CN108318955A - Circular polarization light board and display device - Google Patents

Circular polarization light board and display device Download PDF

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Publication number
CN108318955A
CN108318955A CN201810146064.0A CN201810146064A CN108318955A CN 108318955 A CN108318955 A CN 108318955A CN 201810146064 A CN201810146064 A CN 201810146064A CN 108318955 A CN108318955 A CN 108318955A
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Prior art keywords
circular polarization
light board
phase separation
photosphere
separation layer
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CN201810146064.0A
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CN108318955B (en
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幡中伸行
小林忠弘
横田明�
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3083Birefringent or phase retarding elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3016Polarising elements involving passive liquid crystal elements
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528Polarisers
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363Birefringent elements, e.g. for optical compensation
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polarising Elements (AREA)
  • Electroluminescent Light Sources (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

The purpose of the present invention is to provide slim and wide band circular polarization light board and equipped with the display device of the circular polarization light board.A kind of circular polarization light board, it is characterized in that, with base material and phase separation layer and polarization photosphere, the birefringence Δ n (λ) of the light of wavelength X nm relative to the phase separation layer meets formula (1) and formula (2), phase separation layer is coat with polarization photosphere, phase separation layer with polarization photosphere overall thickness be 10 μm hereinafter, also, the polarization photosphere contain dichroism pigment.Δn(450)/Δn(550)≦1.00 (1);1.00≦Δn(650)/Δn(550) (2).

Description

Circular polarization light board and display device
The application is the divisional application based on following Chinese patent application:
The original bill applying date:On August 29th, 2013
Original bill application number:201310385767.6
Original bill application title:Circular polarization light board and display device
Technical field
The present invention relates to a kind of circular polarization light board and display devices.
Background technology
A kind of known liquid crystal display device has polarization film and 1/2 wave that the polyvinyl alcohol through iodine staining is formed The broadband circular polarization light board that long slab and 1/4 wavelength plate laminated are formed.In such broadband circular polarization light board, need to make 1/2 The absorption axiss institute of the slow axis and polarization film of angle and 1/4 wavelength plate formed by the slow axis of wavelength plate and the absorption axiss of polarization film At angle be staggered 15 ° or 75 ° respectively and lamination, it is therefore difficult to manufacture the circular polarization light board by roll-to-roll fitting.It is another Aspect requires the slimming of display device also to become strong, so, also require the slimming of circular polarization light board.
A kind of circular polarization light board has been recorded in patent document 1, passes through the lamination inverse wave length dispersible film on phase separation layer It is formed with the polarizer, thickness is 130~370 μm, and the polarizer is obtained by being coated with dichroism pigment.In patent document 2 A kind of circular polarization light board is described, by the polarizer containing thermotropic liquid crystal or the substance of lyotropic liquid crystalline in phase separation layer Upper lamination forms, and thickness is 36~205 μm.
The prior art
Patent document 1:Japanese Patent Laid-Open 2006-337892 bulletins
Patent document 2:Japanese Patent Laid-Open 2009-251288 bulletins
Invention content
The subject that the invention solves
It is formed via adhesive or bonding agent lamination however, the circular polarization light board described in patent document 1 is 2 films , so, in terms of the thickness of manufacturing process's summary and circular polarization light board, and it is unsatisfactory.Described in patent document 2 Circular polarization light board, phase separation layer shows positive wavelength dispersibility, so, the performance as broadband circular polarization light board is not filled Point.
The means to solve the problem
The present invention includes following invention.
[1] a kind of circular polarization light board, which is characterized in that there is base material, phase separation layer and polarization photosphere, the phase separation layer is to wave The birefringence Δ n (λ) of the light of long λ nm meets formula (1) and formula (2), and phase separation layer is coat, phase with polarization photosphere Poor layer with polarization photosphere overall thickness be 10 μm hereinafter, also, the polarization photosphere contain dichroism pigment.
Δn(450)/Δn(550)≦1.00(1)
1.00≦Δn(650)/Δn(550)(2)
[2] circular polarization light board recorded according to [1], phase separation layer are formed by a kind or more of polymerizable liquid crystal polymerize.
[3] circular polarization light board recorded according to [1] or [2], polarization photosphere are polymerize by shape by a kind or more of polymerizable liquid crystal At.
[4] circular polarization light board recorded according to [2] or [3], makes polymerizable liquid crystal polymerize by irradiation light.
[5] according to any one of them circular polarization light board of [1]~[4], wherein polarizing layer obtains in X-ray diffraction measure Bragg peak.
[6] circular polarization light board recorded according to any one of [1]~[5], wherein phase separation layer and the thickness point for polarizing photosphere Not at 5 μm or less.
[7] circular polarization light board recorded according to any one of [1]~[6], wherein phase separation layer or polarization photosphere or the two It is formed in alignment films.
[8] circular polarization light board recorded according to [7], wherein alignment films are that the orientation of orientation anchorage force is generated by irradiation light Film.
[9] circular polarization light board recorded according to [7] or [8], wherein the thickness of alignment films is in 500nm or less.
[10] circular polarization light board recorded according to any one of [1]~[9], wherein on base material, via or not via alignment films Form phase separation layer, on phase separation layer, via or do not form polarization photosphere via alignment films.
[11] circular polarization light board recorded according to any one of [1]~[9], wherein on base material, via or not via alignment films Formed polarization photosphere, polarize photosphere on, via or not via alignment films formed phase separation layer.
[12] circular polarization light board recorded according to [10] or [11], wherein there is protective layer between polarization photosphere and phase separation layer.
[13] circular polarization light board recorded according to any one of [1]~[9], wherein on a face of base material, via or be not situated between Form polarization photosphere by alignment films, on another face of base material, via or do not form phase separation layer via alignment films.
[14] circular polarization light board recorded according to any one of [1]~[13], further also in phase separation layer or polarization There is adhesive phase on the surface of photosphere.
[15] circular polarization light board recorded according to [14] has base material, first orientation film, polarization photosphere, second orientation successively Film, phase separation layer and adhesive phase.
[16] circular polarization light board recorded according to [15], wherein the peel strength (F1) of base material and first orientation film is less than first Peel strength (F2), the peel strength (F3) and phase separation layer of second orientation film and phase separation layer of alignment films and polarization photosphere With the peel strength (F4) of adhesive phase.
[17] a kind of display device, any one of them circular polarization light board and display element with [1]~[16].
[18] a kind of display device with circularly polarized light film is the circular polarization light board removing that any one of [14]~[16] is recorded Circularly polarized light film obtained from base material be fitted on the display surface of display element via the adhesive phase of the circularly polarized light film and It obtains.
[19] display device recorded according to [18], wherein the thickness of circularly polarized light film is at 5 μm or more 15 μm or less.
[20] display device recorded according to any one of [17]~[19], wherein display element is liquid crystal cell, organic electroluminescence hair Optical element or touch panel.
[21] a kind of manufacturing method of the display device with circularly polarized light film, wherein record any one of [14]~[16] Circular polarization light board is fitted in via the adhesive phase of the circular polarization light board on the display surface of display element, and the circular polarization light board Eliminate base material.
The effect of invention
According to the present invention it is possible to provide slim and wide band circular polarization light board and be equipped with the display of the circular polarization light board Device.
Description of the drawings
【Fig. 1】The schematic cross-section of the circular polarization light board of the present invention.
【Fig. 2】The schematic diagram of the liquid crystal display device of circular polarization light board containing the present invention.
【Fig. 3】The schematic diagram of the organic EL display device of circular polarization light board containing the present invention.
Symbol description
1 circular polarization light board
2 base materials
3 phase separation layers
4 polarization photospheres
5 dichroism pigments
10 liquid crystal display devices
This circular polarization light board of 11a, 11b
12a, 12b substrate
13 colour filters
14 transparent electrodes
15 liquid crystal layers
16 interlayer dielectrics
17 back light units
18 black matrix"s
19 thin film transistor (TFT)s
20 pixel electrodes
21 separation layers
30 organic EL display devices
31 circular polarization light boards
32 substrates
33 interlayer dielectrics
34 pixel electrodes
35 luminescent layers
36 cathode electrodes
37 sealants
38 thin film transistor (TFT)s
39 ribs
Specific implementation mode
Base material is typically transparent base material.In addition, the circular polarization light board (hereinafter, being referred to as this circular polarization light board) of the present invention Base material when being not arranged on the display surface of display element, for example, this circular polarization light board to be eliminated to the circularly polarized light film of base material It is arranged when on the display surface of display element, base material can be opaque.Transparent base refers to that can penetrate light, particularly can The light-exposed base material with the transparency, the transparency refer to, to the transmitance of the light of 380~780nm of wavelength 80% or more Characteristic.Specifically as transparent base, for example there are translucent resin base materials.As the resin for constituting translucent resin base material, lift Example has the polyolefin such as polyethylene, polypropylene;The annular ethylene series resins such as the dilute based polymer of norborneol;Polyvinyl alcohol;Gather to benzene two Formic acid second diester;Polymethacrylates;Polyacrylate;Triacetyl cellulose, diacetyl cellulose, cellulose acetate propionic acid The cellulose esters such as ester;Polyethylene naphthalate;Makrolon;Polysulfones;Polyether sulfone;Polyether-ketone;Polyphenylene sulfide and polyphenyl Ether etc..From easy purchase and transparent aspect, preferably polyethylene terephthalate, polymethacrylates, fiber Plain ester, annular ethylene series resin or makrolon.
Cellulose esters on the market may be used obtained from some or all esterifications for the hydroxyl that will include in cellulose To easily purchase.In addition, cellulose esters base material is can be easily commercially available.As commercially available cellulose esters Base material, for example there are for example, " FUJITAC (Off ジ タ ッ Network) film " (photographic film Co., Ltd. of Fuji);“KC8UX2M”、 " KC8UY " and " KC4UY " (Konica Minolta Opto Inc.) etc..
Annular ethylene series resin is easy to buy on the market.As commercially available annular ethylene series resin, for example there are " Topas " [Ticona societies (moral)];" ア ー ト Application (Arton) " [JSR (strain)];" ZEONOR (ゼ オ ノ ア) " and " ZEONEX Annular ethylene series resin as (ゼ オ ネ ッ Network ス) " [Japan auspicious father-in-law's (strain)] and " ア ペ Le " [Mitsui Chemicals (strain) system] Such as it is burnt after method well known to casting or extrusion by melting etc. is film-made by solvent and is used as base material.Meanwhile it also can be used commercially available The annular ethylene series resin base material of film-forming state.As such commercially available annular ethylene series resin base material, for example there are " エ ス シ ー Na ", " SCA40 " [ponding chemical industry (strain)];" ゼ オ ノ ア films " [オ プ テ ス (Optes) (strain)] and " ア ー ト Application (Arton) film " [JSR (strain)] etc..
When annular ethylene series resin is cyclic annular alkene with chain alkene or when the copolymer of the aromatic compound with vinyl, Come be originated from cyclic annular alkene structural units content ratio, relative to the entire infrastructure unit of copolymer, usually 50 moles of % with Under, the range of preferably 15~50 moles %.As chain alkene, for example there are ethylene and propylene, as the fragrance with vinyl Compounds of group, for example there are styrene, α-methylstyrene and alkyl-substituted styrenes.When annular ethylene series resin is cyclic annular alkene When with the terpolymer of chain alkene and the aromatic compound with vinyl, the structural units to be originated from chain alkene is contained Ratio, relative to the entire infrastructure unit of copolymer, usually 5~80 moles of %, to be originated from the aromatic series with vinyl The content ratio for closing the structural units of object, relative to the entire infrastructure unit of copolymer, usually 5~80 moles of %.It is such Terpolymer during fabrication, has the advantages that more a small amount of high price ring-type alkene can be used.
Characteristic required by base material is different according to the structure of circular polarization light board, generally, it is preferred to which phase difference is as much as possible Small base material.The base material as small as possible as phase difference, for example there are ゼ ロ タ ッ Network (Konica Minolta Opto Inc.), Z タ ッ Network (Fuji Photo Film Co., Ltd.) etc. does not have dephased cellulose ester membrane.In addition it is also preferred that non-stretched cycloolefin Resin base material.
On base material, via or be not formed with polarization photosphere via alignment films, polarize on photosphere, via or not via taking The circular polarization light board that phase separation layer is formd to film, on the face of no base material for forming polarization photosphere, it is possible to implement hard applies Layer processing, antireflection process, antistatic process etc..In addition, in the range of not influencing performance, hard coat can contain ultraviolet The additives such as light absorbers.
When the thickness of base material is excessively thin, intensity can reduce, and processability also has the tendency that deterioration, so, usually 5~300 μm, It is preferred that 20~200 μm.
Phase separation layer is the coat for meeting formula (1) and formula (2) to the birefringence Δ n (λ) of the light of wavelength X nm.It applies Coating refers to by applying the layer formed.
Δn(450)/Δn(550)≦1.00(1)
1.00≦Δn(650)/Δn(550)(2)
The length of delay of measurement divided by the thickness of phase separation layer obtain birefringence Δ n (λ).Specifically assay method has been It shows in embodiment, at this point, as measuring obtained by film on the base material that the base material as glass substrate does not postpone itself Object can measure the characteristic of actual phase separation layer.
The polymerizable liquid crystal that preferably a kind or more of phase separation layer is (hereinafter, referred to as polymerizable liquid crystal (A).) polymerization formed Layer.
Polymerizable liquid crystal is the compound with polymerizable group, also, with liquid crystal liquid crystal property.Polymerizable group refers to participating in The group of polymerisation, preferably polymerism group.Herein, polymerism group refers to by being caused by aftermentioned photopolymerization Living radical or acid that agent generates etc., can participate in the group of polymerisation.As polymerizable group, for example there are vinyl, Vinyl hydroxy, 1- chlorovinyls, isopropenyl, 4- ethenylphenyls, acryloyl group hydroxyl, methacryl hydroxyl, epoxy Ethyl group, propylene oxide base etc..Wherein, preferably acryloyl group hydroxyl, methacryl hydroxyl, ethyleneoxy, Oxyranyle And propylene oxide base, more preferable acryloyl group hydroxyl.Liquid crystal liquid crystal property can be thermotropic liquid crystal or lysotropic liquid crystal, thermotropic liquid crystal Can be nematic crystal or smectic liquid crystal when being classified with the degree of order.
Wherein, from easy film aspect, preferably thermotropic nematic crystal, in addition, from assign the formula (1) with And set out in terms of the phase difference represented by the formula (2), the compound preferably represented by following formula (A) is (hereinafter, be referred to as to change Close object (A)).The polymerizable liquid crystal may be used alone, can also be used in combination.
[in formula (A),
X1Indicate oxygen atom, sulphur atom or NR1-。R1Indicate hydrogen atom or the alkyl of carbon atom number 1~4.
Y1Indicate can with or without 1 valence of the carbon atom number 6~12 of substituent group aromatic hydrocarbyl or can have Or the heteroaromatic formula basis representation of 1 valence of the carbon atom number 3~12 without substituent group.
Q3And Q4Separately indicate hydrogen atom, can be with or without 1 valence of the carbon atom number 1~20 of substituent group Aliphatic alkyl, carbon atom number 3~20 1 valence alicyclic type hydrocarbon, can be with or without the carbon atom number 6 of substituent group Aromatic hydrocarbyl, halogen atom, cyano, the nitro ,-NR of~20 1 valence2R3Or-SR2Or Q3With Q4It is combined with each other, with carbon original The aromatic rings or heteroaromatic that son is formed together.R2And R3Separately indicate hydrogen atom or the alkyl of carbon atom number 1~6.
D1And D2Separately indicate singly-bound ,-C (=O)-O- ,-C (=S)-O- ,-CR4R5-、-CR4R5-CR6R7-、-O- CR4R5-、-CR4R5-O-CR6R7-、-CO-O-CR4R5-、-O-CO-CR4R5-、-CR4R5-O-CO-CR6R7-、-CR4R5-CO-O- CR6R7Or NR4-CR5R6Or CO-NR4-。
R4、R5、R6And R7Separately indicate the alkyl of hydrogen atom, fluorine atom or carbon atom number 1~4.
G1And G2The alicyclic type hydrocarbon for separately indicating the divalent of carbon atom number 5~8, constitutes the methylene of the alicyclic type hydrocarbon Base can use oxygen atom, sulphur atom or NH- substitutions, and constituting the methyl of the alicyclic type hydrocarbon can be replaced by tertiary N atom.
L1And L2Separately indicate the organic group of 1 valence, L1And L2At least one of have polymerizable group.]
L in compound (A)1The group that preferred formula (A1) indicates, in addition, L2The group that preferred formula (A2) indicates.
P1-F1-(B1-A1)k-E1-(A1)
P2-F2-(B2-A2)l-E2-(A2)
[in formula (A1) and formula (A2),
B1、B2、E1And E2Separately expression-CR4R5-、-CH2-CH2-、-O-、-S-、-CO-O-、-O-CO-O-、-CS- O-、-O-CS-O-、-CO-NR1-、-O-CH2-、-S-CH2Or singly-bound.
A1And A2Separately indicate the virtue of the alicyclic type hydrocarbon of the divalent of carbon atom number 5~8 or the divalent of carbon atom number 6~18 Fragrant race's alkyl, constituting the methylene of the alicyclic type hydrocarbon can be replaced by oxygen atom, sulphur atom or NH-, constitute the ester ring type hydrocarbon The methyl of base can be replaced by tertiary N atom.
K and l separately indicates 0~3 integer.
F1And F2Indicate the aliphatic alkyl of the divalent of carbon atom number 1~12.
P1Indicate polymerizable group.
P2Indicate hydrogen atom or polymerizable group.
R4And R5Separately indicate the alkyl of hydrogen atom, fluorine atom or carbon atom number 1~4.]
As preferred compound (A), for example there are the compounds described in special table 2011-207765 bulletins.
As the concrete example of polymerizable liquid crystal, for example there are liquid crystal handbook, (liquid crystal handbook compiles committee's volume, ball is apt to (strain) and is put down At on October 30th, 12 issue) " 3.8.6network (fully crosslinked type) ", " 6.5.1 liquid crystal material b. polymerism nematics Compound with polymerizable group in compound described in liquid crystal material ".
Phase separation layer is typically by the way that the composition containing a kind or more of polymerizable liquid crystal (A) is coated on base material, is orientated Film or polarization photosphere on, so as to get film in the polymerizable liquid crystal (A) polymerization and formed.
Alignment films in the present invention have and make the orientation anchorage force that polymerizable liquid crystal is orientated towards desired direction.
As alignment films, preferably there is the undissolved solvent resistant in the case where being coated with the composition etc. containing polymerizable liquid crystal Property, in addition, having heat resistance in the heat treatment carried out to remove the orientation of solvent or polymerizable liquid crystal.As in this way Alignment films, for example there are alignment films and optical alignment film containing orientation polymer.
As orientation polymer, for example there are polyamide of the intramolecular with amido bond or gelatin class, intramolecular with acyl The polyimides of imine linkage and its polyamic acid of hydrolysate, alkyl-modified polyvinyl alcohol, polyacrylamide, gather polyvinyl alcohol Oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylate.Wherein, preferably poly- Vinyl alcohol.Orientation polymer of more than two kinds can be combined to use.
Alignment films containing orientation polymer are usually by by orientation polymer lysed composition in a solvent (below, it is known as orientation polymer composition.) be coated on base material, solvent is removed, alternatively, by orientation polymer composition It is coated on base material, removes solvent, obtained after friction (rubbing manipulation).
As the solvent, for example there are water, methanol, ethyl alcohol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, fourths The alcoholic solvents such as base cellosolve, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, Ethylene glycol methyl ether acetic acid esters, γ-Ding Nei The ester solvents such as ester, methyl proxitol acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl The aromatic hydrocarbons such as the aliphatic hydrocarbon solvents such as the ketone solvents such as ketone, methyl iso-butyl ketone (MIBK), pentane, hexane, normal heptane, toluene, dimethylbenzene The ether solvents such as the nitrile solvents such as solvent, acetonitrile, tetrahydrofuran, dimethoxy-ethane, and, the chlorinated hydrocarbon solvents such as chloroform, chlorobenzene.These Solvent can be used alone, can also two kinds of combination of the above uses.
The concentration of orientation polymer in orientation polymer composition, as long as orientation polymer material is in energy In the range of being enough completely dissolved in a solvent, relative to solution, after solid constituent conversion, preferably 0.1~20%, further It is preferred that 0.1 to 10% degree.
As orientation polymer composition, commercially available aligning film material can be directly used.As commercially available alignment films Material, for example there are サ Application エ バ ー (registered trademark, Nissan Chemical Industries (strain) system), オ プ ト マ ー (registered trademark, JSR (strain) System) etc..
It is coated with method on base material as by orientation polymer composition, for example there are spin-coating method, extrusion, intaglio process Method well known to print processes such as the rubbing methods such as brush cladding process, mold cladding process, stick coating method, applicator method, flexo method etc..By rear When the method for continuous production for the roll-to-roll form stated manufactures this circular polarization light board, coating method generally use intaglio printing coating The print processes such as method, mold cladding process or flexo method.
As the method for removing the solvent that orientation polymer composition contains, for example there are natural seasoning, aeration-dryings Method, heat drying and hypobaric drying method etc..
It is orientated anchorage force in order to assign alignment films, can be rubbed as needed (rubbing manipulation).
As assigned by rubbing manipulation the method that is orientated anchorage force for example there are, make to be wound with friction cloth rotating rub The method that the film of wiping roller and orientation polymer contacts with each other, the film of the orientation polymer is by orientation combination of polymers Object is coated on base material, is formed on substrate surface by annealing.
Optical alignment film be typically by containing polymer or monomer and solvent with photoreactive group composition (with Under, be referred to as " optical alignment film formation composition ".) be coated on base material, it is obtained after irradiation polarised light (preferably, polarizing UV) 's.Optical alignment film can arbitrarily control the direction for being orientated anchorage force, from this by the polarization direction for the polarised light for selecting to irradiate It is preferred that point, which sets out,.
Photoreactive group is that the group for generating liquid crystal aligning energy is irradiated by light.Specifically for example there are, irradiated by light, It is anti-to participate in the light such as induction orientation or isomerization reaction, dimerization reaction, photo-crosslinking or the photolysis reactions of product molecule The group answered, these light reactions become the origin of liquid crystal aligning energy.Wherein, it participates in dimerization reaction or the group of photo-crosslinking takes Tropism is excellent, so it is preferred that.As photoreactive group, group preferably with unsaturated bond, particularly double bond, particularly preferably With carbon-to-carbon double bond (C=C keys), carbon-to-nitrogen double bond (C=N keys), nitrogen-nitrogen double bond (N=N keys) and carbon-oxygen double bond (C=O keys) It is formed by least one group selected in group.
As the photoreactive group that C=C keys have, for example there are miscellaneous with vinyl, polyene-based, stilbene radicals, stilbene oxazolyl, class Stilbene base, chalcone base and cinnamoyl.As the photoreactive group with C=N keys, for example there are with aromatic series schiff bases, The isostructural group of aromatic series hydrazone.As the photoreactive group with N=N keys, for example there are with azobenzene, azonaphthalene The group of base, heteroaromatic azo group, bisazo base, formazans base and azoxybenzene structure.As the light with C=O keys Reactive group, for example there are benzophenone base, cumarin base, anthraquinonyl and maleic anhydride contracting imido grpups.These groups can have There are or do not have following substituent groups:Alkyl, alkoxy, aryl, allyloxy, cyano, alkoxy carbonyl group, hydroxyl, sulfonic group, halogen Change alkyl etc..
Wherein, the photoreactive group that light dimerization reaction can preferably occur, from light orientation when required polarizing light irradiation amount It is less and, set out in terms of being easy to get thermal stability or the excellent optical alignment film of ageing stability, preferably cinnamoyl and look into ear Ketone group.As the polymer with photoreactive group, the terminal part of the particularly preferred polymer lateral chain, which has, is used as cinnamic acid The cinnamyl of structure.
By the way that optical alignment film formation to be coated on composition on base material, light orientation induced layer can be formed on base material. As the solvent contained in the composition, for example there are the identical solvent of the solvent contained with above-mentioned orientation polymer composition, It can be adapted suitable for the dissolubility of selection and polymer or monomer with photoreactive group.
The amount of polymer or monomer with the photoreactive group in optical alignment film formation composition, Ke Yigen Come suitable for adjusting according to the thickness of the type or target optical alignment film of polymer or monomer, more preferably at least 0.2 mass %, more preferably The range of 0.3~10 mass %.In the range of unobvious lose the characteristic of optical alignment film, optical alignment film formation composition can To contain the high molecular materials such as polyvinyl alcohol or polyimides or photosensitizing agent.
Be coated with method on base material as by optical alignment film formation composition, for example there are with by orientation polymer group It closes object and is coated on the identical method of method on base material.As the side for removing solvent from the optical alignment film formation composition of coating Method, for example there are for example, method identical with the method for solvent is removed from orientation polymer composition.
When carrying out polarizing light irradiation, it can take after removing solvent to the optical alignment film formation composition being coated on substrate The form of direct irradiation polarised light UV can also be to irradiate polarised light from substrate side, the form for making polarised light penetrate.In addition, special Preferably the polarised light is not substantially directional light.As long as irradiating the wavelength of polarised light in the polymer with photoreactive group Or the photoreactive group of monomer can absorb in the wavelength field of luminous energy.In particular it is especially preferred that wavelength 250~ The UV (ultraviolet light) of the range of 400nm.As the light source used in the polarizing light irradiation, for example there are xenon lamp, high-pressure sodium lamp, superelevation Ultraviolet lasers such as pressure mercury lamp, metal halide lamp, KrF, ArF etc., more preferable high-pressure sodium lamp, ultrahigh pressure mercury lamp and metal halide lamp. These lamps and lanterns have the larger luminous intensity of the ultraviolet light of wavelength 313nm, so it is preferred that.Light from above-mentioned light source is through appropriate Polarizer when being irradiated, polarization UV can be irradiated.As such polarizer, polarized light filter device or lattice can be used The polarizer of the polarizing prisms such as orchid-thomson prism, Glan-Taylor prism or wire grid type.
In addition, when carrying out friction or polarizing light irradiation, if implementing masking, the direction that can form liquid crystal aligning is different Multiple regions (pattern (pattern)).
The thickness of alignment films (alignment films containing orientation polymer and optical alignment film) is usually 10nm~10000nm's Range, the preferably range of 10nm~1000nm, more preferable 500nm hereinafter, further preferably 10nm~100nm range.
The composition containing a kind or more of polymerizable liquid crystal (A) used in the formation of phase separation layer (below, is referred to as Composition A.) solvent is usually contained, as solvent, for example there are the solvent contained with above-mentioned orientation polymer composition is identical Solvent, can be according to the dissolubility of polymerizable liquid crystal (A) suitable for selection.
The coating of composition A usually penetrate spin-coating method, extrusion, intaglio printing cladding process, mold cladding process, stick coating method, Method well known to print processes such as the rubbing methods such as applicator method or flexo method etc. carries out.After coating, usually in obtained coated film The polymerizable liquid crystal (A) contained removes solvent under conditions of not polymerizeing, form dry coationg.As drying means, for example there are certainly Right seasoning, aeration-drying method, heat drying and hypobaric drying method.
The polymerization of polymerizable liquid crystal (A) can pass through the well known side for the compound polymerization for making that there are polymerizable functional groups to roll into a ball Method carries out.Specifically, for example there are thermal polymerization and photopolymerization, from the easness aspect of polymerization, preferably photopolymerization.It is preferred that passing through When photopolymerization makes polymerizable liquid crystal (A) polymerize, it is coated with the composition A containing Photoepolymerizationinitiater initiater, the drying obtained after to be dried Polymerizable liquid crystal (A) in envelope keeps the mesomorphic state, makes its photopolymerization in after liquid crystal phase.
Usually by dry coationg irradiation light implement photopolymerization.As irradiation light, contained according to dry coationg Type, the type of polymerizable liquid crystal (A) (the especially, kind for the photopolymerization base that polymerizable liquid crystal (A) includes of Photoepolymerizationinitiater initiater Class) and its suitable selection of amount, specifically, for example there are be formed by the light selected in group, activity from visible light, ultraviolet light and laser Electron beam.Wherein, in terms of the progress for being easy to control polymerisation, and widely used device conduct in the field can be used It sets out in terms of photo-polymerization device, preferably ultraviolet light, the type of the polymerizable liquid crystal (A) or Photoepolymerizationinitiater initiater that preferably select can To carry out photopolymerization by ultraviolet light.In addition, when polymerization, dry coationg, Bian Zhao can be cooled down by suitably cooling means with side It penetrates light, thus controls polymerization temperature.By using such cooling way, implement polymerizable liquid crystal (A) at lower temperatures When polymerization, even if using the poor base material of heat resistance, phase separation layer can also be properly formed.When photopolymerization, by being covered It covers and develops, figuratum phase separation layer can also be obtained.
The overall thickness of phase separation layer and polarization photosphere in this circular polarization light board is at 10 μm or less.The thickness of phase separation layer is excellent Select 0.5 μm or more 9.5 μm hereinafter, more preferable 1 μm or more 5 μm or less.Polarize preferably 0.5 μm or more 9.5 μm of the thickness of photosphere with Under, more preferable 1 μm or more 5 μm or less.Phase separation layer and the thickness for polarizing photosphere usually can be by interfering film thickness gauge, laser aobvious The measurement of micro mirror or contact pin type film thickness gauge is found out.
Polarization photosphere contains dichroism pigment." dichroism pigment " refer to have absorbance in the long axis direction of molecule with The pigment of the different property of absorbance on short-axis direction.As long as having the quality that, then to dichroism pigment, there is no limit, It can be dyestuff, can also be pigment.Dye combinations that can also be two kinds or more use, and can be two kinds or more of pigment combinations It uses, it can also dyestuff and pigment combination use.
With maximum absorption wavelength (λ MAX) in the range of dichroism pigment preferably 300~700nm.As such two Color pigment, for example there are acridine pigment, oxazines pigment, anthocyanidin, naphthalene pigment, azopigment and anthraquinone pigments, wherein preferably Azopigment.As azopigment, it is even that for example there are monoazo pigment, bisazo pigment, trisazo- pigment, four azopigments and stilbenes Nitrogen pigment, preferably bisazo pigment and trisazo- pigment.
Azopigment conduct, the compound indicated for example there are formula (1) (below, are known as " compound (1) " according to occasion.).
A1(- N=N-A2)p- N=N-A3(1)
[in formula (1),
A1And A3Separately indicating can be with or without the phenyl of substituent group, can be with or without substitution The naphthalene of base can be with or without the heterocycle of 1 valence of substituent group.A2Expression can be with or without substitution Base to phenylene, can with or without substituent group naphthalene-Isosorbide-5-Nitrae-diyl or can be with or without substituent group Divalent heterocycle.P indicates 1~4 integer.When the integer that p is 2 or more, multiple A2It can be the same or different.]
As the heterocycle of 1 valence, for example there are quinoline, thiazole, benzothiazole, thiophene-thiazole, imidazoles, benzimidazole, oxazoles, The group of 1 hydrogen atom is eliminated in the heterocyclic compounds such as benzoxazole.As the heterocycle of divalent, for example there are above-mentioned jeterocyclic chemistries Close the group that 2 hydrogen atoms are eliminated in object.
As A1And A3In phenyl, the heterocycle and A of naphthalene and 1 valence2In to phenylene, naphthalene-Isosorbide-5-Nitrae-diyl and divalent The substituent group that can arbitrarily have of heterocycle, for example there are the alkyl of carbon atom number 1~4;Methoxyl group, ethyoxyl, butoxy etc. The alkoxy of carbon atom number 1~4;The fluoroalkyl of the carbon atom numbers such as trifluoromethyl 1~4;Cyano;Nitro;Halogen atom;Amino, (substituted-amino refers to having 1 or 2 carbon atom numbers 1 for the substitution such as lignocaine, pyrrolidines pyridyl group or unsubstituted amino The amino of~6 alkyl or 2 substitution alkyl are bound to each other to form the amino of the alkylidene of carbon atom number 2~8.Unsubstituted ammonia Base is-NH2。)。
In compound (1), preferably following formula (1-1)~formula (1-6) any one indicate compound.
[in formula (1-1)~(1-6),
B1~B20Separately indicate hydrogen atom, the alkyl of carbon atom number 1~6, the alkoxy of carbon atom number 1~4, cyano, Nitro, substituted or unsubstituted amino (substituted-amino and unsubstituted amino are as defined above), chlorine atom or trifluoromethyl.
N1~n4 separately indicates 0~3 integer.
N1 is at 2 or more, multiple B2It can be the same or different,
N2 is at 2 or more, multiple B6It can be the same or different,
N3 is at 2 or more, multiple B9It can be the same or different,
N4 is at 2 or more, multiple B14It can be the same or different.]
The compound indicated as above-mentioned anthraquinone pigment, preferred formula (1-7).
[in formula (1-7),
R1~R8Separately indicate hydrogen atom ,-Rx、-NH2、-NHRx、-NRx 2、-SRxOr halogen atom.
RxIndicate the alkyl of carbon atom number 1~4 or the aryl of carbon atom number 6~12.]
The compound indicated as Shang Shu oxazine pigments, preferred formula (1-8).
[in formula (1-8),
R9~R15Separately indicate hydrogen atom ,-Rx、-NH2、-NHRx、-NRx 2、-SRxOr halogen atom.
RxIndicate the alkyl of carbon atom number 1~4 or the aryl of carbon atom number 6~12.]
The compound indicated as above-mentioned acridine pigment, preferred formula (1-9).
[in formula (1-9),
R16~R23Separately indicate hydrogen atom ,-Rx、-NH2、-NHRx、-NRx 2、-SRxOr halogen atom.
RxIndicate the alkyl of carbon atom number 1~4 or the aryl of carbon atom number 6~12.]
In formula (1-7), formula (1-8) and formula (1-9), as RxCarbon atom number 1~6 alkyl, for example there are methyl, ethyl, third Base, butyl, amyl and hexyl, as the aryl of carbon atom number 6~12, for example there are phenyl, tolyl, xylyl and naphthalenes.
The compound that the compound and formula (1-11) indicated as above-mentioned anthocyanidin, preferred formula (1-10) indicates.
[in formula (1-10),
D1And D2The group that separately any one of expression (1-10a)~formula (1-10d) indicates.
N5 indicates 1~3 integer.]
[in formula (2-11),
D3And D4The group that separately any one of expression (1-11a)~formula (1-11h) indicates.
N6 indicates 1~3 integer.]
It is coat to polarize photosphere.Additionally, it is preferred that other than dichroism pigment, coating contains 1 as main compound Kind or more polymerizable liquid crystal (following, be referred to as polymerizable liquid crystal (B)) composition (following, be referred to as composition B), pass through Polymerizable liquid crystal (B) polymerization in the film made forms polarization photosphere.
The preferred smectic phase of mesomorphic state of polymerizable liquid crystal (B) display, from the higher polarization of ordered orientation degree can be manufactured It sets out in terms of photosphere, more preferable high order smectic phase." high order smectic phase " refers to smectic B, smectic D phases, smectic E phases, smectic F Phase, smectic G phases, smectic H phases, smectic I phases, smectic J phases, smectic K phases and smectic L phases, wherein more preferable smectic B, smectic F Phase and smectic I phases.The high polarization photosphere of ordered orientation degree in X-ray diffraction measure, obtain from hexagonal phase (hexatic) or The bragg peak of the higher order structures such as crystalline phase." bragg peak " refers to the peak of the face periodic structure from molecularly oriented, preferably all Period is divided intoPolarization photosphere.
The polymerizable liquid crystal (B) of display smectic phase is known as polymerism smectic liquid crystal compound.As polymerism smectic liquid crystal Compound, the compound indicated for example there are formula (B) (below, are known as compound (B).).
U1-V1-W1-X1-Y1-X2-Y2-X3-W2-V2-U2(B)
[in formula (B),
X1、X2And X3Separately indicate can with or without substituent group Isosorbide-5-Nitrae-phenylene or can have or 1 or 4 cyclohexylidene without substituent group.But X1、X2And X3At least one of for can be with or without substitution Isosorbide-5-Nitrae-phenylene of base.Constitute-the CH of 1 or 4 cyclohexylidene2It can be replaced by-O- ,-S- or-NR-.R indicates carbon atom number 1 ~6 alkyl or phenyl.
Y1And Y2Separately expression-CH2CH2-、-CH2O- ,-COO- ,-OCOO-, singly-bound ,-N=N- ,-CRa=CRb-、-C ≡ C- or CRa=N-.RaAnd RbSeparately indicate hydrogen atom or the alkyl of carbon atom number 1~4.
U1Indicate hydrogen atom or polymerizable group.
U2Indicate polymerizable group.
W1And W2Separately indicate singly-bound ,-O- ,-S- ,-COO- or OCOO-.
V1And V2It separately indicates to constitute with or without the alkylidene of the carbon atom number 1~20 of substituent group - the CH of the alkylidene2It can be replaced by-O- ,-S- or NH-.]
It is preferred that X1、X2And X3In at least two be can be with or without Isosorbide-5-Nitrae-phenylene of substituent group.
It is preferred that can be unsubstituted with or without Isosorbide-5-Nitrae-phenylene of substituent group.It is preferred that can have or not Isosorbide-5-Nitrae with substituent group-Asia hexamethylene is can preferably may be used with or without the anti-form-1 of substituent group, 4- cyclohexylidenes With the anti-form-1 with or without substituent group, 4- cyclohexylidenes are unsubstituted.
As can with or without substituent group Isosorbide-5-Nitrae-phenylene or can be with or without substituent group The substituent group that 1 or 4 cyclohexylidene can arbitrarily have, for example there are the alkyl of the carbon atom numbers such as methyl, ethyl, propyl 1~4, Cyano and halogen atom.
It is preferred that Y1For-CH2CH2,-COO- or singly-bound, preferably Y2For-CH2CH2Or CH2O-。
U2For polymerizable group.U1Indicate hydrogen atom or polymerizable group, preferred polymeric group.U1And U2It is preferred that simultaneously Preferably it is polymerism group simultaneously for polymerizable group." polymerism group " is to refer to draw by aftermentioned photopolymerization Send out the group that living radical or the acid etc. that agent generates participate in polymerisation.
U1The polymerism group and U of expression2Although the polymerizable group of expression can be mutually different, it is preferred that of the same race The group of class.As polymerizable group, for example there are vinyl, ethyleneoxy, 1- chlorovinyls, isopropenyl, 4- vinyl benzenes Base, acryloxy, methacryloxy, Oxyranyle and propylene oxide base.Wherein, preferably acryloxy, methyl Acryloxy, ethyleneoxy, Oxyranyle and propylene oxide base, more preferable acryloxy.
As V1And V2The alkylidene of expression, for example there are methylene, ethylidene, 1,3- propylidene, 1,3- butylidenes, Isosorbide-5-Nitraes- Butylidene, 1,5- pentylidene, 1,6- hexylidenes, 1,7- heptamethylenes, 1,8- octamethylenes, 1,10- decylenes, the Asias the 1,14- tetradecane Base and 1,20- alkylene eicosyls.V1And V2, the preferred alkylidene of carbon atom number 2~12, the alkylene of more preferable carbon atom number 6~12 Base.
As the substituent group that the alkylidene can arbitrarily have, for example there are cyano and halogen atoms, preferably the alkylidene For unsubstituted, more preferable unsubstituted and straight chain alkylidene.
W1And W2It is preferably separately singly-bound or the group of O-.
As compound (B), for example there are the compounds that formula (B-1)~formula (B-25) indicates.Compound (B) has Isosorbide-5-Nitrae-Asia When cyclohexyl, the preferably trans- body of the 1 or 4 cyclohexylidene.
Wherein, preferred formula (B-2), formula (B-3), formula (B-4), formula (B-5), formula (B-6), formula (B-7), formula (B-8), formula (B- 13), the compound that formula (B-14), formula (B-15), formula (B-16) and formula (B-17) indicate is formed by least 1 selected in group Kind.
(B) Ke Yi Unit are only or are applied in combination for the polymerizable liquid crystal of illustration.In addition, when combining polymerizable liquid crystal of more than two kinds, Preferably at least a kind is polymerizable liquid crystal (B), and more preferably two or more is polymerizable liquid crystal (B).It, can be in liquid crystal-by combination Liquid crystal liquid crystal property also can be temporarily kept when crystallization phase transition temperature temperature below.It is mixed as it when combining 2 kinds of polymerizable liquid crystal compounds Composition and division in a proportion, usually 1:99~50:50, preferably 5:95~50:50, more preferable 10:90~50:50.
Polymerizable liquid crystal (B) is for example, by Lub et al.Recl.Trav.Chim.Pays-Bas 115,321-328 (1996) or known method described in patent the 4719156th etc. manufactures.
Solid constituent of the content ratio of polymerizable liquid crystal (B) in composition B relative to composition, preferably 70~99.9 Quality %, more preferable 80~99.9 mass %.Polymerizable liquid crystal (B) if content ratio within the above range, polymerism liquid The orientation of brilliant (B) has the tendency that getting higher.Herein, " solid constituent " refer to from composition B eliminate the volatility such as solvent at The total amount of ingredient after point.
The amount of dichroism pigment in composition B can suitably be adjusted according to type of dichroism pigment etc., still, Relative to 100 mass parts of polymerizable liquid crystal (B), more than preferably 0.1 mass parts 50 is below mass part, more preferable 0.1 mass parts with Upper 20 is below mass part, and more than further preferred 0.1 mass parts 10 is below mass part.The amount of dichroism pigment if it is Within the scope of this, its polymerization can be made in the case where not upsetting the orientation of polymerizable liquid crystal (B).The amount of dichroism pigment When excessive, the orientation of polymerizable liquid crystal (B) can be probably hindered.
Composition B preferably comprises solvent.Usually, because the viscosity of smectic liquid crystal compound is high, the combination containing solvent It is in the majority with the occasion for being readily formed polarization film to be easy coating , Knot fruits for object.As solvent, for example there are poly- with above-mentioned orientation The identical solvent of solvent that polymer composition contains, can be suitable according to the dissolubility of polymerizable liquid crystal (B) and dichroism pigment Selection.
Total amount of the amount of solvent relative to composition B, preferably 50~98 mass %.In other words, in composition B Solid constituent preferably 2~50 mass %.
Composition A and/or composition B preferably comprises a kind or more of levelling agent.Levelling agent can adjust the stream of composition B Dynamic property, has the function of keeping the obtained coated films of coating composition B more flat, specifically, for example there are surfactants.As Levelling agent, preferably using levelling agent that polyacrylic acid ester compounds are main ingredient and using the compound containing fluorine atom as principal component It is selected in the group that levelling agent is formed at least one kind of.
As with polyacrylic acid ester compounds be main ingredient levelling agent, for example there are " BYK-350 ", " BYK-352 ", " BYK-353 ", " BYK-354 ", " BYK-355 ", " BYK-358N ", " BYK-361N ", " BYK-380 ", " BYK-381 " and " BYK-392 " [BYK Chemie societies].
As using the compound containing fluorine atom as the levelling agent of principal component, for example there are " メ ガ Off ァ ッ Network (registered trademark) It is R-08 ", same " R-30 ", same " R-90 ", same " F-410 ", same " F-411 ", same " F-443 ", same " F-445 ", same " F-470 ", same " It is F-471 ", same " F-477 ", same " F-479 ", same " F-482 " and same " F-483 " [DIC (strain)];” サ ー Off ロ Application (registrars Mark) it is S-381 ", same " it is S-382 ", same " it is S-383 ", same " it is S-393 ", same " it is SC-101 ", same " SC-105 ", " KH-40 " and " SA- 100 " [AGC セ イ ミ ケ ミ カ Le (strain)];" E1830 ", " E5844 " [(strain) daikin fine chemical research institutes];”エ Off ト ッ プ EF301 ", " エ Off ト ッ プ EF303 ", " エ Off ト ッ プ EF351 " and " エ Off ト ッ プ EF352 " [and Mitsubishi Materials electricity Son chemical conversion (strain)].
When composition A and/or composition B contain levelling agent, amount therein is relative to 100 mass of polymerizable liquid crystal Part, more than preferably 0.05 mass parts 5 is below mass part, and more than more preferable 0.05 mass parts 3 is below mass part.Levelling agent contains Amount makes polymerizable liquid crystal horizontal alignment become easy in above-mentioned range, and, obtained polarization photosphere tends to smoother. Relative to polymerizable liquid crystal, in above-mentioned range, obtained polarization photosphere tends to not allow to be also easy to produce the amount of levelling agent It is uneven.
Composition A and/or composition B preferably comprises a kind or more of polymerization initiator.Polymerization initiator be can cause it is poly- The compound of the polymerisation of conjunction property liquid crystal (B) can also set out under more cryogenic conditions in terms of initiated polymerization, excellent Select Photoepolymerizationinitiater initiater.Specifically, for example there are by light action can generate living radical or acid Photoepolymerizationinitiater initiater, In, the Photoepolymerizationinitiater initiater that is preferably generated free radicals by light action.
As polymerization initiator, for example there are benzoin compound, benzophenone cpd, benzene alkyl ketone compound, acyl groups Phosphine oxide compound, triaizine compounds, salt compounded of iodine and sulfonium salt.
As benzoin compound, for example there are styrax, styrax methyl ether, styrax ethylether, benzoin isobutyl propyl ethers And benzoin isobutyl butyl ether.
As benzophenone cpd, for example there are benzophenone, o-benzoyl base benzoic acid methyl esters, 4- phenyl hexichol first Ketone, 4- benzoyls -4 '-methyldiphenyl base sulphur, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone and 2,4,6- tri- Methyl benzophenone.
As benzene alkyl ketone compound, for example there are diethoxy acetophenone, 2- methyl -2- morpholines -1- (4- methylthio phenyls Base) propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholinyl phenyls) butane -1- ketone, 2- hydroxy-2-methyl -1- phenyl Propane -1- ketone, 1,2- diphenyl -2,2- dimethoxy-ethane -1- ketone, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) Phenyl] propane -1- ketone, 1- hydroxycyclohexyl phenyl ketones and 2- hydroxy-2-methyls -1- (4- (1- methyl ethylenes) phenyl) The oligomer of propane -1- ketone.
As acylphosphine oxide compound, for example there are 2,4,6- trimethylbenzoyl biphenylyl phosphine oxides and it is bis- (2, 4,6- trimethylbenzoyls) phenyl phosphine oxide.
As triaizine compounds, for example there are bis- (trichloromethyl) -6- (4- the methoxyphenyls) -1,3,5-triazines of 2,4-, 2, 4- bis- (trichloromethyl) -6- (4- methoxyl groups naphthalene) -1,3,5-triazines, bis- (trichloromethyl) -6- (the 4- methoxy styrenes of 2,4- Base) -1,3,5-triazines, bis- (the trichloromethyl) -6- of 2,4- (2- (5- methylfuran -2- bases) vinyl) -1,3,5-triazines, 2,4- Bis- (trichloromethyl) -6- (2- (furans -2- bases) vinyl) -1,3,5-triazines, bis- (trichloromethyl) -6- (2- (the 4- diethyls of 2,4- Base amino-2-methyl phenyl) vinyl) -1,3,5-triazines, bis- (the trichloromethyl) -6- of 2,4- (2- (3,4- Dimethoxyphenyl) Vinyl) -1,3,5-triazines.
Polymerization initiator can use commercially available product.As commercially available polymerization initiator, for example there are " イ Le ガ キ ュ ア (Irgacure) (registered trademark) 907 ", " イ Le ガ キ ュ ア (registered trademark) 184 ", " イ Le ガ キ ュ ア (registered trademark) 651 ", " イ Le ガ キ ュ ア (registered trademark) 819 ", " イ Le ガ キ ュ ア (registered trademark) 250 ", " イ Le ガ キ ュ ア (notes Volume trade mark) 369 " (vapour bar Japan (strains));" セ イ ク オ ー Le (Seikuol) (registered trademark) BZ ", " セ イ ク オ ー Le (Seikuol) (registered trademark) Z ", " セ イ ク オ ー Le (Seikuol) (registered trademark) BEE " (Seiko chemistry (strain));“カ ヤ キ ュ ア ー (kayacure) (registered trademark) BP100 " (Japanese chemical drug (strain));" カ ヤ キ ュ ア ー (registered trademark) UVI-6992 " (Tao Shi societies system);“アデカオプトマー(Adeka Optomer)SP-152”、“アデカオプトマー (Adeka Optomer) SP-170 " ((strain) ADEKA);" TAZ-A ", " TAZ-PP " (Japanese シ イ ベ Le ヘ グ ナ ー societies);And " TAZ-104 " (three and chemical society).
When composition A and/or composition B contain polymerization initiator, amount can be according to containing in the composition The type and its amount of polymerizable liquid crystal are appropriate to be adjusted, but relative to 100 mass parts of polymerizable liquid crystal, preferably 0.1~30 mass Part, more preferable 0.5~10 mass parts, further preferred 0.5~8 mass parts.As long as the amount of polymerizing initiator is in the model In enclosing, so that it may which the orientation not upset polymerizable liquid crystal (B) makes its polymerization.
When composition A and/or composition B contain Photoepolymerizationinitiater initiater, the composition can further contain photosensitizing agent. As photosensitizing agent, for example there are the xanthones such as xanthone and thioxanthones based compound (such as 2,4- diethyl thioxanthones, 2- Isopropyl thioxanthone etc.), the anthracenes based compound such as anthracene and the anthracene (such as dibutoxy anthracene etc.) containing alkoxy, phenthazine and Rubrene.
When composition A and/or composition B contain Photoepolymerizationinitiater initiater and photosensitizing agent, can more it promote in the composition The polymerisation of the polymerizable liquid crystal contained.The usage amount of photosensitizing agent can be according to Photoepolymerizationinitiater initiater and polymerizable liquid crystal Type and its amount is appropriate adjusts, still, relative to 100 mass parts of polymerizable liquid crystal, preferably 0.1~30 mass parts, more preferable 0.5 ~10 mass parts, further preferred 0.5~8 mass parts.
In order to make the polymerisation of polymerizable liquid crystal more stably carry out, composition A and/or composition B can be containing suitable The polymerization inhibitor of amount, by this, it is possible to the easily carry out degree of the polymerisation of control polymerizable liquid crystal.
As polymerization inhibitor, the quinhydrones for example there are quinhydrones, containing alkoxy, (such as the butyl of the catechol containing alkoxy Tea phenol etc.), pyrogallic acid class, free radical scavengers, the benzenethiol such as 2,2,6,6- tetramethyl -1- piperidinyloxi free radicals Class, betanaphthyl amine and betanaphthol class.
When composition A and/or composition B contain polymerization inhibitor, amount can according to the type of polymerizable liquid crystal and its The amount and usage amount etc. of photosensitizing agent is appropriate adjusts, relative to 100 mass parts of polymerizable liquid crystal, preferably 0.1~30 mass parts, More preferable 0.5~10 mass parts, further preferred 0.5~8 mass parts.It, can be with as long as the amount of polymerization inhibitor is in the range Not upsetting the orientation of polymerizable liquid crystal makes its polymerization.
In general, composition B is coated on base material, alignment films or phase separation layer, pass through the polymerization in the film that makes Property liquid crystal (B) polymerize formed polarization photosphere.The method of coating the composition does not limit.As the alignment films, for example there are with it is upper The identical film stated.
Coating composition B is dry under conditions of polymerization by the polymerizable liquid crystal (B) contained in obtained coated film Solvent is removed, dry coationg is formed.As drying means, for example there are natural seasoning, aeration-drying method, heat drying and decompressions Seasoning.When polymerizable liquid crystal (B) is polymerism smectic liquid crystal compound, the polymerism smectic liquid that preferably contains dry coationg After nematic phase (nematic crystal state) is presented in the mesomorphic state of brilliant compound, it is changed into smectic phase.In order to via nematic Smectic phase is mutually formed, using for example, the polymerism smectic liquid crystal compound that heat drying envelope to dry coationg contains mutually becomes It is more than the temperature when mesomorphic state of nematic phase, then cooling until polymerism smectic liquid crystal compound is shown as smectic phase The method of the temperature of mesomorphic state.
Then, after becoming smectic phase to the mesomorphic state of the polymerizable liquid crystal (B) in dry coationg, the liquid of smectic phase is kept Crystalline state makes the method for polymerizable liquid crystal (B) photopolymerization illustrate.In photopolymerization, as the light being radiated on dry coationg, Type, the type of polymerizable liquid crystal (B) of the Photoepolymerizationinitiater initiater contained according to the dry coationg (are especially the polymerizable liquid crystal (B) type for the photopolymerization base for including) and its suitable selection of amount, as concrete example, for example there are visible light, ultraviolet light and laser institutes The light or active electron beam selected in the group of formation.Among these, from being easy to control polymerisation aspect, and it is poly- from light Attach together that set set out in terms of device commonly used in the art, preferably ultraviolet light.It is preferred, therefore, that containing in selection above-mentioned composition B Polymerizable liquid crystal (B) or Photoepolymerizationinitiater initiater type so that it can carry out photopolymerization by ultraviolet light.In addition, when polymerization, Cooling envelope can be dried suitably by cooling way, thus marginal ray irradiation controls polymerization temperature with side.By using in this way Cooling way, when implementing the polymerization of polymerizable liquid crystal (B) at lower temperatures, even if can if using heat-resisting relatively low base material It is properly formed polarization photosphere.When photopolymerization, by being sheltered or being developed, figuratum polarization photosphere can also be obtained.
By carrying out photopolymerization, polymerizable liquid crystal (B) may remain in the liquid crystal shape of smectic phase, the preferred smectic phase of high order It polymerize under state, forms polarization photosphere.The polarization photosphere polymerizeing under the mesomorphic state of polymerizable liquid crystal (B) holding smectic phase, Have the function of above-mentioned dichroism pigment, and with previous host and guest's build polarization film, that is, the mesomorphic state of nematic phase is formed Polarization film compare, have the advantages that polarised light performance is high.Further, with the phase that only applies dichroism pigment or lysotropic liquid crystal Than having the advantages that excellent strength.
The slow axis of phase separation layer in this circular polarization light board and the absorption axiss of polarization photosphere are not parallel to each other, in addition, mutually Also out of plumb.In order to allow circular polarization light board to give expression to good function, the preferably slow axis of phase separation layer and polarization photosphere Practical absorption axiss angulation is 45 °.
When manufacturing this circular polarization light board, forming the sequence of phase separation layer and polarization photosphere can be arbitrary.It can be in base After forming phase separation layer on material, polarization photosphere is formed on phase separation layer.After polarization photosphere can also be formed on base material, inclined It shakes and forms phase separation layer on photosphere.Polarization photosphere can also be formed in the one side of base material, formed in the other faces of base material Phase separation layer.It can be formed and be taken between base material and phase separation layer, base material and polarization photosphere and/or phase separation layer and polarization photosphere To film.
It, as needed, can be in phase separation layer when forming polarization photosphere after forming phase separation layer on base material, on phase separation layer Upper formation protective layer forms polarization photosphere on protective layer.Polarised light can be formed thereon to form alignment films on above-mentioned protective layer Layer.After forming polarization photosphere on base material, protective layer is formed on polarization photosphere, forms phase separation layer thereon.Also After alignment films can be formed on above-mentioned protective layer, phase separation layer is formed thereon.
Protective layer is generally preferably by containing polyfunctional acrylic ester (methacrylate), urethane acrylate, polyester third The acrylic oligomers or polymer of the formation such as olefin(e) acid ester, epoxy acrylate, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, The water-soluble polymers such as polyvinylpyrrolidone, starch, methylcellulose, carboxymethyl cellulose, sodium alginate and solvent Protective layer formation formed with composition.
The solvent contained in protective layer formation composition, for example there are have solvent identical with above-mentioned solvent.Wherein, water, Alcoholic solvent and ether solvents are formed by least one solvent selected in group, the insoluble layer for forming protective layer, from this aspect It is preferred to set out.As alcoholic solvent, methanol, ethyl alcohol, butanol, ethylene glycol, isopropanol, propylene glycol, Ethylene glycol methyl ether, second two Alcohol butyl ether and propylene glycol monomethyl ether;As ether solvents, for example there are Ethylene glycol methyl ether acetic acid esters and propylene glycol methyls Ether acetic acid ester, wherein preferred alcohol, isopropanol, propylene glycol monomethyl ether and propylene glycol monomethyl ether.
The thickness of protective layer is usually at 20 μm or less.Preferably 0.5 μm or more 9.5 μm of the thickness of protective layer is hereinafter, more preferable 1 μm or more 5 μm or less.The thickness of protective layer usually can be by interfering film thickness gauge, laser microscope or contact pin type film thickness gauge to measure It finds out.
On the surface of phase separation layer or polarization photosphere that the surface of this circular polarization light board is formed, can further have bonding Oxidant layer.In addition, can have priming coat between phase separation layer or polarization photosphere, adhesive phase.
Adhesive phase is formed by adhesive, and adhesive usually contains polymer, can also contain solvent.
As above-mentioned polymer, can enumerate for example, acrylic acid series polymeric compounds, polysiloxanes based polymer, polyester, poly- ammonia Ester or polyethers etc..Wherein, the acrylic binder containing acrylic acid series polymeric compounds, optical transparence is excellent, keeps appropriateness Wettability or cohesiveness, close property is also excellent, and against weather and heat resistance are high, will not under conditions of heating or humidification The stripping problems such as float or peel off, so it is preferred that.
As above-mentioned acrylic acid series polymeric compounds, the preferably alkyl of ester moiety is the carbon atom numbers 20 such as methyl, ethyl or butyl Alkyl below (methyl) acrylate (hereinafter, general name acrylate, methacrylate be (methyl) acrylate, third Olefin(e) acid is (methyl) acrylic acid with methacrylate.) and with the officials such as (methyl) acrylic acid or (methyl) hydroxy-ethyl acrylate The copolymer of (methyl) acrylic monomer that can be rolled into a ball.
Such adhesive tack containing copolymer is excellent, in addition, after fitting on the display apparatus, when stripping, no The remnants etc. that paste can be generated on the display apparatus, can be relatively easy to stripping, so it is preferred that.The acrylic acid series polymeric compounds Preferably 25 DEG C of glass transition temperature is hereinafter, more preferable 0 DEG C or less.The weight average molecular weight of such acrylic acid series polymeric compounds is preferred 100000 or more.
As above-mentioned solvent, for example, for example there are the solvents that the solvent as above-mentioned orientation polymer composition is enumerated Deng.
In addition, adhesive can contain light diffusing agent.Light diffusing agent can assign adhesive phase light diffusing, as long as tool There is the particle of the refractive index different from the above-mentioned polymer contained by adhesive phase, as light diffusing agent, for example there are inorganization Close the particle that object is formed or the particle that organic compound (polymer) is formed.Including above-mentioned acrylic acid series polymeric compounds, constitute bonding The polymeric matrix of oxidant layer has 1.4 or so refractive index, so, can be 1 suitable for selecting its refractive index as light diffusing agent ~2 or so.Contained by adhesive as the polymer of active ingredient and the refringence of light diffusing agent, usually 0.01 with On, in addition, from the point of view of liquid crystal display device brightness and visuality, it is advisable with 0.01 or more 0.5 or less.Make as light diffusing agent Particle, it is preferably spherical, close to monodispersed, it is, for example, possible to use average grain diameter is in 2~6 μm or so of range Particle.
Refractive index is generally measured by angle of minimum deviation method or Abbe refractometer.
As the particle that inorganic compound is formed, can illustrate for example, aluminium oxide (refractive index 1.76) and silica (refraction Rate 1.45) etc..
In addition, as the particle that organic compound (polymer) is formed, can illustrate for example, (the refraction of melamine particle Rate 1.57), polymethyl methacrylate particle (refractive index 1.49), the fit resin particle of methyl methacrylate/styrene copolymerized Sub (refractive index 1.50~1.59), makrolon particle (refractive index 1.55), polyethylene particles (refractive index 1.53), polystyrene Particle (refractive index 1.6), particulate polyvinyl chloride (refractive index 1.46) and silicone resin particle (refractive index 1.46) etc..
The combined amount of light diffusing agent is according to disperseing necessary to its adhesive phase haze value or to be applicable in its liquid crystal display Brightness of device etc. determines, usually, relative to resin 100 parts by weight for constituting adhesive phase, on 3~30 parts by weight left side It is right.
It is dispersed with the haze value of the adhesive phase of light diffusing agent, is being ensured using the circular polarization light board for having adhesive phase Liquid crystal display device brightness while, from the aspect of the fuzzy or scattered scape of display image is not easy appearance, preferably 20~ 80% range.Haze value is the value that (diffusion light transmittance/total light transmittance) × 100 (%) indicate, is measured according to JIS K 7105.
As long as the thickness of adhesive phase is just not particularly limited according to decisions such as its clinging forces, but in general, is 1 ~40 μm or so.In order not to damage the characteristics such as processability or durability, has the circular polarization of slim adhesive phase in order to obtain Tabula rasa, the preferably thickness of adhesive phase are 3~25 μm or so.In addition, by the thickness of adhesive phase at 3~25 μm or so, it can Brightness can be kept when so that liquid crystal display device is in terms of front or in terms of inclined-plane, it is not easy to occur showing the fuzzy of image Or scattered scape.
Priming coat usually contains transparent resin, is formed by transparent resin solution.Priming coat can be with when forming adhesive phase Inhibit phase separation layer or polarizes the defect of photosphere.As transparent resin, preferably apply that work is excellent, and priming coat formed after it is transparent Property and adherence are excellent.
The solvent of above-mentioned transparent resin solution can use benzene,toluene,xylene etc. according to above-mentioned transparent dissolubility Aromatic hydrocarbon solvents;The ketone solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK);The esters such as ethyl acetate, i-butyl base Solvent;The chlorinated hydrocarbon solvents such as dichloromethane, trichloro ethylene, chloroform;Alcoholic solvents such as ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol etc. one As organic solvent, but using containing organic solvent transparent resin solution formed priming coat when, in order to not influence liquid crystal cured film Optical characteristics, it is preferable to use using water as solvent solution formed priming coat.
As above-mentioned transparent resin, can illustrate epoxy resin.Epoxy resin can be a solution curing type, can be two liquid Curing type.Particularly preferred water-soluble epoxy resin.As water-soluble epoxy resin, for example there are make polyamide polyamines and table chlorine Alcohol Polyamide Epoxy obtained by the reaction, the polyamide polyamines gather Asia as diethylenetriamines or trien Dicarboxylic acids is obtained by the reaction as alkyl polyamine and adipic acid.As the commercially available product of such Polyamide Epoxy, for example there are Firmly change " ス ミ レ ー ズ レ ジ Application (registered trademark) 650 (30) " or " ス ミ レ ー ズ レ ジ Application that ケ system テ ッ Network ス (strain) are sold (registered trademark) 675 " (registered trademark) etc..
When using water-soluble epoxy resin as above-mentioned transparent resin, in order to further increase coating, it is preferably used in combination The others water-soluble resin such as polyvinyl alcohol resin.Polyvinyl alcohol resin can be partly-hydrolysed polyvinyl alcohol, complete soap Change polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl modified polyvinyl alcohol, methylol-modified polyvinyl alcohol, amino to change The modified polyvinyl alcohol resin of property polyethanol etc.As the commercially available product of suitable polyvinyl alcohol resin, for example there are The polyvinyl alcohol " KL-318 " (trade name) containing anionic group etc. of (strain) KURARAY sale.
When forming priming coat by containing water-soluble epoxy resin solution, epoxy resin preferably with respect to 100 parts by weight of water, In the range of 0.2~1.5 parts by weight or so.In addition, in the solution when mixing pva system resin, amount is relative to water 100 Parts by weight, preferably 1~6 parts by weight or so.The range that preferably 0.1~10 μm or so of the thickness of priming coat.
To the forming method of priming coat, there is no limit can use direct intagliotype, reversed intagliotype, die coating (ダ イ コ ー ト) method, the various well known rubbing methods of comma coating (カ Application マ コ ー ト) method, rod coating method etc..
Except through above-mentioned adhesive to be coated on the surface of phase separation layer, polarization photosphere or priming coat, make it dry Method to be formed except adhesive phase, can also use adhesive is coated on implement demoulding processing film demoulding processing It on face, makes it dry after forming adhesive phase, which is fitted in phase separation layer, polarization photosphere or primary coat On the surface of layer, adhesive phase side is made to become the method for binding face.It is preferred that pre- to the base coating surface for foring adhesive phase First implement Corona discharge Treatment.By this, it is possible to further increase the close property of priming coat and adhesive phase.
As the method for coating adhesive, for example there are for example, being coated on above base material with by orientation polymer composition Identical method illustrated by method.As the method for removing solvent from the adhesive of coating, for example there are for example, with poly- from orientation The identical method of method of solvent is removed in polymer composition.
The peel strength of this circular polarization light board with adhesive phase is for example following on surface is measured.
The test film of wide 25mm × length about 200mm under being cut out in this circular polarization light board with adhesive phase from surface, will After its adhesive face paste is closed on a glass, using cupping machine, one end (wide 25mm of the length direction of test film is clamped One side), under 23 DEG C of temperature, the atmosphere of relative humidity 60%, crosshead speed (clamping movement speed) 200mm/ timesharing, according to According to JIS K 6854-1:1999 " adhesives-separation adhesion strength test method-the 1:90 degree of separation " carry out 90 ° of stripping examinations It tests.
Circularly polarized light with base material, first orientation film, polarization photosphere, second orientation film, phase separation layer and adhesive in order In plate, the peel strength (F1) of preferred substrates and first orientation film is less than first orientation film and polarizes the peel strength of photosphere (F2), the peel strength (F4) of the peel strength (F3) and phase separation layer and adhesive phase of second orientation film and phase separation layer.It can Peel strength (F1) is adjusted with the alignment films by base material and first.
For example, there is the base material for the functional group for forming chemical bond with alignment films, with base material and first orientation film on surface The tendency that peel strength (F1) is got higher.Therefore, the base material reduced as peel strength (F1), the functional group on preferably surface are few Base material, additionally, it is preferred that the base material for the surface treatment for forming functional group on the surface is not carried out.
In addition, the alignment films with the functional group for forming chemical bond with base material, the stripping with base material and first orientation film are strong The tendency that degree (F1) is got higher.Therefore, the alignment films reduced as peel strength (F1) preferably form the function of chemical bond with base material The few alignment films of group.In addition, in order to reduce (F1), preferred orientation polymer composition or optical alignment film formation composition In without containing base material and the crosslinked reagent of alignment films is made, further preferably, without containing ingredients such as the solvents for dissolving base material.By taking Tropism polymer composition or optical alignment film formation composition dissolve substrate surface so that the stripping of base material and first orientation film Intensity (F1) is tended to become larger.
In order to increase peel strength (F2), (F3) and (F4), as long as in first orientation film and polarization photosphere, second orientation film and phase Chemical bond is formed between potential difference layer and phase separation layer and adhesive phase.
The circular polarization light board with adhesive phase removes base material from surface, can obtain the circular polarization with adhesive phase Light film.As the method for removing base material, for example there are arbitrary methods.
The thickness of circularly polarized light film with adhesive phase is usually at 5 μm or more 15 μm hereinafter, it is preferred that 5 μm or more 10 μm or less. The thickness of circularly polarized light film with adhesive phase is in general, interference film thickness gauge, laser microscope or contact pin type film thickness can be used Meter is measured, is found out.
Then, the method for being continuously manufactured by this circular polarization light board is illustrated.It is continuously manufactured by circle partially as such The suitable method of the tabula rasa that shakes, for example there are the methods of roll-to-roll form.
Specifically, for example there are the method carried out in the following order,
(1) prepare base material be wound in core roller process,
(2) by the roller continuously send out the base material process,
(3) be continuously formed on the substrate alignment films process,
(4) the coating composition A in the alignment films, be continuously formed phase separation layer process,
(5) be continuously formed on the phase separation layer for the roller that above-mentioned (4) obtain protective layer process,
(6) alignment films are coated on the protective layer that above-mentioned (5) obtain, be continuously formed process,
(7) the coating composition B in the alignment films that above-mentioned (6) obtain, be continuously formed polarization photosphere process,
(8) it is bonded the film with adhesive phase on the polarization photosphere that above-mentioned (7) obtain, adhesive phase side is made to become binding face Process,
(9) continuously by obtained circular polarization light board in the 2nd core, the process that obtains the 2nd roller.
Furthermore it is possible to omit process (5) and (8) as needed.
In addition, for example there are the method carried out in the following order,
(1a) prepare base material be wound in core roller process,
(2a) continuously sent out by the roller base material process,
(3a) be continuously formed on the substrate alignment films process,
(4a) coating composition B in the alignment films, be continuously formed phase separation layer process,
(5a) be continuously formed on the polarization photosphere of above-mentioned (4a) obtained roller protective layer process,
(6a) is coated with alignment films on the protective layer that above-mentioned (5a) is obtained, be continuously formed process,
(7a) coating composition A in the alignment films that above-mentioned (6a) is obtained, be continuously formed phase separation layer process,
(8a) is bonded the film with adhesive phase on the phase separation layer that above-mentioned (7a) is obtained, and adhesive phase side is made to become binding face Process,
(9a) continuously by obtained circular polarization light board in the 2nd core, the process that obtains the 2nd roller
Furthermore it is possible to omit process (5a) and (8a) as needed.
In addition, for example there are the method carried out in the following order,
(1b) prepare base material be wound in core roller process,
(2b) continuously sent out by the roller base material process,
(3b) be continuously formed on the substrate alignment films process,
(4b) coating composition A in the alignment films, be continuously formed phase separation layer process,
(5b) is coated with alignment films on the opposite face of the phase separation layer of roller obtained with above-mentioned (4b), be continuously formed process,
(6b) coating composition B in the alignment films that above-mentioned (5b) is obtained, be continuously formed polarization film process,
(7b) continuously by obtained circular polarization light board in the 2nd core, the process that obtains the 2nd roller.
In addition, for example there are the method carried out in the following order,
(1c) prepare transparent base be wound in core roller process,
(2c) continuously sent out by the roller transparent base process,
(3c) be continuously formed on the transparent base alignment films process,
In (4c) alignment films be coated with the composition containing composition B, be continuously formed polarization photosphere process,
(5c) be continuously formed on the opposite face of the polarization photosphere of the roller obtained with above-mentioned (4c) alignment films process,
(6c) coating composition A in the alignment films that above-mentioned (5c) is obtained, be continuously formed phase separation layer process,
(7c) continuously by obtained circular polarization light board in the 2nd core, the process that obtains the 2nd roller.
Fig. 1 is the skeleton diagram of this circular polarization light board.Fig. 1 (a) is shown by base material, phase separation layer, the sequence for polarizing photosphere The circular polarization light board of lamination.Fig. 1 (b) show by base material, polarization photosphere, phase separation layer sequential laminating circular polarization light board.
This circular polarization light board can be used in diversified display device.In addition, the circle with adhesive phase on surface Polarization plate can be used for manufacturing various display devices.Specifically, the circular polarization light board with adhesive phase on surface It is fitted in the display surface of display device by the adhesive phase, the display device for having this circular polarization light board can be obtained, into one Step removes base material, can obtain the display device with circularly polarized light film for having the circularly polarized light film of the present invention.
Display device refers to the device for having display element, contains light-emitting component or light-emitting device as light emitting source.As display Device for example there are liquid crystal display device, organic electroluminescent (EL) display device, inorganic EL (EL) display device, touches Touch display apparatus, electron emission display (such as field emission display device (FED), surface conduction electron emission display Device (SED)), Electronic Paper it is (aobvious using the display device of e-inks or electrophoresis element, plasm display device, porjection type Showing device (such as grating light valve (GLV) display device, display device with digital micromirror device (DMD)) and piezoelectric ceramics are aobvious Show device etc..Liquid crystal display device includes that transmission type liquid crystal display device, semitransparent liquid crystal display, reflective liquid crystal are shown Either one or two of device, direct view liquid crystal display device and projection type liquid crystal display apparatus etc..These display devices can be aobvious The display device for showing 2 dimension images can also be the 3 d display device for showing 3 d image.Especially in organic electroluminescent (EL) it can be efficiently used in the display device of display device or inorganic EL (EL) display device.
Fig. 2 is the skeleton diagram of the liquid crystal display device 10 of one of display device of the present invention.Liquid crystal layer 15 is clamped in 2 bases Between plate 12a and substrate 12b.15 side of liquid crystal layer of substrate 12a is configured with colour filter 13.Colour filter 13 clips liquid crystal layer 15, matches It sets in the position opposite with pixel electrode 20, the configuration of black matrix" 18 is in the opposite position in the boundary between pixel electrode.It is transparent Electrode 14 is covered on these.There can be outer covering layer between colour filter 13 and transparent electrode 14.
15 side of liquid crystal layer of substrate 12b is regularly configured with thin film transistor (TFT) 19 and pixel electrode 20.Pixel electrode 20 Liquid crystal layer 15 is clipped, is configured on the position opposite with colour filter 13.It is configured between thin film transistor (TFT) 19 and pixel electrode 20 Interlayer dielectric 16 with connecting hole (not shown in figure).
As substrate 12a and substrate 12b, for example there are glass substrate and plastic bases.Manufacture the filter formed on these substrates When color device 13 or thin film transistor (TFT) 19, when needing to heat at high temperature, preferable substrate 12a and substrate 12b are glass substrate.
As thin film transistor (TFT) 19, for example there are shapes on the high temperature polysilicon silicon transistor formed on quartz base plate, glass substrate At low-temperature polycrystalline silicon transistor and glass substrate or plastic base on the amorphous silicon transistor that is formed.In order to enable liquid crystal The miniaturization of display device can form driving IC on substrate 12b.
Liquid crystal layer 15 is configured between transparent electrode 14 and pixel electrode 20.In order to make to be protected between substrate 12a and substrate 12b Certain distance is held, separation layer 21 is formed in liquid crystal layer 15.In the layer formed on substrate 12a and substrate 12b with 15 phase of liquid crystal layer The face of contact, can be configured with makes the alignment films that the liquid-crystal compounds contained in liquid crystal layer 15 is orientated with desired direction.
Each component is with substrate 12a, colour filter 13 and black matrix" 18, transparent electrode 14, liquid crystal layer 15, pixel electrode 20, the sequential lamination of interlayer dielectric 16 and thin film transistor (TFT) 19 and base material 12b.
Be clamped with the outside of the substrate 12a and substrate 12b of such liquid crystal layer 15, lamination have this circular polarization light board 11a and This circular polarization light board 11b.The outside of this circular polarization light board 11b is configured with the back light unit 17 as light emitting source.Back light unit 17 Contain light source, light guide, reflecting plate, diffusion sheet and visual angle trimmer.As light source, electroluminescent (EL), cold the moon can be used The various light sources such as pole pipe, thermionic-cathode tube, light emitting diode (LED), strong light source, mercury lamp.
Fig. 3 is the skeleton diagram of the organic EL display device 30 of one of display device of the present invention.This hair shown in Fig. 3 (a) There is bright organic EL display device 30 this circular polarization light board 31 to be formed with pixel electrode 34 via interlayer dielectric 33 Lamination luminescent layer 35 and cathode electrode 36 on substrate 32 and formed.Substrate 32 is clipped on the opposite side of luminescent layer 35, is configured There is this circular polarization light board 31.Positive voltage is applied to pixel electrode 34, cathode electrode 36 applies negative voltage, by pixel electrode 34 And it is passed through DC current between cathode electrode 36 so that luminescent layer 35 shines.Luminescent layer 35 is by electron supplying layer, luminescent layer and sky The formation such as cave transfer layer.The light projected by luminescent layer 35 is by pixel electrode 34, interlayer dielectric 33, substrate 32, this circular polarization Tabula rasa 31.
When manufacturing organic EL display device 30, first, the thin film transistor (TFT) 38 of intended shape is formed on substrate 32.Then So that interlayer dielectric 33 is formed a film, then so that pixel electrode 34 is formed a film with sputtering method, forms pattern.Later, lamination luminescent layer 35.
Then, in the opposite face of the one side of the thin film transistor (TFT) 38 equipped with substrate 32, this circular polarization light board 31 is set.This When, 1/4 wavelength layer of this circular polarization light board 31 is configured in 32 side of substrate.
As substrate 32, for example there are the potteries such as sapphire glass substrate, quartz glass substrate, soda glass substrate and aluminium oxide Porcelain substrate;The metal substrates such as copper;Plastic base etc..Although it is not shown in the figure that heat conductivity film can be formed on base material 32. As heat conductivity film, for example there are DLC films (DLC etc.) etc..Pixel electrode 34 be reflection-type when, light to base material 32 Opposite direction outgoing.Therefore, it is not only transparent material, the non-permeable materials such as stainless steel can also be used.Substrate can be single One, can also be with binder by laminated substrate made of multiple base boards.Meanwhile these substrates are not limited to plate, It can also be film.
As thin film transistor (TFT) 38, such as polysilicon transistors can be used etc..Thin film transistor (TFT) 38 is set to pixel electrode 34 end, size is at 10~30 μm or so.In addition, the size of pixel electrode 34 is in 300 μm of 20 μ m, 20 μm~300 μ m Left and right.
The wire electrode of thin film transistor (TFT) 38 is provided on base material 32.The resistance of wire electrode is low, and pixel electrode 34 is electrically connected with it Have after connecing and resistance value inhibited into function in reduced levels, its general wire electrode use containing Al, Al and transition metal (but Do not include Ti), Ti either wantonly a kind or materials of more than two kinds in titanium nitride (TiN).
Interlayer dielectric 33 is set between thin film transistor (TFT) 38 and pixel electrode 34.Interlayer dielectric 33 can be SiO2Equal oxygen Material that the inorganic based material such as SiClx, silicon nitride forms a film through splash or vacuum evaporation, with SOG (spin on glass, spin coating glass Glass method) film etc. of the resins based material such as silicon oxide layer, photoresist, polyimides and acrylic resin that is formed has insulating properties Material any one.
Rib 39 is formd on interlayer dielectric 33.The configuration of rib 39 (adjacent pixel around pixel electrode 34 Between).As the material of rib 39, for example there are acrylic resin and polyimide resins etc..The thickness of rib 39 preferably 1.0 μm or more 3.5 μm, more preferable 1.5 μm or more 2.5 μm or less.
Then to pixel electrode 34, luminescent layer 35, with cathode electrode 36 formed EL element illustrate.Luminescent layer 35 is each It is defeated containing electron injection transfer layer, luminescent layer, hole from the hole transporting layer and luminescent layer at least with 1 layer, such as successively Send layer and hole injection layer.
As pixel electrode 34, for example there are for example, ITO (indium doping tin oxide), IZO (zinc doping indium oxide), IGZO, ZnO、SnO2And In2O3Deng particularly preferred ITO or IZO.As long as the thickness of pixel electrode 35 can fully carry out hole injection Regulation more than thickness, preferably 10~500nm or so.
Pixel electrode 34 can be formed by vapour deposition method (preferably sputtering method).As sputter gas, it is not particularly limited, it can To use the inert gases such as Ar, He, Ne, Kr and Xe or these mixed gas.
Constituting the material of cathode electrode 36 can lift for example, K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn And the metallic elements such as Zr, in order to improve the job stability of electrode, it is preferable to use by selecting 2 kinds of ingredients in the metallic element that illustrates Or the alloy system of 3 kinds of ingredients.As alloy system, preferably such as AgMg (Ag:1~20at%), AlLi (Li:0.3~ 14at%), InMg (Mg:50~80at%) and AlCa (Ca:5~20at%) etc..
Cathode electrode 36 passes through the formation such as vapour deposition method and sputtering method.The preferred 0.1nm or more of thickness of cathode electrode 37, preferably 1~500nm or more.
Hole injection layer has the function of being easy to inject hole from pixel electrode 34, and hole transporting layer has conveying hole Function and the function of hindering electronics, also referred to as electric charge injection layer or charge transport layer.
The thickness of the thickness of luminescent layer, the overall thickness of hole injection layer and hole transporting layer and electron injection transfer layer does not have It is particularly limited to, can be different according to forming method, preferably 5~100nm's or so.Hole injection layer or hole transporting layer can make With various organic compounds.Hole is injected in the formation of transfer layer, luminescent layer and electron injection transfer layer, equal from that can be formed From the aspect of matter film, vacuum vapour deposition can be used.
As luminescent layer 35, the material of luminous (fluorescence) using singlet excitons can be used, utilize triplet exciton Shine (phosphorescence) material, containing using singlet excitons shine (fluorescence) material with using triplet exciton shine The material of the material of (phosphorescence), the material formed by organic matter containing the material that is formed by organic matter and pass through inorganic matter Material, high molecular material, low molecule material, the material containing high molecular material Yu low molecule material of the material of formation.To material There is no limit the luminescent layer 35 used as various material well known to used in EL element can be used for this EL display dresses to material It sets in 30.
There is drier (figure is not shown) in space between cathode electrode 36 and sealant 37, this is because luminescent layer 35 is not Moisture-proof.The deterioration of luminescent layer 35 can be prevented by absorbing moisture by drier.
Organic EL display device 30 of the invention shown in Fig. 3 (b) has this circular polarization light board 31, via interlayer dielectric 33, on the substrate 32 for foring pixel electrode 34, formed by luminescent layer 35 and 36 lamination of cathode electrode.Shape on cathode electrode At sealant 37, with this circular polarization light board 31 is configured on 32 opposite side of substrate.Passed through by the light that luminescent layer 35 projects Cathode electrode 36, sealant 37, this circular polarization light board 31.
Embodiment
Hereinafter, by embodiment, further the present invention will be described in detail." % " and " part " in following embodiments is recorded In be not particularly limited, indicate quality % and mass parts.
Embodiment 1
[preparation of phase separation layer formation composition]
Following compositions are mixed, obtained mixture is stirred 1 hour at 80 DEG C, phase separation layer formation composition is obtained.
Compound A1 and compound A2 is synthesized according to the method that special open 2010-31223 bulletins are recorded.
Compound A1 (80 parts):
Compound A2 (20 parts):
Polymerization initiator (6 parts):
2- dimethylamino -2- benzyls -1- (4- morphlinophenyls) butane -1- ketone
(イルガキュア369;Ciba Co., Ltd system)
Levelling agent (0.1 part):Polyacrylic acid ester compounds (BYK-361N;BYK-Chemie societies system
Solvent:The mixed solvent of ortho-xylene (300 parts) and cyclopentanone (130 parts)
[preparation of optical alignment film formation composition]
Following compositions are mixed, obtained mixture is stirred 1 hour at 80 DEG C, optical alignment film formation composition is obtained.
Light orientation material (5 parts):
Solvent (95 parts):Cyclopentanone
[preparation of polarization photosphere formation composition]
Following compositions are mixed, obtained mixture is stirred 1 hour at 80 DEG C, polarization photosphere formation composition is obtained.Change Object B1 and compound B2 is closed to be synthesized according to the method that No. 4719156 bulletins of special open are recorded.
Compound B-11 (compound (B-6);75 parts)
Compound B2 (compounds (B-7);25 parts)
Dichroism pigment;
2.5 parts of bis-azo compound (1-1-1)
2.5 parts of bis-azo compound (1-1-2)
2.5 parts of bis-azo compound (1-4-1)
Polymerization initiator;
2- dimethylamino -2- benzyls -1- (4- morphlinophenyls) butane -1- ketone (イ Le ガ キ ュ ア 369;Ciba is limited Corporation) 6 parts
Levelling agent;
Polyacrylic acid ester compounds (BYK-361N;BYK-Chemie societies system)
1.5 part
Solvent;250 parts of cyclopentanone
[measurement of phase transition temperature]
Obtained polarization photosphere formation is coated on composition on glass, after dry, is fabricated to the sample of measurement.By inclined Shake light microscope texture observation determine phase transition temperature, after being warming up to 140 DEG C, in temperature-fall period, can confirm respectively at 108 DEG C Lower phase becomes nematic phase, mutually becomes smectic C at 101 DEG C, mutually becomes smectic B at 76 DEG C.
[preparation of adhesive formation composition]
Following compositions are mixed at 55 DEG C of nitrogen atmosphere, obtain acrylic resin.
Further, CORONET (U ロ ネ ー ト L) (75% vinegar of the trimethylolpropane addition product of toluene di-isocyanate(TDI) is mixed Isocyanates radix in acetate solution, 1 molecule:3, Nippon Polyurethane Industry Co., Ltd.'s system) 0.5 part, it is silane coupled 0.5 part of agent X-12-981 (SHIN-ETSU HANTOTAI's silicone Co. Ltd. system) finally adds ethyl acetate and so that total solids constituent concentration is 10%, Adhesive formation composition is made.By to adhesive formation be coated on the processed poly terephthalic acid of demoulding with composition It in the demoulding process face of second diester film (リ Application テ ッ Network Co. Ltd. system), is coated with using painting machine so that the thickness after dry is It is 1 minute dry at 10 μm, 100 DEG C, obtain the film (1) with adhesive.
[manufacture of circular polarization light board]
1. polarizing the formation of the alignment films of photosphere
Cellulose mesentery KC4UY (TAC film, Konica Minolta Opto Inc.'s system) is used as transparent base film.Pass through stick Formula rubbing method is coated with above-mentioned optical alignment film formation composition on the film, heat drying 1 minute in 60 DEG C of drying oven. Polarised light UV treatment with irradiation is implemented to obtained drying overlay film and forms first orientation film.Polarised light UV processing uses UV irradiation units (SPOT CURE SP-7;ウ シ オ Electric Co., Ltd system), the condition when intensity measured at wavelength 365nm is 100mJ Lower progress.In addition, the polarization direction of polarization UV is 0 ° relative to the slow axis of phase separation layer.
2. polarizing the formation of photosphere
It is coated on the first orientation film of formation by bar type coating and polarizes photosphere formation composition, in drying at 120 DEG C Heat drying 1 minute in oven.It is cooled to room temperature.Use UV irradiation units (SPOT CURE SP-7;ウ シ オ motor strain formula meetings Society's system), in light exposure 1200mJ/cm2Under (benchmark of 365nm), ultraviolet light is irradiated to dry coationg, forms polarization photosphere. To polarization photosphere thickness by laser microscope (Olympus Co., Ltd OLS3000) measure, be 1.8 μm.
3. the formation of protective layer
By rod coating method by dipentaerythritol hexaacrylate (ア ロ ニ ッ Network ス M-403 Toagosei Co., Ltd system) 50 parts, 50 parts of acrylate (エ ベ Network リ Le 4858Daicel-UCB Co. Ltd. systems) and 2- methyl-1s-[4- (first sulphur Base) phenyl] -2- morpholinopropane -1- ketone (イ Le ガ キ ュ ア 907;Society of Ciba Co., Ltd system) 3 parts be dissolved in isopropyl The solution (protective layer forms composition) being configured in 250 parts of alcohol is coated on the polarization photosphere to be formed, in 50 DEG C of drying Heat drying 1 minute in oven.By using UV irradiation units (SPOT CURE SP-7;ウ シ オ Electric Co., Ltd system), In ultraviolet exposure amount 400mJ/cm2The dry coationg irradiated under conditions of (benchmark of 365nm), on the polarization photosphere Form protective layer.
4. the formation of the alignment films of phase separation layer
Above-mentioned optical alignment film formation composition is coated on the protective layer of formation by bar type coating, is baked dry at 60 DEG C Heat drying 1 minute in case.Polarized UV radiation processing is implemented to obtained drying overlay film, forms second orientation film.It polarizes at UV Reason is to use UV irradiation units (SPOT CURE SP-7;ウ シ オ Electric Co., Ltd system), measure intensity at wavelength 365nm To be carried out under conditions of 100mJ.In addition, the polarization direction of polarization UV is at 45 ° relative to the absorption axiss of polarization photosphere.
5. the formation of phase separation layer
It is coated with phase separation layer formation composition on the second orientation film of formation by bar type coating, in drying at 120 DEG C Heat drying 1 minute in oven.It is cooled to room temperature.By using UV irradiation units, (SPOT CURE SP-7;ウ シ オ motors Co. Ltd. system), light exposure 1000mJ/cm2Under (benchmark of 365nm), ultraviolet light is irradiated to obtained dry coationg, forms phase Potential difference layer.The thickness of obtained phase separation layer is measured by laser microscope (Olympus Co., Ltd OLS3000), is 2.0μm。
In this case, broadband circular polarization light board can be made.The circular polarization light board is measured by contact film thickness gauge Overall thickness is 45 μm.
[evaluation of circular polarization light board]
1.X ray diffraction determinations
To obtained polarization photosphere, X is carried out by X-ray diffraction device X ' Pert PRO MPD (spectris Co. Ltd. systems) Ray diffraction determination.Using Cu as target, make the X generated under conditions of x-ray tube current 40mA, x-ray tube voltage 45kV Ray (finds out the frictional direction of alignment films under polarization photosphere for 1/2 ° in advance by fixed divergent slit by frictional direction.) incident, In the range of 2 θ=4.0~40.0 ° of scanning range, measurement is scanned with the step width of 2 θ=0.01671 °.As a result, in 2 θ It pays for=20.12 ° and closely obtains the sharp diffraction maximum of half-peak breadth (FWHM)=about 0.29 °.In addition, X-ray is hung down along with friction When straight direction incidence measures, identical result is also obtained.It is about by the order period (d) that peak position is found out, thus It learns, forms the structure that can reflect high order smectic phase.
2. the measurement of reflectivity
In order to confirm the serviceability of circular polarization light board, such as following measurement reflectivity.Using adhesive by manufactured circular polarization light board Phase separation layer be bonded with reflecting plate (minute surface aluminium sheet), measurement sample is made.
Using spectrophotometer (Shimadzu Corporation UV-3150), with the light of the range of wavelength 400 to 700nm with The step width of 2nm measures the reflectivity of the light of reflection to measuring sample from 12 ° of incidences of normal direction.Not to be bonded circular polarization light board It is 100% to be only provided with the reflectivity measured when reflecting plate, calculates reflectivity, as a result the light of the wavelength of the range of 400~700nm Reflectivity be 1~10% or so, can learn can obtain sufficient preventing reflection characteristic in entire visible light region.
Embodiment 2
It is same as Example 1, formed on a face of transparent base film first orientation film (polarization direction of polarization UV relative to The long side direction of base material film is 45 °), form phase separation layer on this optical alignment film.Then, protective layer is formed on phase separation layer Afterwards, second orientation film (polarization direction of polarization UV is 0 ° relative to the long side direction of base material film) is formed, on this optical alignment film Polarization photosphere is further formed, this circular polarization light board is made.
It is same as Example 1, the transparent base film of the circular polarization light board of making is bonded with reflecting plate using adhesive, is surveyed Determine reflectivity, as a result the reflectivity of the light of the range of wavelength of 400~700nm is 1~10% or so, it follows that entirely may be used Light-exposed region can obtain sufficient preventing reflection characteristic.
Embodiment 3
As polymerizable liquid crystal compound B1, using compound (B-14) substituted compound (B-6), as polymerizable liquid crystal chemical combination Object B2, it is in addition to this, other same as Example 1 using compound (B-17) substituted compound (B-7), make circularly polarized light Plate.
It is same as Example 1, the transparent base film of the circular polarization light board of making is bonded with reflecting plate using adhesive, is surveyed Determine reflectivity, as a result the reflectivity of the light of the range of wavelength of 400~700nm is 1~10% or so, it follows that entirely may be used Light-exposed region can obtain sufficient preventing reflection characteristic.
Comparative example 1
As phase difference film, 1/4 wavelength plate (ゼ オ ノ ア films, the day of the monadic stretching membrane used as annular ethylene series resin Ben Ruiweng Co., Ltd., plane phase difference Ro:It 138nm) is used as phase difference film, similarly to Example 1, in phase difference film A face on form first orientation film (polarization direction of polarization UV is 45 ° relative to the slow axis of phase difference film), this first Polarised light layer further is formed in alignment films, makes circular polarization light board.
Similarly to Example 1, the circular polarization light board of making is fitted on reflecting plate using adhesive and measures reflectivity, The light reflectivity of the wavelength of 500~600nm is good, 1~10% or so, still, the light of the wavelength of 400~500nm and 600 The reflectivity of the light of~700nm wavelength is 10% or more, and bluish violet is presented in reflected light, it follows that not obtaining sufficient counnter attack Penetrate function.
Comparative example 2
100 × 100mm that iodo- PVA polarization plates (105 μm of ス ミ カ ラ Application Sumitomo Chemical Co thickness) are cut into Small pieces as polarization plate, make its absorption axis at 0 °.1/2 wavelength plate used in embodiment 1 is cut into 100 × 100mm Small pieces, make slow axis at 15 °.1/4 wavelength plate used in comparative example 1 is cut into the small pieces of 100 × 100mm, make slow axis at 15°.The each film cut out is subjected to piece fitting using acrylic adhesive (25 μm of film thickness), becomes polarization plate+1/2 + 1/4 wavelength plate of wavelength plate, is made circular polarization light board.
It is same as Example 1, the circular polarization light board of making is fitted on reflecting plate using adhesive, measures reflectivity, As a result the light reflectivity of the wavelength of the range of 400~700nm be 1~10% or so, it follows that entire visible light region all It can obtain sufficient anti-reflective function.But the overall thickness that circular polarization light board is measured by contact film thickness gauge is 240 μm, probably It is 5 times of the overall thickness of the circular polarization light board of embodiment 1.
Embodiment 4
In addition to using polyethylene terephthalate film to replace cellulose mesentery KC4UY (TAC film, Konica Minolta strain formula meeting Society's system) it is used as except base material, it is other to make circular polarization light board using method same as Example 1.In the circular polarization light board Phase separation layer on fitting with adhesive film (1), obtain the circular polarization light board with adhesive phase.The sample size is cut out It is cut to 40mm × 40mm, the film of the film with adhesive of fitting is peeled, is pressed against on reflecting plate (minute surface aluminium sheet), at leisure Base material is removed, the reflecting plate with circularly polarized light film is obtained.First orientation film, polarization photosphere, protective layer, second orientation film, phase The thickness for the above-mentioned circularly polarized light film that potential difference layer and adhesive phase are formed is 14.7 μm.
Due to the peel strength of alignment films of the peel strength (F1) of base material and first alignment films less than first and polarization photosphere (F2), the peel strength (F4) of the peel strength (F3) and phase separation layer and adhesive phase of second alignment films and phase separation layer, Therefore stripping is generated between base material and first alignment films, can remove base material.
It is same as Example 1, measure reflectivity, as a result the light reflectivity of the wavelength of the range of 400~700nm be 1~ 10% or so, it follows that sufficient anti-reflective function can be obtained in entire visible light region.The antireflection principle with have The principle that the metal electrode of machine EL display reflects outer light is identical, so similarly suitable for organic el display.
Industrial availability
There is the circular polarization light board of the present invention performance being enough as broadband circular polarization light board, thickness also to meet The requirement of display device slimming, in addition, its manufacturing process is also easy.In addition, the display of the circular polarization light board with the present invention Device can reach slimming.

Claims (20)

1. a kind of circular polarization light board, which is characterized in that there is base material, phase separation layer and polarization photosphere,
There is protective layer between the phase separation layer and the polarization photosphere,
It is 45 ° that the slow axis of the phase separation layer is practical with the absorption axiss angulation for polarizing photosphere,
The phase separation layer meets formula (1) and formula (2) to the birefringence Δ n (λ) of the light of wavelength X nm,
Phase separation layer is coat with polarization photosphere, and the overall thickness of phase separation layer and polarization photosphere is for 10 μm hereinafter, also, institute It states polarization photosphere and contains the two or more dichroism pigments with maximum absorption wavelength λ MAX in the range of 300~700nm,
Δn(450)/Δn(550)≦1.00 (1)
1.00≦Δn(650)/Δn(550) (2)。
2. circular polarization light board according to claim 1, wherein the thickness of the protective layer is at 1 μm or more, 5 μm or less.
3. circular polarization light board according to claim 1, wherein the protective layer is formed by protective layer formation with composition, The protective layer formation composition contains acrylic oligomers or acrylic acid series polymeric compounds, with solvent.
4. circular polarization light board according to claim 1, wherein the protective layer is by containing water-soluble polymer and solvent Protective layer formation is formed with composition.
5. circular polarization light board according to claim 1, wherein phase separation layer by a kind or more polymerizable liquid crystal polymerization and It is formed.
6. circular polarization light board according to claim 1, wherein polarization photosphere by a kind or more polymerizable liquid crystal polymerization and It is formed.
7. circular polarization light board according to claim 5 or 6 makes polymerizable liquid crystal polymerize by irradiation light.
8. circular polarization light board according to claim 1, wherein polarization photosphere is to obtain Bradley in X-ray diffraction measure The polarization photosphere at lattice peak.
9. circular polarization light board according to claim 1, wherein the thickness of phase separation layer and polarization photosphere is respectively at 5 μm Below.
10. circular polarization light board according to claim 1, wherein phase separation layer or polarization photosphere or the two are formed in In alignment films.
11. circular polarization light board according to claim 10, wherein alignment films are to generate orientation anchorage force by irradiation light Alignment films.
12. the circular polarization light board according to claim 10 or 11, wherein the thickness of alignment films is in 500nm or less.
13. circular polarization light board according to claim 1 further has adhesive also on the surface of phase separation layer Layer.
14. circular polarization light board according to claim 13 has base material, first orientation film, polarization photosphere, protection successively Layer, second orientation film, phase separation layer and adhesive phase.
15. circular polarization light board according to claim 14, wherein the peel strength F1 of base material and first orientation film is less than the The peel strength F3 and phase separation layer of one alignment films and the polarization peel strength F2 of photosphere, second orientation film and phase separation layer with The peel strength F4 of adhesive phase.
16. a kind of display device, any one of them circular polarization light board with claim 1~15 and display element.
17. a kind of display device with circularly polarized light film is any one of them circular polarization light board of claim 13~15 Eliminate the display surface that circularly polarized light film obtained from base material is fitted in display element via the adhesive phase of the circularly polarized light film Obtained from upper.
18. display device according to claim 17, wherein the thickness of circularly polarized light film is at 5 μm or more 15 μm or less.
19. according to any one of them display device of claim 16~18, wherein display element is liquid crystal cell, Organic Electricity Electroluminescent element or touch panel.
20. a kind of manufacturing method of the display device with circularly polarized light film, wherein described in any one by claim 13~15 Circular polarization light board, be fitted on the display surface of display element via the adhesive phase of the circular polarization light board, and the circularly polarized light Plate eliminates base material.
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Cited By (1)

* Cited by examiner, † Cited by third party
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CN110969955A (en) * 2018-09-28 2020-04-07 深圳光峰科技股份有限公司 LED display screen

Families Citing this family (52)

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Publication number Priority date Publication date Assignee Title
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US20160146995A1 (en) * 2014-11-26 2016-05-26 Sumitomo Chemical Company, Limited Optical film
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US11697695B2 (en) 2015-01-16 2023-07-11 Dic Corporation Polymerizable composition and optically anisotropic body using same
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004524568A (en) * 2001-03-13 2004-08-12 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング Combination of twisted A plate and optical film including polarizer
JP2005189393A (en) * 2003-12-25 2005-07-14 Nitto Denko Corp Elliptical polarizing plate and image display device
US20080309854A1 (en) * 2007-06-15 2008-12-18 Zhibing Ge Wide Viewing Angle and Broadband Circular Polarizers for Transflective Liquid Crystal Displays
CN101519502A (en) * 2008-02-29 2009-09-02 住友化学株式会社 Method for manufacturing polarizing film, polarizing sheet and optical laminate
JP2012108465A (en) * 2010-05-28 2012-06-07 Fujifilm Corp Three-dimensional image printing photographic paper, three-dimensional image printing object, three-dimensional image printing object manufacturing method and three-dimensional image provision method

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001337225A (en) * 2000-05-29 2001-12-07 Nitto Denko Corp Laminated optical element and liquid crystal display device
WO2002093213A1 (en) * 2001-05-10 2002-11-21 Nippon Kayaku Kabushiki Kaisha Liquid crystalline compound and phase difference film using the same
JP2005049865A (en) * 2003-07-17 2005-02-24 Arisawa Mfg Co Ltd Manufacturing method of optical phase difference element
JP2005062472A (en) * 2003-08-12 2005-03-10 Kyodo Printing Co Ltd Liquid crystal display device, portable medium, and method for manufacturing electrode substrate of liquid crystal display device
WO2005045485A1 (en) * 2003-11-06 2005-05-19 Koninklijke Philips Electronics N.V. Dichroic guest-host polarizer comprising an oriented polymer film
JP2005208415A (en) * 2004-01-23 2005-08-04 Nitto Denko Corp Reverse wavelength dispersion retardation film, and polarizing plate and display apparatus using the same
JP2005208416A (en) * 2004-01-23 2005-08-04 Nitto Denko Corp Reverse wavelength dispersion retardation film, polarizing plate and display apparatus using the same
JP2006259038A (en) * 2005-03-16 2006-09-28 Nitto Denko Corp Method of manufacturing elliptically polarizing plate, and image display apparatus using elliptically polarizing plate
JP2006337892A (en) * 2005-06-06 2006-12-14 Nitto Denko Corp Elliptically polarizing plate, liquid crystal panel, liquid crystal display device, and image display device
JP4937252B2 (en) * 2005-06-27 2012-05-23 住友化学株式会社 Dichroic guest-host polarizer
JP2007264403A (en) 2006-03-29 2007-10-11 Fujifilm Corp Retardation plate, polarizing plate, luminance-improving film and liquid crystal display
TW200811492A (en) * 2006-07-12 2008-03-01 Nitto Denko Corp Polarizing plate with optical compensation layer, method of producing the same, and liquid crystal panel, liquid crystal display, and image display including the same
JP4998941B2 (en) * 2006-11-20 2012-08-15 日東電工株式会社 Laminated optical film, liquid crystal panel and liquid crystal display device using laminated optical film
JP2009193014A (en) * 2008-02-18 2009-08-27 Fujifilm Corp Patterning elliptical polarizer
JP2009251288A (en) * 2008-04-07 2009-10-29 Nitto Denko Corp Elliptical polarization plate and method of manufacturing the same
JP5336206B2 (en) 2009-01-16 2013-11-06 富士フイルム株式会社 Liquid crystalline composition, light absorption anisotropic film, polarizing element and liquid crystal display device using the same
KR101195852B1 (en) * 2009-02-04 2012-10-30 삼성코닝정밀소재 주식회사 Optical filter for display device and display device having the same
JP2010243858A (en) * 2009-04-07 2010-10-28 Nitto Denko Corp Polarizing plate, liquid crystal panel, and liquid crystal display device
JP5754086B2 (en) * 2009-06-26 2015-07-22 住友化学株式会社 Phase difference plate, display device, and method of manufacturing phase difference plate
JP5375644B2 (en) * 2010-02-10 2013-12-25 住友化学株式会社 Composition and optical film
JP2012063387A (en) * 2010-09-14 2012-03-29 Sumitomo Chemical Co Ltd Polymerizable liquid crystal composition and optical film
KR101906596B1 (en) * 2010-09-14 2018-10-10 스미또모 가가꾸 가부시키가이샤 Polymerizable liquid crystal composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004524568A (en) * 2001-03-13 2004-08-12 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング Combination of twisted A plate and optical film including polarizer
JP2005189393A (en) * 2003-12-25 2005-07-14 Nitto Denko Corp Elliptical polarizing plate and image display device
US20080309854A1 (en) * 2007-06-15 2008-12-18 Zhibing Ge Wide Viewing Angle and Broadband Circular Polarizers for Transflective Liquid Crystal Displays
CN101519502A (en) * 2008-02-29 2009-09-02 住友化学株式会社 Method for manufacturing polarizing film, polarizing sheet and optical laminate
JP2012108465A (en) * 2010-05-28 2012-06-07 Fujifilm Corp Three-dimensional image printing photographic paper, three-dimensional image printing object, three-dimensional image printing object manufacturing method and three-dimensional image provision method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110969955A (en) * 2018-09-28 2020-04-07 深圳光峰科技股份有限公司 LED display screen
CN110969955B (en) * 2018-09-28 2024-04-05 深圳光峰科技股份有限公司 LED display screen

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