the liquid crystal display cells of this polarization element diaphragm by polarization element that polyvinyl alcohol (PVA) constituted.This polarization element diaphragm of the present invention has cellulose esters system transparent substrate layer, and has the micro concavo-convex shape that is formed on described substrate layer inner face, and the alignment diagram surface roughness (Ra) of substrate layer inner face is below the above 10 μ m of 1 μ m.The mean roughness (Rz) at ten places of described substrate layer inner face is preferably below the above 60 μ m of 2 μ m, and the mean roughness (Rz) at ten places of substrate layer inner face is preferably more than 1 below 15 with respect to the roughness ratio (Rz/Ra) of arithmetic average roughness (Ra).The present invention has obvious improvement technically, and has tangible good effect, really is a new and innovative, progressive, practical new design.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of instructions, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
Fig. 1 is the diagrammatic cross-section of the polarization element diaphragm of an expression example of the present invention.
Fig. 2 is the diagrammatic cross-section of Polarizer with polarization element diaphragm of Fig. 1.
Fig. 3 is the schematic representation of apparatus of the Polarizer of expression shop drawings 2.
Fig. 4 is the diagrammatic cross-section of liquid crystal display cells with Polarizer of Fig. 2.
Fig. 5 is the diagrammatic cross-section of structure that expression utilizes the general liquid crystal display cells of conventional art.
1: polarization element diaphragm 2: substrate layer
3: concaveconvex shape 4: Polarizer
5: polarization element 6: adhesion agent layer
7: Polarizer manufacturing installation 8: roller
9: roller 10: the solid feed mechanism
11: roller 12: liquid crystal indicator
13: liquid crystal cells 14: transparent dielectric layer
15: liquid crystal layer 16: adhesion agent layer
21: liquid crystal display cells 22: Polarizer
23: polarization element diaphragm 24: polarization element
25: liquid crystal cells 26: transparent dielectric layer
27: liquid crystal layer 28: adhesion agent layer
Embodiment
Reach technological means and the effect that predetermined goal of the invention is taked for further setting forth the present invention; below in conjunction with accompanying drawing and preferred embodiment; to its embodiment of polarization element diaphragm, Polarizer and liquid crystal display cells, structure, feature and the effect thereof that foundation the present invention proposes, describe in detail as after.
The polarization element diaphragm 1 of Fig. 1 has transparent substrate layer 2.
Substrate layer 2 is a cellulose esters system.The low-grade fatty acid ester system of substrate layer 2 special preferred celluloses.Lower fatty acid in the so-called cellulosic low-grade fatty acid ester is meant that carbon number is the fatty acid below 6, for example can enumerate cellulose acetate, cellulose propionate, cellulose butyrate etc., preferred especially cellulose-acetate propionate.In addition, as described later, except that cellulose esters such as cellulose-acetate propionate, can in substrate layer 2, add one or more adjuvants.
Because substrate layer 2 be cellulose esters system, therefore utilize saponification to handle ester group with the surface and be replaced to hydroxyl, thereby follow easily on by the polarization element that polyvinyl alcohol (PVA) constituted as hydrophilic resin as hydrophilic radical.Particularly according to cellulose-acetate propionate, available commercial run easily carries out saponification to be handled, and can be accurately and form the micro concavo-convex shape 3 of substrate layer 2 inner faces described later economically.In addition, cellulose-acetate propionate is excellent and can utilize and extrude the thin slice forming process and be shaped owing to meltbility, does not therefore need halogenated solvent, and is also excellent with regard to environment aspect and energy-conservation aspect.
Substrate layer 2 has the micro concavo-convex shape 3 that is formed at inner face.Surfaceness by these micro concavo-convex shape 3 caused substrate layer 2 inner faces, the lower limit of preferred Ra (arithmetic average roughness) is 1 μ m, be preferably 2 μ m, 3 μ m more preferably, and the higher limit of preferred Ra is 10 μ m, be preferably 8 μ m, more preferably 6 μ m, especially be preferably 4 μ m, be preferably 3 μ m especially.Because this polarization element diaphragm 1 is the micro concavo-convex shape 3 that has described size at the whole inner face of substrate layer 2, so the surface area of substrate layer 2 inner faces obviously increases.Therefore, according to this polarization element diaphragm 1, polarization element or adhesion agent layer can increase with the area that substrate layer 2 inner faces contact, thus with the then property raising of polarization element and adhesion agent layer.In addition, if the cellulose esters system substrate layer 2 that inner face as mentioned above has the surface area of obvious broadness is carried out saponification with alkali, can produce a large amount of hydroxyls in interior face surface so as hydrophilic radical, also can improve effectively therefore in this way, with by the polarization element that polyvinyl alcohol (PVA) constituted and the then property of adhesion agent layer.In addition, if the surfaceness of substrate layer 2 inner faces less than described scope, therefore then the surface area of inner face can not increase fully so, the raising of property and not obvious.In addition, if the surfaceness of substrate layer 2 inner faces surpasses described scope, the surface uniformity of the light that sees through so descends.
In addition, because the inner face of substrate layer 2 has described concaveconvex shape 3, so when this substrate layer 2 or polarization element diaphragm 1 are shaped, and when reeling, can utilize this concaveconvex shape 3 to prevent intermembranous close contact with roller.Therefore, according to this polarization element diaphragm 1, the adhesion after can preventing to reel also makes film realize long size.
The mean roughness (Rz) at preferred ten places of surfaceness of substrate layer 2 inner faces is below the above 60 μ m of 2 μ m, is preferably below the above 30 μ m of 2 μ m.Surfaceness by making substrate layer 2 inner faces and can further enlarge the surface area of inner face in described scope, and can raising and the property of following of polarization element and adhesion agent layer.If the mean roughness (Rz) at ten places of substrate layer 2 inner faces surpasses described scope, can form the thickness position as thin as a wafer of substrate layer 2 so, so the intensity of substrate layer 2 can descend.If the mean roughness (Rz) at ten places of substrate layer 2 inner faces is less than described scope, the surface area of inner face can not increase fully so, and can not show the then raising effect of property.
In addition, the mean roughness (Rz) at ten places of preferred substrates layer 2 inner face is more than 1 below 15 with respect to the roughness ratio (Rz/Ra) of arithmetic average roughness (Ra), is preferably more than 1.5 below 15, more preferably more than 2 below 15.Usually the polarization element diaphragm is preferably the few polarization element diaphragm of bright spot.So-called bright spot is meant two Polarizers of orthogonal configuration, disposes cellulose ester membrane between these Polarizers, and when the face of a slice Polarizer was observed cellulose ester membrane, the light of light source leaked and visible point.The mean roughness at ten places (Rz) is the parameter of the local concavo-convex size of expression, if roughness ratio (Rz/Ra) is big, so local exist a large amount of concavo-convex greatly.This part concavo-convex becomes one of bright spot on the film.Therefore; micro concavo-convex shape 3 by substrate layer 2 inner faces becomes the mode of described scope with roughness ratio (Rz/Ra), and integral body roughly is formed uniformly, and can reduce the concavo-convex inequality of inner face; therefore reduce bright spot, and improve quality as the diaphragm of polarization element.If the roughness ratio (Rz/Ra) of substrate layer 2 inner faces surpasses described scope, so owing to can produce between polarization element and substrate layer 2 inner faces because of concaveconvex shape 3 caused fine gaps, and the decline of connecting airtight property is followed property and is descended on the contrary.In addition,, can form the thickness position as thin as a wafer of substrate layer 2 so if the roughness ratio (Rz/Ra) of substrate layer 2 inner faces surpasses described scope, so the strength degradation of substrate layer 2.
The average thickness of substrate layer 2 is preferably below the above 200 μ m of 10 μ m, more preferably below the above 100 μ m of 20 μ m.By the thickness that makes substrate layer 2 is more than the 10 μ m, and can obtain appropriate intensity and rigidity, and can stablize and easily carry out the film manufacturing, on the other hand, by the thickness that makes substrate layer 2 is below the 200 μ m, and can improve linear velocity when making, productivity, controlled etc.
The cellulose esters that is used for substrate layer 2 is to be raw material with the cellulose, makes by the acidylate of hydroxyl.In the employed in the present invention cellulose esters, be not particularly limited, can measure the conjugation of fatty acid on cellulosic hydroxyl, obtain degree of substitution by calculating for the degree of substitution of cellulosic hydroxyl.The mensuration of degree of substitution can be utilized ASTM (American society for testing materials), and (American Society for TestingMaterial, the method for stipulating among D-817-91 ASTM) is carried out.
Be used for cellulose-acetate propionate of the present invention and preferably satisfy following formula (A) and (B).
2.0≤X+Y≤3.0??(A)
1.2≤X≤2.8????(B)
In the formula, X represents the degree of substitution of acetyl group with respect to hydroxyl, and Y represents the degree of substitution of propiono with respect to cellulosic hydroxyl.So-called " degree of substitution " is meant the total of hydrogen atom substituted ratio of each hydroxyl of cellulosic 2,3 and 6.When all hydroxyls of 2,3 and 6 during by acyl substituted degree of substitution be 3.
Employed cellulose-acetate propionate more preferably satisfies following formula (A ') and (B ') among the present invention, especially preferably satisfies following formula (A ") and (B ").
2.2≤X+Y≤2.9????(A′)
1.3≤X≤2.7??????(B′)
2.4≤X+Y≤2.8????(A″)
1.4≤X≤2.6??????(B″)
Satisfy the cellulose-acetate propionate of described formula, the hydrophobicity by making acyl group and the water wettability of hydroxyl be balance moderately, can shape easily to membranaceous.These cellulose-acetate propionates can utilize known method synthetic.
The preferred operating weight average molecular weight Mw of employed cellulose esters/number average molecular weight Mn is preferably 2.0～5.0 especially than the cellulose esters that is 1.5～5.5 among the present invention, and more preferably 2.5～5.0, especially preferably use 3.0～5.0 cellulose esters.
The raw cellulose of employed cellulose esters can be wood pulp and also can be velveteen among the present invention, and wood pulp can be conifer and also can be broad leaf tree, more preferably conifer.With regard to the fissility aspect during with regard to film forming, preferably use velveteen.The cellulose esters of being made by these raw materials can suitably mix, and perhaps uses separately.
For example can be to be derived from the cellulose esters of velveteen: the cellulose esters that is derived from wood pulp (conifer): the ratio that is derived from the cellulose esters of wood pulp (broad leaf tree) be used in 100: 0: 0,90: 10: 0,85: 15: 0,50: 50: 0,20: 80: 0,10: 90: 0,0: 100: 0,0: 0: 100,80: 10: 10,85: 0: 15,40: 30: 30.
The few cellulose esters of bright spot when in addition, employed cellulose esters is preferably film forming among the present invention.Think that one of the reason of bright spot is to contain unreacted cellulose in the cellulose esters, can remove unreacted cellulose, reduce bright spot by the cellulose esters of filtering molten.In addition, have following tendency: the thickness of film is thin more, and the bright spot number of per unit area is few more, and the content of contained cellulose esters is few more in the film, and bright spot is few more.
The above bright spot of the preferred diameter 0.01mm of bright spot is 200/cm
2Below, 100/cm more preferably
2Below, and then be preferably 50/cm
2Below, especially be preferably 30/cm
2Below, be preferably 10/cm especially
2Below, most preferably being does not have bright spot fully.In addition, for the bright spot below 0.005mm～0.01mm, also be preferably 200/cm
2Below, 100/cm more preferably
2Below, and then be preferably 50/cm
2Below, especially be preferably 30/cm
2Below, be preferably 10/cm especially
2Below, most preferably being does not have bright spot fully.
When removing the bright spot foreign matter by filtration, compared with filter the fused solution that the plain ester of independent fused fiber forms, filter the bright spot foreign matter that adds the constituent that has mixed plastifier to remove efficient higher, and preferred.Also can filter the suitable constituent that has mixed ultraviolet light absorber, other additives.As for filtration, preferably the viscosity with the fused mass that contains cellulose esters is to filter below the 10000P, more preferably below the 5000P, especially is preferably below the 1000P, is preferably below the 500P especially.Filter medium preferably uses known in the past filter mediums such as fluororesin such as glass fibre, cellulose fibre, filter paper, tetrafluoroethylene resin, preferred especially pottery, the metal etc. of using.Absolute filtering accuracy preferably uses the following filter medium of 50 μ m, and more preferably the following filter medium of 30 μ m especially is preferably the following filter medium of 10 μ m, especially preferably uses the following filter medium of 5 μ m.Also these filter medium appropriate combination can be used.Filter medium can use surface type (surface type) also can use degree of depth type (depth type), the difficult obstruction of the filter medium of degree of depth type and preferred the use.
Preferred use at least once cellulose esters with raw material to be dissolved in the solvent after, the cellulose esters that solvent seasoning is formed.More preferably together be dissolved in the cellulose esters that the back drying forms in the solvent with more than the cellulose esters of raw material and plastifier, ultraviolet light absorber and matting agent at least a.More preferably in the process of dissolving, be cooled to the cellulose esters below-20 ℃ in addition.By adding this cellulose esters, can improve the uniformly dispersed of each additive when becoming molten condition, and make optical characteristics even, therefore also excellent.This cellulose esters of preferred especially interpolation is more than 1 percentage by weight (wt%) of the plain ester of total fiber, more preferably more than the 5wt%, and then be preferably more than the 10wt%, especially be preferably more than the 30wt%, be preferably especially more than the 50wt%, most preferably be with solvent once with the plain ester raw material dissolving of all fibres.
Polarization element diaphragm 1 of the present invention also can be the suitable film that has mixed the macromolecule component except that cellulose esters.The macromolecule component that is mixed is preferably the macromolecule component with the compatibility excellence of cellulose esters, and the transmissivity when being preferably film forming is more than 80%, more preferably more than 90%, especially is preferably more than 92%.
Employed cellulose esters also can contain more than one adjuvant among the present invention.Adjuvant can mix with cellulose esters in advance, also can be in extrusion by melting goes into the mixing midway of extruder.In order to add equably, preferably use static mixer mixing arrangements such as (static mixer).Adjuvant can be enumerated: plastifier, antioxidant, sour trapping agent, light stabilizer, peroxide decomposer, radical scavenger, metal deactivator (metal deactivator), ultraviolet light absorber, matting agent, dyestuff etc.In addition, as long as the adjuvant for having described function also can use unfiled adjuvant in above-mentioned scope.
Preferably contain plastifier in the cellulose esters of formation substrate layer 2.With regard to improving engineering properties, give flexibility, give water absorption resistance, reducing with regard to the viewpoint of upgrading of film of moisture transmitance etc., preferably in substrate layer 2, add well-known compound as plastifier.In addition, add plastifier and comprise following purpose: when substrate layer 2 being shaped, by adding plastifier, and make the melt temperature of film constituent material be lower than the glass transition temperature of independent use cellulose esters with extrusion by melting; Perhaps under identical heating-up temperature, can make the viscosity of the film constituent material that contains plastifier be lower than the viscosity of cellulose esters.Here, in the present invention, the melt temperature of so-called film constituent material is meant at this material of heating to show under the mobile state temperature of heating material.
When using cellulose esters separately,, can not show flowability so in order to film forming if be lower than the glass transition temperature.Yet cellulose esters is under the temperature more than the glass transition temperature, and module of elasticity or viscosity descend owing to absorb heat, and show flowability.In order to make the fusion of film constituent material, in order to satisfy described purpose, and the plastifier that is preferably interpolation has the fusing point or the glass transition temperature of the glass transition temperature that is lower than cellulose esters.
Plastifier for example can be enumerated: phosphates such as triphenyl phosphate, tricresyl phosphate, tricresyl phosphate base phenyl ester, octyl diphenyl phosphate, di(2-ethylhexyl)phosphate phenyl biphenyl ester, trioctyl phosphate, tributyl phosphate, tri naphthyl phosphate, tricresyl phosphate (dimethylbenzene) ester, the adjacent biphenyl ester of tricresyl phosphate are plastifier; Diethyl phthalate, DMEP, repefral, dioctyl phthalate, dibutyl phthalate, phthalic acid two phthalic esters such as (2-Octyl Nitrites) are plastifier; Ethyl glycolates such as glycerol triacetate, glycerin tributyrate, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycollate, methyl phthalyl ethyl glycollate are plastifier etc.Wherein, phthalic ester system or ethyl glycolate are that plastifier is because of being difficult to cause that the hydrolysis of cellulose esters is preferred.In addition, preferably containing solidifying point is plastifier below 20 ℃.This plastifier for example can be enumerated: tricresyl phosphate, tricresyl phosphate base phenyl ester, tributyl phosphate, diethyl phthalate, repefral, dioctyl phthalate, dibutyl phthalate, phthalic acid two (2-Octyl Nitrite), ethyl phthalyl ethyl glycollate etc.
In addition, in the plastifier, preferred especially the use has nonvolatile plastifier.So-called non-volatile plasticisers is meant that the vapor pressure under 200 ℃ is the following compound of 10mmHg, and is meant the compound that has extremely low vapor pressure and have the character of low volatile grade.Be preferably below the 5mmHg, more preferably below the 1mmHg.Specifically can enumerate non-volatile phosphate, for example be preferably arlydene two (diaryl phosphate).
With regard to the viewpoint of dimensional stability, the content of above plastifier is preferably 0.1wt%～30wt% with respect to cellulose esters, is preferably 0.5wt%～15wt% especially.
In addition, preferred more be that the solidifying point of the plastifier that contained is, the plastifier below 14 ℃ particularly below 20 ℃.Utilize the low plastifier of solidifying point, and improve the flexibility of cellulose ester membrane, thereby improve the processability of film.
Preferably contain antioxidant in the cellulose esters of formation substrate layer 2.It is that antioxidant, phosphorous antioxidant, sulphur are antioxidant, heat-resisting processing stabilizers, deoxidant (oxygen scavenger) etc. that antioxidant for example can be enumerated phenol, in these antioxidants, being preferably phenol is that antioxidant, particularly alkyl-substituted phenols are antioxidant.By allocating these antioxidants, can not make reductions such as the transparency, thermotolerance, the painted or strength degradation of formed body that heat in the time of can preventing by shaping or oxidative degradation etc. are caused.These antioxidants can be distinguished use separately, perhaps be used in combination two or more, the allotment amount of these antioxidants can suitably be selected in the scope that does not undermine purpose of the present invention, be preferably 0.001 weight portion～5 weight portions with respect to polymkeric substance 100 weight portions of the present invention, more preferably 0.005 weight portion～1 weight portion.
Also can add sour trapping agent in the cellulose esters of formation substrate layer 2.The acid trapping agent is preferably and contains the sour trapping agent that the epoxy compound as sour trapping agent forms.This epoxy compound as sour trapping agent is known in this technical field, the diglycidyl ether that comprises various polyglycols, the polyglycols of deriving particularly by about 8 moles～40 moles oxirane of per 1 mole polyglycols condensation etc., the diglycidyl ether of glycerine etc., becket oxide (the compound that always in the vinyl chloride-base polymer constituent, has utilized since in the past for example, and the compound that had always utilized in the lump with the vinyl chloride-base polymer constituent in the past), epoxidation ether condensation product, bisphenol-A (promptly 4,4 '-dihydroxy diphenyl dimethylmethane) diglycidyl ether, epoxidation unsaturated fatty acid ester, and various epoxidation long-chain fatty acid triglycerides etc. epoxidized vegetable oil and other unsaturated natural oil of constituent representatives such as epoxidised soybean oil (for example with).
Preferably contain ultraviolet light absorber in the cellulose esters of formation substrate layer 2.Just prevent that polarization element or display device are for regard to the viewpoint of ultraviolet deterioration, optimal wavelength is the following excellent ultraviolet light absorber of ultraviolet absorption energy of 370nm, and with regard to the viewpoint of liquid crystal expressivity, optimal wavelength is the few ultraviolet light absorber of absorption of the above visible light of 400nm.For example can enumerate: oxygen base benzophenone based compound, benzotriazole based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel complex salt based compound etc. are preferably benzophenone based compound or painted few benzotriazole based compound.
The concrete example of benzotriazole based compound can be enumerated: 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 '-(3 "; 4 " 5 ", 6 "
The tetrahydric phthalimide ylmethyl)-5 '-aminomethyl phenyl) benzotriazole, 2, (4-(1 for the 2-di-2-ethylhexylphosphine oxide, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol), 2-(2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-the 5-chlorobenzotriazole, 2-(2H-benzotriazole-2-yl)-6-(straight chain and side chain dodecyl)-4-methylphenol, 3-[3-tertiary butyl-4-hydroxy-5-(chloro-2H-benzotriazole-2-yl) phenyl] octyl propionate and 3-[3-tertiary butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl) phenyl] potpourri etc. of propionic acid-2-Octyl Nitrite, but be not limited to these compounds.
In addition, commercially available product also can be used TINUVIN 109, TINUVIN 171, TINUVIN 360 (being Ciba (Ciba Specialty Chemicals) company makes).
The concrete example of benzophenone based compound can be enumerated: 2; 4-dihydroxy benaophenonel, 2; 2 '-dihydroxy-4-methoxy benzophenone, 2-hydroxyl-4-methoxyl-5-diphenylsulfone ketone, two (2-methoxyls-4-hydroxyl-5-benzoyl phenylmethane) etc., but be not limited to these compounds.
Ultraviolet light absorber preferably adds 0.1wt%～20wt% with respect to cellulose esters, more preferably adds 0.5wt%～10wt%, especially preferably adds 1wt%～5wt%.These ultraviolet light absorbers also can be also with two or more.
The manufacture method of substrate layer 2 is not particularly limited, and for example can utilize adjuvants such as the slice raw material of known mixed method mixed cellulose ester and plastifier, make thermoplastic resin composition in advance after, make substrate layer 2.This thermoplastic resin composition for example can be by after carrying out premixed with universal mixer mixers such as (omni mixer), and the potpourri that is obtained is extruded mixing and obtained.At this moment, be used to extrude mixing mixing roll and be not particularly limited, for example can use known in the past mixing rolls such as extruder such as single shaft extruder, biaxial extruder or pressurization kneader.
The method that the film of substrate layer 2 is shaped for example can be enumerated known method such as solution casting method (flow of solution casting), extrusion by melting, press polish method (calendar), compression forming method.In these methods, preferred solution casting method (flow of solution casting) or extrusion by melting, special preferred molten extrusion molding.Extrusion by melting does not use solvent and is shaped, and is aspect environment and the manufacturing process of energy-conservation aspect excellence therefore.In addition, be not shaped,, can make cellulose membrane shaping thus with stable delay (retardation) value so contained residual organic solvent amount is stable and less than 0.1wt% in the cellulose ester membrane after the film forming because do not use solvent.
The solvent that is used for solution casting method (flow of solution casting) for example can be enumerated: chlorine series solvents such as chloroform, methylene chloride; The aromatic series series solvents such as mixed solvent of toluene, dimethylbenzene, benzene and these solvents; Pure series solvents such as methyl alcohol, ethanol, isopropyl alcohol, normal butyl alcohol, 2-butanols; Methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethyl formamide, dimethyl sulfoxide (DMSO), dioxan, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (methyl ethyl ketone, MEK), ethyl acetate, diethyl ether etc.These solvents can only use a kind of, also can be also with two or more.For example can enumerate drum-type casting machine, band casting machine, spin coater etc. in order to the device that carries out solution casting method (flow of solution casting).
Extrusion by melting can be enumerated: the roller die of the counter-rotating shape of the cellulose esters that makes molten condition by having the substrate layer inner face around and the bite of other rollers and the described shape of transfer printing extrude thin slice forming process, plavini (inflation method) etc., with regard to the easiness that forms concaveconvex shape 3 at inner face, preferably extrude the thin slice forming process.
When carrying out film when being shaped to extrude the thin slice forming process, can carry out in the following manner: the leading section at known single shaft extruder or biaxial extruder is installed the T mould, the plain ester of fused fiber is become membranaceous extruding from the T mould, the roller die of the counter-rotating shape of the cellulose esters that makes molten condition by having substrate layer 2 inner faces around and the bite of other rollers, after the described shape of transfer printing, reel through the film of shaping.
The melt temperature of extruding in the thin slice forming process is preferably 170 ℃～270 ℃, more preferably 175 ℃～265 ℃, is preferably 180 ℃～260 ℃.In addition, preferably become 230 ℃～260 ℃ mode and adjust melt temperature with the temperature of the molten resin from T mould etc., extruded.By making melt temperature in described scope, can alleviate the deterioration of the deterioration and the yellow (yellow index, YI value) of celluosic resin.
In addition, have the roller die of counter-rotating shape of substrate layer 2 inner faces and the surface temperature of other rollers around and be preferably 60 ℃～150 ℃, more preferably 70 ℃～140 ℃, especially be preferably 80 ℃～135 ℃.Surface temperature by making two rollers can improve formability in described scope.
According to this thin slice forming process of extruding,, therefore can easily and carry out the adjustment of the size of concaveconvex shape 3 or the surfaceness of shape and substrate layer 2 inner faces etc. exactly owing to utilize so-called embossing processing that the concaveconvex shape 3 of substrate layer 2 inner faces is shaped.In addition, extrude the thin slice forming process by utilization and carry out the concaveconvex shape 3 that film is shaped with substrate layer 2 inner faces simultaneously and be shaped, and when the film of reeling,, and reduce intermembranous connecting airtight property owing to the existence of the concaveconvex shape 3 of substrate layer 2 inner faces through being shaped.Therefore, according to this method, can prevent the adhesion after film is reeled, and can make the film of speciality volume.
In addition, when reeling film, suitably adjust the temperature of take up roll, apply extension, also can become the uniaxial extension step thus towards extruding direction through being shaped.In addition, by the step of the adding direction extension that film court is vertical with extruding direction, and also can add steps such as twin shaft extension successively, twin shaft extension simultaneously.
Substrate layer 2 can be not stretched PTFE film, also can be stretched PTFE film.During extension, can be the uniaxial extension film, also can be biaxial stretchable film.When being made as biaxial stretchable film, can be the film that twin shaft extension simultaneously forms, also can be one by one twin shaft and extend the film that forms.When carrying out the twin shaft extension, physical strength improves and film properties improves.
Elongating temperature when extending step preferably carries out near the glass transition temperature as the cellulose esters of pleurodiaphragmatic in terspace material, particularly, preferably under (glass transition temperature-30) ℃～(glass transition temperature+100) ℃, carry out more preferably (glass transition temperature-20) ℃～(glass transition temperature+80) ℃.If elongating temperature is lower than (glass transition temperature-30) ℃, can't obtain sufficient extension ratio so, thereby bad.If elongating temperature is higher than (glass transition temperature+100) ℃, resin flow (flow) can be caused so and stable extension can't be carried out, therefore bad.
The extension ratio that recently defines with area can preferably be made as 1.1 times～25 times scope, more preferably is made as 1.3 times～10 times scope.If extension ratio less than 1.1 times, can not improve toughness along with extension so, thereby bad.If extension ratio greater than 25 times, can't confirm only to improve the effect of extension ratio so, and the surfaceness that is formed on the concaveconvex shape 3 of inner face descends.
Extension speed (folk prescription to) is preferably 10%/minute～20000%/minute scope, more preferably 100%/minute～10000%/minute scope.If be slower than 10%/minute, the spended time in order to obtain sufficient extension ratio so, and since manufacturing cost uprise, and bad.If faster than 20000%/minute, may cause the fracture of stretched PTFE film etc. so, thus bad.In addition, stable for the optical isotropy or the mechanical characteristic that make substrate layer 2, also can extend the laggard capable thermal treatment of processing (annealing) etc.
The manufacturing process of the roller die on knurling rolls surface (the counter-rotating shape of the concaveconvex shape 3 of substrate layer 2 inner faces) for example also can be jet by implementing, wet shotcrete technology, injection processing such as sandblast form this roller die.Utilize this method can form roller die more easily as the counter-rotating shape of concaveconvex shape 3.In above-mentioned, when utilization is sandblasted and formed the counter-rotating shape mould of concaveconvex shape 3, can more be formed uniformly this roller die.According to the roller die of such formation, can form the little concaveconvex shape 3 of value of roughness ratio (Rz/Ra) at the inner face of substrate layer 2.In addition, be under the situation of stretched PTFE film at substrate layer 2, suitably adjust the geomery of roller die according to extension ratio.
In addition, this injection processing is preferably carried out repeatedly.Utilize this method can form more uniform roller die.According to the roller die of such formation, can further reduce the value of roughness ratio (Rz/Ra) of substrate layer 2 inner faces of polarization element diaphragm 1.In addition, with regard to the atomic mean grain size of in spraying processing roller die being sprayed, be preferably below the 10 μ m under the situation of stretched PTFE film not, more preferably 1 μ m～5 μ m especially are preferably 2 μ m～3 μ m.
In addition, for example also there is following method etc. in the manufacture method of this polarization element diaphragm 1 except that described method:
(a) lamination cellulose acetate on the thin slice mould of the counter-rotating shape with concaveconvex shape 3 is by peelling off the method that this thin slice mould forms this polarization element diaphragm 1;
(b) injection molding method of injection fusion cellulose acetate in the mould of counter-rotating shape with concaveconvex shape 3;
(c) cellulose acetate that will become thin slice heats again, be clamped in described identical mould and sheet metal between suppress and the method for transfer printing shape.
In polarization element diaphragm 1; the surface of the substrate layer 2 of exterior side (not forming the side of micro concavo-convex shape 3) can be arbitrarily by various functional layers, and for example anti-reflecting layers such as antiglare layer (anti-glare layer), anti-reflecting layer, antiglare layer, low-index layer, antistatic backing, hard conating (hard resin-layer), optical compensating layer etc. are covered.For example further have antiglare layer (anti-reflecting layer), and when this polarization element diaphragm 1 of lamination of the polarization element outside, except that defencive function, also can bring into play anti-dazzle function polarization element by the polarization element diaphragm.In addition, further have hard conating, and strengthen defencive function polarization element by the polarization element diaphragm.
This antiglare layer for example can adopt following technology: utilize the embossing processing method to form concaveconvex shape on the film surface; Perhaps will form the masking liquid of sneaking into particle in the material and be coated on the film surface, particle is dispersed in the adhesive stroma, form concaveconvex shape thus at adhesive stroma.In addition, hard conating for example can use by the formed hard conating of active wire hardening resin.The example of this active wire hardening resin can be enumerated: the acrylic amine carbamate is that resin, polyester acrylate are that resin, epoxy acrylate are that resin, polyalcohol acrylate are resin, epoxy resin etc.
As mentioned above; according to polarization element diaphragm 1 of the present invention; for make with contain polyvinyl alcohol (PVA) polarization element then become easy; and has the substrate layer 2 that inner face side has micro concavo-convex shape 3; this cellulose esters utilizes the saponification of alkali to handle and produce hydroxyl through described later, improves effectively thus and the then property as the polyvinyl alcohol (PVA) of hydrophilic resin that constitutes polarization element.
The Polarizer 4 of Fig. 2 has the structure that has the polarization element diaphragm 1 of Fig. 1 in two face sides by the polarization element 5 that polyvinyl alcohol (PVA) constituted.Engage by adhesion agent layer 6 between each polarization element 5 and the polarization element diaphragm 1.
The representational manufacture method of polarization element 5 be adopt by with polyvinyl alcohol resin film swelling, dyeing, crosslinked, extend, washing and the dry a series of manufacturing step that step constituted.In the various processes except that drying steps, handle by the bath that polyvinyl alcohol resin film is immersed in the solution that is used for each step.Swelling, dyeing, crosslinked, extend, washing and dry having or not of each order, number of times and enforcement of handling can suitably set according to purpose, materials used and condition etc.For example extend to handle and before dyeing is handled, to carry out, also can carry out simultaneously with swelling processing etc.In addition, preferably carry out crosslinking Treatment in the front and back of extending processing.
Swelling step in a series of manufacturing step of polarization element 5 can be undertaken by polyvinyl alcohol resin film being immersed in the processing bath of filling water.This processing can suitably be added glycerine or potassium iodide etc. in bathing.The temperature that is typically the processing bath of swelling step is about 20 ℃～60 ℃, is about 0.1 minute～10 minutes at the dip time of handling in bathing.Staining procedure can be undertaken by polyvinyl alcohol resin film being immersed in the processing bath that contains dichroic substance such as iodine.Employed solvent makes water usually in the solution that this processing is bathed.Dichroic substance is being that the ratio of 0.1 weight portion～1.0 weight portions is used with respect to solvent 100 weight portions.The temperature that is typically the processing bath of staining procedure is about 20 ℃～70 ℃, and dip time is about 1 minute～20 minutes.
Cross-linking step can be carried out in the processing that contains crosslinking chemical is bathed by the polyvinyl alcohol resin film immersion with dyed processing.The example of crosslinking chemical can enumerate boron compounds such as boric acid, glyoxal, glutaraldehyde etc.Employed solvent makes water usually in the solution that this processing is bathed.The temperature that is typically the processing bath of cross-linking step is about 20 ℃～70 ℃, and dip time is about 1 second～15 minutes.Extending step can carry out in a stage in office.The extension ratio of polyvinyl alcohol resin film is preferably more than 5 times.Extension method for example can adopt the wet type extension method.At this moment the solution that processing is bathed is preferably the solution that has added the compound of various slaines, iodine, boron or zinc in water or organic solvent.
Water-washing step can be immersed in by the polyvinyl alcohol resin film that will implement various processing in the washing bath and carry out.Utilize this water-washing step, but the unnecessary remnant of flush away polyvinyl alcohol resin film.Washing is bathed and be can be pure water, also can be the aqueous solution of iodide (potassium iodide, sodium iodide etc.).The temperature that washing is bathed is preferably 10 ℃～60 ℃.Being typically dip time is 1 second～1 minute.The number of times of washing can also can be repeatedly only for once.Drying steps for example can adopt air dry, forced air drying, heat drying.Being typically baking temperature is 20 ℃～80 ℃, and be 1 minute～10 minutes drying time.By carrying out described each step, can make polarization element 5.
Polarization element diaphragm 1 preferably carry out with polarization element 5 then before, with alkali the inner face side of substrate layer 2 (forming the side of concaveconvex shape 3) 3 is at least carried out saponification.Utilize this saponification; the ester group of cellulose esters is replaced to hydroxyl as hydrophilic radical; can improve thus polarization element diaphragm 1 with by chemical affinity as the formed polarization element 5 of the polyvinyl alcohol (PVA) of hydrophilic resin, and mutual then property obviously improves.
Be used for the aqueous solution etc. that aqueous alkali that saponification handles for example can use NaOH, potassium hydroxide, calcium hydroxide, lithium hydroxide.The concentration of these metal hydroxides is generally below the above 40wt% of 5wt%.In addition, the temperature handled of saponification is preferably more than 10 ℃ below 80 ℃.The concentration of metal hydroxides be 5wt% when following or the temperature handled of saponification be below 10 ℃ the time, it is elongated that the required time is handled in saponification, thereby bad.Appropriate time carries out in the described aqueous alkali bath by polarization element diaphragm 1 is immersed in the saponification processing.
Employed solid in the adhesion agent layer 6 that the substrate layer 2 of polarization element diaphragm 1 and polarization element 5 are fitted for example can be enumerated polyethenol series solids such as polyvinyl alcohol (PVA), tygon butyraldehyde, or ethene such as butyl acrylate is latex etc.Usually these solids being made aqueous solution uses.Consider coating or shelf-stability etc., the solid component concentration in the resin solution of solid is preferably 0.1wt%～15wt%.In addition, the viscosity of the resin solution of solid for example is preferably the scope of 1mPas～50mPas.
The Polarizer manufacturing installation 7 that utilizes Fig. 3 to schematically show will be fitted through saponification polarization element diaphragm of handling 1 and the polarization element 5 that contains polyvinyl alcohol (PVA).Polarizer manufacturing installation 7 in order to the applying multilayer film shown in Figure 3 has: polarization element 5 is wound into the roller 8 of the polarization element of roller shape, polarization element diaphragm 1 is wound into roller 9, solid feed mechanism 10, and the roller 11 in order to polarization element 5 and polarization element diaphragm 1 are pushed, engaged via solid of the polarization element diaphragm of roller shape.
In the Polarizer manufacturing installation 7; the membranaceous polarization element 5 that to supply with from roller 8, polarization element diaphragm 1 court that handled with the saponification of supplying with from roller 9 send towards the direction of roller 11; supply with an amount of solid in the mode that is clamped between these films; then; push and polarization element 5 and polarization element diaphragm 1 are fitted with roller 11, and the tectosome of polarization element diaphragm 1 that obtained on the single face of polarization element 5 lamination.Then, for the face of the polarization element 5 of lamination polarization element diaphragm 1 one sides not, also use identical mechanism, lamination polarization element diaphragm 1 obtains Polarizer 4 thus.The thickness of Polarizer 4 is typically below the above 100 μ m of 10 μ m.
As mentioned above; according to Polarizer 4 with polarization element diaphragm 1 of the present invention; because the inner face at the polarization element diaphragm 1 of two face sides that are disposed at the polarization element that is made of polyvinyl alcohol (PVA) has been implemented micro concavo-convex shape 3; so can improve the then property of the polarization element 5 that constitutes by polyvinyl alcohol (PVA) and adhesion agent layer 6 and polarization element diaphragm 1 and peel off permanance, can improve the intensity and the operability of Polarizer 4 thus.
The liquid crystal display cells 12 of Fig. 4 is to be made of following manner: to two faces with the liquid crystal cells 13 of transparent dielectric layer 14 (for example glass) clamping liquid crystal layer 15, the Polarizer 4 of the Fig. 2 of the present invention that fits via adhesion agent layer 16 (being made of polarization element diaphragm 1, polarization element 5 and adhesion agent layer 6).Constitute the liquid crystal layer 15 of liquid crystal cells 13 and the material of transparent dielectric layer 14 and adhesion agent layer 16, be not particularly limited, can use material known.In addition, in the liquid crystal display cells, can use the Polarizer 4 (Polarizer of the present invention) of Fig. 2, use other Polarizers of conventional art in another face side of liquid crystal cells in a face side of liquid crystal cells.
According to liquid crystal display cells 12 with the Polarizer 4 that has disposed polarization element diaphragm 1 of the present invention; because polarization element diaphragm 1 is configured as the easy then shape that is provided with micro concavo-convex shape 3; so then property, the permanance height of polarization element 5 and adhesion agent layer 6 and polarization element diaphragm 1, and the intensity of Polarizer 4, operability excellence to peeling off.Therefore, each characteristic that liquid crystal display cells 12 is had can long-time continuous and is stably obtained performance, thereby uprises for the reliability of entire machine.
In addition, polarization element diaphragm of the present invention, Polarizer and liquid crystal display cells are not limited to described example, and for example lamination also can use existing polarization element diaphragm at the polarization element diaphragm of single face side in Polarizer.By using existing polarization element diaphragm, can cut down manufacturing cost in the face side that does not need the strong cohesiveness property.
[embodiment]
Below, according to embodiment the present invention is described in detail, but does not illustrate that the present invention is limited by the record of this embodiment.
In addition, in the present embodiment " arithmetic average roughness (Ra) " to reach " mean roughness at ten places (Rz) " be according to JIS B0601-1994, setting cutoff value λ c is that 2.5mm, evaluation length are 12.5mm, and the contact pin type surface roughness measurement device " Surfcom 470A " that uses Tokyo Seimitsu Co., Ltd. to make is measured.
[embodiment 1]
[the substrate layer preparation of resin combination]
Use cellulose-acetate propionate (CAP482-20 that Eastman Chemical company makes) 100 weight portions as cellulose esters; use triphenyl phosphate (big eight chemical industrial companies make) 10 weight portions and ethyl phthalyl ethyl glycollate (big eight chemical industrial companies make) 2 weight portions as plastifier; use IRGANOX-1010 (manufacturing of BASF Japan company) 0.01 weight portion as antioxidant; use TINUVIN 109 (manufacturing of BASF Japan company) 0.5 weight portion; TINUVIN 171 (manufacturing of BASF Japan company) 0.5 weight portion; and TINUVIN 360 (manufacturing of BASF Japan company) 0.3 weight portion is as ultraviolet light absorber; use the twin shaft mixing extruder after carrying out melting mixing under 200 ℃; be extruded into the noodles shape; become the potpourri of noodles shape in water, to solidify and severing this, obtain the particle of resin combination thus.
[formation of polarization element diaphragm]
With described pellet supply to extruder, at 250 ℃ of following heating and meltings.Then; resin flakiness shape from extruder of fusion is extruded the roller die by having the micro concavo-convex shape and the bite of other rollers, and replicated fine concaveconvex shape; carry with conveying roller then and carry out cooling curing, obtain the polarization element diaphragm of embodiment 1 thus.In addition, the temperature of the molten resin of extruding from extruder is 240 ℃.In addition, have the roller die of micro concavo-convex shape and the surface temperature of other rollers and be adjusted into 100 ℃.The Ra of the polarization element diaphragm inner face that is obtained is that 1.0 μ m, Rz are that 2.0 μ m, average thickness are 80 μ m.
[embodiment 2～embodiment 5, comparative example 1 and comparative example 2]
Change has the interval of roller die and other rollers of micro concavo-convex shape respectively, and in addition, in the mode identical with embodiment 1, the Ra and the Rz that obtain inner face distinguish the different embodiment 2～embodiment 5 and the polarization element diaphragm of comparative example 1 and comparative example 2.The average thickness of these polarization element diaphragms is 80 μ m.The Ra of each polarization element diaphragm inner face of being obtained and the value of Rz are shown in table 1.
[characteristic evaluation]
Utilize following method, each the polarization element diaphragm that obtains in described is carried out about then property and peels off the characteristic evaluation of permanance.
[saponification of polarization element diaphragm]
With described each polarization element diaphragm dipping 3 minutes in 60 ℃, the sodium hydrate aqueous solution of 2mol/L (about 8wt%), carry out saponification thus.Then, washed 4 minutes, then dipping 4 minutes in the aqueous solution of nitric acid of 30 ℃ 0.01mol/L neutralizes thus, washes then 4 minutes.After the washing, drying is 3 minutes under 90 ℃, carries out air dry 1 hour again, makes the polarization element diaphragm of saponification thus.
[formation of polarization element]
The polyvinyl alcohol film of thickness 200 μ m is carried out uniaxial extension (110 ℃ of temperature, 5 times of extension ratios), is the film of 40 μ m and obtain thickness.This film was flooded 60 seconds in the aqueous solution 100g that contains iodine 0.15g and potassium iodide 10g, then be immersed in 68 ℃ the aqueous solution that contains potassium iodide 12g and boric acid 7.5g.Then to this film wash, drying, and obtain polarization element.
[making of laminate]
The size that the polarization element diaphragm and the polarization element severing of described saponification become 18cm * 5cm; via solid component concentration is that the polyvinyl alcohol water solution of 2wt% is a solid; this polarization element diaphragm and polarization element are overlapped; use hand roller (hand roller); on one side excessive solid or bubble are removed, Yi Bian fit.Utilization adds and is pressed into 2kg/cm
2Make-up machine this laminate is processed, under 80 ℃, carry out drying then, obtain the laminate of polarization element diaphragm and polarization element thus.During this is fitted, be that the inner face (having given the face of micro concavo-convex shape) of the polarization element diaphragm of saponification is followed with described polarization element.
(1) follows property
With hand two-layer (the polarization element diaphragm and the polarization element) of laminate peeled off,, assessed with following Three Estate according to the degree that material damage takes place.Assessment result is shown in table 1.
Well (A): peeling off between film and the polarization element do not taken place, and cause material damage.
Bad a little (B): cause a part of material damage, but peeling off between film and the polarization element taken place.
Bad (C): peel off fully between film and the polarization element.
(2) peel off permanance
Laminate was placed 500 hours under the condition of 75 ℃ of d, 90%RH, measured the width of peeling off that begins from the end.The assessment benchmark is as described below.Assessment result is shown in table 1.
Well (A): less than 0.5mm
More than bad a little (B): the 0.5mm and less than 1.5mm
Bad (C): more than the 1.5mm
[table 1]
| ??Ra | ??Rz | ??Rz/Ra | Follow property | Peel off permanance | |
| Embodiment 1 | ??1.0 | ??2.0 | ??2.0 | ??A | ??A |
| Embodiment 2 | ??1.4 | ??5.6 | ??4.0 | ??A | ??A |
| Embodiment 3 | ??1.2 | ??3.8 | ??3.2 | ??A | ??A |
| |
??2.6 | ??15.8 | ??6.1 | ??A | ??A |
| |
??2.0 | ??30.0 | ??15.0 | ??A | ??A |
| Comparative example 1 | ??0.4 | ??0.8 | ??1.9 | ??B | ??B |
| ??Ra | ??Rz | ??Rz/Ra | Follow property | Peel off permanance | |
| Comparative example 2 | ??12.0 | ??64.0 | ??5.3 | ??C | ??C |
According to the result of table 1, the then property of the Polarizer of embodiment 1～embodiment 5 is good as can be known, and under stringent condition to peel off permanance also excellent.In addition, the polarization element diaphragm of comparative example 1 takes place and the connecting airtight of conveying roller etc. when film forming, during alkali treatment, when Polarizer is made, and handles (knurling treatment) etc. if the roller line is not implemented at the film both ends, is difficult to carry out operation so.
As mentioned above; polarization element of the present invention outside possesses the substrate layer that one of them surface has specific micro concavo-convex shape with diaphragm; compare thus with by the film that substrate layer constituted that does not have this shape, to the adhesion of polyvinyl alcohol (PVA) and peel off permanance be improved significantly.
[utilizability on the industry]
Use has the liquid crystal display cells of the polarisation plate of polarization element diaphragm of the present invention; can carry out reliably between polarization element diaphragm and the polarization element then, so liquid crystal display cells and have the Reliability Enhancement of the whole e-machine of this liquid crystal display cells. Therefore, this kind liquid crystal display cells can be used for from small-sized product such as calculator or clocks, in the various fields of automobile with large-scale product such as instrument, PC display, TVs.
The above, only be better embodiment of the present invention, be not that the present invention is done any formal restriction, although the present invention discloses as above with better embodiment, yet be not to limit the present invention, any those skilled in the art, within not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be not break away from the technical solution of the present invention content,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment does according to technical spirit of the present invention.
Claims (8)
1. polarization element diaphragm, it is characterized in that: it has cellulose esters system transparent substrate layer, and
Have the micro concavo-convex shape that is formed on described substrate layer inner face,
The arithmetic average roughness of substrate layer inner face (Ra) is below the above 10 μ m of 1 μ m.
2. polarization element diaphragm according to claim 1 is characterized in that: the mean roughness (Rz) at ten places of described substrate layer inner face is below the above 60 μ m of 2 μ m.
3. polarization element diaphragm according to claim 1 and 2 is characterized in that: the mean roughness (Rz) at ten places of described substrate layer inner face is more than 1 below 15 with respect to the roughness ratio (Rz/Ra) of arithmetic average roughness (Ra).
4. according to the described polarization element diaphragm of arbitrary claim in the claim 1 to 3, it is characterized in that: described cellulose esters is a cellulose-acetate propionate.
5. according to the described polarization element diaphragm of arbitrary claim in the claim 1 to 4, it is characterized in that: it has anti-reflecting layer or the hard conating of lamination at the exterior side of described substrate layer.
6. according to the described polarization element diaphragm of arbitrary claim in the claim 1 to 5; it is characterized in that: it is to utilize to extrude the thin slice forming process and form; the roller die of the counter-rotating shape that is the cellulose esters that makes molten condition by having described substrate layer inner face around and the bite of other rollers, and the described shape of transfer printing.
7. Polarizer is characterized in that: it possesses polarization element with polyvinyl alcohol (PVA) and the lamination a pair of polarization element diaphragm in the two sides of this polarization element side, and
Use according to the described polarization element diaphragm of arbitrary claim in the claim 1 to 6 as the polarization element diaphragm of a slice at least.
8. liquid crystal display cells is characterized in that: it has liquid crystal cells and the lamination a pair of Polarizer in the two sides of this liquid crystal cells side, and
Use the Polarizer conduct according to claim 7 Polarizer of a slice at least.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009117303 | 2009-05-14 | ||
| JP2009-117303 | 2009-05-14 | ||
| JP2010105920A JP2010286827A (en) | 2009-05-14 | 2010-04-30 | Polarizer protective film, polarizing plate and liquid crystal display element |
| JP2010-105920 | 2010-04-30 |
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| Publication Number | Publication Date |
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| CN101887143A true CN101887143A (en) | 2010-11-17 |
| CN101887143B CN101887143B (en) | 2015-02-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201010180638.XA Active CN101887143B (en) | 2009-05-14 | 2010-05-14 | Polarizer protection film, polarizing plate and liquid crystal display element |
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| KR (2) | KR101258549B1 (en) |
| CN (1) | CN101887143B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102253433A (en) * | 2011-07-04 | 2011-11-23 | 江阴市通利包装材料有限公司 | Prism sheet optical protective film and preparation method thereof |
| CN105739004A (en) * | 2014-12-26 | 2016-07-06 | 日东电工株式会社 | Method of manufacturing polarizing plate |
| CN106908866A (en) * | 2016-06-03 | 2017-06-30 | 住华科技股份有限公司 | Optical film set and method for preventing adhesion |
| CN110154475A (en) * | 2018-02-14 | 2019-08-23 | 住友化学株式会社 | Laminated body |
| CN113544555A (en) * | 2019-03-14 | 2021-10-22 | 株式会社可乐丽 | Polyvinyl alcohol film, polarizing film, and polarizing plate |
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| CN1769932A (en) * | 2004-10-19 | 2006-05-10 | 日东电工株式会社 | Polarizing plate, method of producing a polarizing plate, and liquid crystal panel, liquid crystal television, and liquid crystal display apparatus all using the same |
| CN1942511A (en) * | 2004-04-16 | 2007-04-04 | 柯尼卡美能达精密光学株式会社 | Cellulose ester film |
| US20070128380A1 (en) * | 2005-12-07 | 2007-06-07 | Konica Minolta Opto, Inc. | Cellulose Ester Film, Its Manufacturing Method, Polarizing Plate, and Liquid Crystal Display |
| CN101201423A (en) * | 2003-06-25 | 2008-06-18 | 富士胶片株式会社 | Optical compensating sheet, polarizing plate, and liquid crystal display device |
| JP2008209940A (en) * | 1999-04-15 | 2008-09-11 | Konica Minolta Holdings Inc | Method for producing cellulose ester film |
| JP2009025603A (en) * | 2007-07-20 | 2009-02-05 | Konica Minolta Opto Inc | Polarizing plate and method for manufacturing the same, apparatus for manufacturing polarizing plate, and display device |
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| JP2000347010A (en) * | 1999-06-09 | 2000-12-15 | Nitto Denko Corp | Optical member and liquid crystal display device |
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- 2010-05-14 CN CN201010180638.XA patent/CN101887143B/en active Active
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| JP2008209940A (en) * | 1999-04-15 | 2008-09-11 | Konica Minolta Holdings Inc | Method for producing cellulose ester film |
| CN101201423A (en) * | 2003-06-25 | 2008-06-18 | 富士胶片株式会社 | Optical compensating sheet, polarizing plate, and liquid crystal display device |
| CN1942511A (en) * | 2004-04-16 | 2007-04-04 | 柯尼卡美能达精密光学株式会社 | Cellulose ester film |
| CN1769932A (en) * | 2004-10-19 | 2006-05-10 | 日东电工株式会社 | Polarizing plate, method of producing a polarizing plate, and liquid crystal panel, liquid crystal television, and liquid crystal display apparatus all using the same |
| US20070128380A1 (en) * | 2005-12-07 | 2007-06-07 | Konica Minolta Opto, Inc. | Cellulose Ester Film, Its Manufacturing Method, Polarizing Plate, and Liquid Crystal Display |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102253433A (en) * | 2011-07-04 | 2011-11-23 | 江阴市通利包装材料有限公司 | Prism sheet optical protective film and preparation method thereof |
| CN105739004A (en) * | 2014-12-26 | 2016-07-06 | 日东电工株式会社 | Method of manufacturing polarizing plate |
| CN106908866A (en) * | 2016-06-03 | 2017-06-30 | 住华科技股份有限公司 | Optical film set and method for preventing adhesion |
| CN106908866B (en) * | 2016-06-03 | 2018-12-28 | 住华科技股份有限公司 | Optical film set and method for preventing adhesion |
| CN110154475A (en) * | 2018-02-14 | 2019-08-23 | 住友化学株式会社 | Laminated body |
| CN110154475B (en) * | 2018-02-14 | 2021-11-02 | 住友化学株式会社 | Laminated body |
| CN113544555A (en) * | 2019-03-14 | 2021-10-22 | 株式会社可乐丽 | Polyvinyl alcohol film, polarizing film, and polarizing plate |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101258549B1 (en) | 2013-05-02 |
| KR101258553B1 (en) | 2013-05-02 |
| KR20100123630A (en) | 2010-11-24 |
| CN101887143B (en) | 2015-02-04 |
| KR20120059476A (en) | 2012-06-08 |
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