CN103048721B - Polarization film, circular polarization light board and their manufacture method - Google Patents

Polarization film, circular polarization light board and their manufacture method Download PDF

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CN103048721B
CN103048721B CN201210422001.6A CN201210422001A CN103048721B CN 103048721 B CN103048721 B CN 103048721B CN 201210422001 A CN201210422001 A CN 201210422001A CN 103048721 B CN103048721 B CN 103048721B
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film
polarization film
polarization
light
layer
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CN103048721A (en
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幡中伸行
大川春树
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • C09K19/601—Azoic
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

There is provided a kind of can be used for display device component, film and the polarization film of high polarised light performance etc..There is provided a kind of polarization film formed by composition, the liquid crystal display device for possessing the polarization film etc., the wave-length coverage that said composition contains in 400~800nm has at least one kind of and polymerism smectic shape liquid-crystal compounds of the polyazo system pigment shown in absorption, following formulas (1).[in formula (1), Ar2Selected from group shown below.Above-mentioned polymerism smectic shape liquid-crystal compounds is preferably the compound that senior smectic liquid crystal state is presented.

Description

Polarization film, circular polarization light board and their manufacture method
Technical field
The present invention relates to polarization film, circular polarization light board and their manufacture method etc..
Background technology
It is used for the polarizer in liquid crystal display device, usually using the film being made up of the polyvinyl alcohol after iodine staining.Separately On the one hand, along with the trend of recent strong request liquid crystal display device filming, the polarizer is also required to further thin Type.Recorded in the slim polarization film having for the slim polarizer, such as patent document 1 by containing polymerism nematic Liquid-crystal compounds and the film of the composition of dichroism pigment formation.In addition, for the dichroism pigment, such as in patent document 2 In record and form the specific polyazo system pigment of polarization film as by evaporation.
Prior art literature
Patent document
【Patent document 1】Japanese Patent Laid 2007-510946 publications
【Patent document 2】Japanese Patent Laid-Open 8-278409 publications
The content of the invention
It is required the polarization film of further filming, expects that its polarised light performance is high, especially dichroic ratio is high.
The present invention includes following invention.
(1) a kind of polarization film, by having containing the wave-length coverage in 400~800nm shown in absorption, following formulas (1) Polyazo system pigment at least one kind of and
The composition of polymerism smectic shape liquid-crystal compounds is formed.
[in formula (1),
N is 1 or 2.
Ar1And Ar3The group selected from group shown below is represented independently of one another.
Ar2Represent the group selected from group shown below.
A1And A2The group selected from group shown below is represented independently of one another.
(m is 0~10 integer, and when having 2 m in same group, this 2 m are identical or different each other.)]
(2) polarization film described in above-mentioned (1), its thickness is less than more than 1 μm 10 μm.
(3) polarization film described in above-mentioned (1) or (2), it obtains bragg peak in X-ray diffraction measure.
(4) a kind of polarizer, possesses polarization film described in any one of above-mentioned (1)~(3), alignment films and transparent successively Base material.
(5) a kind of manufacture method of the polarizer, the polarizer possesses inclined described in any one of above-mentioned (1)~(3) successively Shake light film, alignment films and transparent base, and its manufacture method has following process：
The process for possessing the laminate of the alignment films on the transparent base is got out,
In the alignment films of the laminate, formed containing polymerism smectic shape liquid-crystal compounds, 400~ 800nm wave-length coverage has the work of the film of polyazo system pigment shown in the above-mentioned formula (1) of absorption, polymerization initiator and solvent Sequence,
The process that the solvent is removed from the film,
The polymerism smectic shape liquid-crystal compounds contained in the film for making to eliminate the solvent turns into smectic shape liquid crystal The process of state,
By the polymerism smectic shape liquid-crystal compounds in the case where keeping the form of the smectic shape mesomorphic state, make described Polymerism smectic shape liquid-crystal compounds polymerize, in the process that polarization film is formed in the alignment films.
(6) possesses the liquid crystal display device of the polarization film described in any one of above-mentioned (1)~(3).
(7) a kind of circular polarization light board, polarization film and λ/4 layer described in any one with above-mentioned (1)~(3), and Meet the important document of following (A1) and (A2)：
(A1) absorption axiss of the polarization film and the slow axis angulation of λ/4 layer are substantially 45 °；
(A2) scope of the front retardation value of λ/4 layer determined under wavelength 550nm light in 100~150nm.
(8) a kind of circular polarization light board, the polarization film described in any one, λ/2 layer successively with above-mentioned (1)~(3), λ/4 layer, and meet the important document of following (B1), (B2), (B3) and (B4)：
(B1) absorption axiss of the polarization film and substantially 15 ° of the slow axis angulation of λ/2 layer；
(B2) slow axis of λ/2 layer and substantially 60 ° of the slow axis angulation of λ/4 layer；
(B3) λ/2 layer determined under wavelength 550nm light, the front retardation values of λ/4 layer 200~ 300nm scope；
(B4) λ/4 layer determined under wavelength 550nm light, the front retardation values of λ/4 layer 100~ 150nm scope.
(9) possess circular polarization light board described in above-mentioned (7) or (8), the organic EL display of organic EL element.
The effect of invention
According to the present invention, it is possible to provide the high polarization film of slim and dichroic ratio, the polarizer containing the polarization film, liquid Crystal device, circular polarization light board and organic EL display.
Brief description of the drawings
【Fig. 1】The schematic cross-section of the major part of the method for continuous production (volume to volume form) of this polarization film.
【Fig. 2】The section signal of the section constitution of the liquid crystal display device of the polarizer containing this polarization film is used Figure.
【Fig. 3】The section amplification of the lamination order of the polarizer containing this polarization film set in liquid crystal display device is shown It is intended to.
【Fig. 4】The section amplification of the lamination order of the polarizer containing this polarization film set in liquid crystal display device is shown It is intended to.
【Fig. 5】Section of the section constitution of the liquid crystal display device (embedded) of the polarizer containing this polarization film is used Face schematic diagram.
【Fig. 6】The schematic cross-section being most simply formed of circular polarization light board containing this polarization film.
【Fig. 7】The schematic cross-section of the major part of the method for continuous production of circular polarization light board containing this polarization film.
【Fig. 8】Illustrate in section using the section constitution of the EL display devices of the circular polarization light board containing this polarization film Figure.
【Fig. 9】The section amplification of the lamination order of the circular polarization light board containing this polarization film set in EL display devices Schematic diagram.
【Figure 10】The section of the section constitution of the EL display devices of the circular polarization light board containing this polarization film has been used to show It is intended to.
【Figure 11】Use the section of the section constitution of the projection-type liquid crystal display device of the polarizer containing this polarization film Schematic diagram.
Symbol description
1 transparent base
2 optical alignment films
3 polarization films
100 polarizers
101 the 1st laminates
102 the 2nd laminates
103 the 3rd laminates
210 the 1st roller 210A core
220 the 2nd roller 220A core
211A, 211B apparatus for coating
212A, 212B drying oven
213A polarised light UV irradiation units
213B light irradiation devices
300 auxiliary cylinders
10 liquid crystal display devices
12a, 12b polarization film
13a, 13b phase retardation film
14a, 14b substrate
15 colour filters
16 transparency electrodes
17 liquid crystal layers
18 interlayer dielectrics
19 backlight modules
20 black matrix"s
21 thin film transistor (TFT)s
22 pixel electrodes
23 septs
24 liquid crystal display devices
30 EL display devices
31 polarization films
32 phase retardation films
33 substrates
34 interlayer dielectrics
35 pixel electrodes
36 luminescent layers
37 cathode electrodes
38 drier
39 caps
40 thin film transistor (TFT)s
41 ribs
42 film sealing films
44 EL display devices
111 light sources
112 the 1st lens arrays
112a lens
113 the 2nd lens arrays
114 polarization light conversion elements
115 compound lenses
121st, 123,132 dichronic mirror
122 speculums
140R, 140G, 140B liquid crystal panel
142,143 polarizers
150 cross colour splitting prisms
170 projecting lens
180 projection screens
Embodiment
The polarization film (being referred to as " this polarization film " below according to situation) of the present invention is characterised by, by containing above-mentioned formula (1) composition of polyazo system pigment and polymerism smectic shape liquid-crystal compounds shown in (is referred to as " polarised light below according to situation Film formation composition ") formed.This polarization film is applicable not only to liquid crystal display device, as described later, by using this polarization Light film, can also be manufactured suitable for the polarizer (being referred to as " this polarizer " below according to situation) of organic EL display or circular polarization Tabula rasa (is referred to as " this circular polarization light board ") below according to situation.Hereinafter, will as needed referring to the drawings, to this polarization film and its Manufacture method, this polarizer and its manufacture method and this circular polarization light board and its manufacture method are illustrated.Separately, this specification In accompanying drawing size only for ease of viewing.
<Polyazo system pigment>
The polyazo system pigment (being referred to as " azo system pigmen (1) " below according to situation) used in the manufacture of this polarization film As shown in formula (1), azo system pigmen (1) has in the range of 400~800nm of wavelength to be absorbed.
It is preferred that the alloisomerism at the azobenzene position of azo system pigmen (1) is trans.
Azo system pigmen (1) can be enumerated, compound represented respectively by formula (1-1)~formula (1-27) etc..
More than azo system pigmen (1) concrete example among, more preferably respectively by formula (1-2), formula (1-5), formula (1-6), Formula (1-8), formula (1-10), formula (1-12), formula (1-13), formula (1-15), formula (1-16), formula (1-19), formula (1-20), formula (1- 21), the compound that formula (1-22), formula (1-23), formula (1-24) and formula (1-26) are represented, particularly preferably respectively by formula (1-2), formula The compound that (1-5), formula (1-8), formula (1-10), formula (1-15), formula (1-21), formula (1-22) and formula (1-26) are represented.
The content of azo system pigmen (1) in above-mentioned polarization film formation composition, near relative to aftermentioned polymerism The content of the crystalline mass parts of liquid-crystal compounds 100 is represented, below preferably 50 mass parts, more than more preferably 0.1 mass parts 20 mass Below part, more than further preferred 0.1 mass parts below 10 mass parts.When within the above range, formed with polarization film When polymerism smectic shape liquid-crystal compounds when being polymerize, it is orientated the advantage not being disturbed.Polarization film formation is combined The azo system pigmen (1) contained in thing can be a kind, or two or more.Contain when in polarization film formation composition Azo system pigmen (1) be two or more when, its total amount is within the above range.
<Polymerism smectic shape liquid-crystal compounds>
The polymerism smectic shape liquid-crystal compounds contained in above-mentioned polarization film formation composition refers to, with polymerism Group, and the compound of smectic liquid crystal state is presented.Polymerizable group, refers to participate in the polymerism smectic shape liquid-crystal compounds Polymerisation group.
The mesomorphic state that above-mentioned polymerism smectic shape liquid-crystal compounds is presented, preferably senior smectic phase.Herein senior Smectic phase refers to smectic B, smectic D phases, smectic E phases, smectic F phases, smectic G phases, smectic H phases, smectic I phases, smectic J phases, near Brilliant K phases and smectic L phases, wherein, more preferably smectic B, smectic F phases and smectic I phases.According to polymerism smectic shape liquid-crystal compounds The mesomorphic state presented, can obtain this high polarization film of ordered orientation degree.In addition, the high sheet of such ordered orientation degree is inclined Shaken light film, and bragg peak can be obtained in X-ray diffraction measure.
Bragg peak refers to that origin is used in the peak of the face periodic structure of molecularly oriented according to different polarization film formation Composition, can obtain period distances isThis polarization film.
It is preferred that polymerism smectic shape liquid-crystal compounds can enumerate, for example the compound shown in formula (2) is (below according to situation Referred to as " compound (2)).
U1-V1-W1-X1-Y1-X2-Y2-X3-W2-V2-U2 (2)
[in formula (2),
X1、X2And X3Expression independently of one another can be with substituent is to phenylene or can have Isosorbide-5-Nitrae-ring of substituent sub- Hexyl.Wherein, X1、X2And X3Among at least 1 be can have substituent to phenylene.
Y1And Y2Expression-CH independently of one another2CH2-、-CH2O- ,-COO- ,-OCOO-, singly-bound ,-N=N- ,-CRa= CRb- ,-C ≡ C- or-CRa=N-.RaAnd RbThe alkyl of hydrogen atom or carbon number 1~4 is represented independently of one another.
U1Represent hydrogen atom or polymerizable group.
U2Represent polymerizable group.
W1And W2Singly-bound ,-O- ,-S- ,-COO- or-OCOO- are represented independently of one another.
V1And V2Represent there can be the alkylidene of the carbon number 1~20 of substituent independently of one another, constitute the alkylidene - CH2- can be replaced by-O- ,-S- or-NH-.]
It is preferred that X1、X2And X3Among at least 2 be can have substituent to phenylene.
Preferred pair phenylene is unsubstituted.It is preferred that Isosorbide-5-Nitrae-cyclohexylene is anti-form-1, and 4- cyclohexylenes, more preferably this is anti- Formula-Isosorbide-5-Nitrae-cyclohexylene is also to be unsubstituted.
The substituent that phenylene or Isosorbide-5-Nitrae-cyclohexylene have can be enumerated, the carbon number such as methyl, ethyl and butyl 1 ~4 alkyl；Cyano group；Halogen atom etc..Separately ,-the CH of Isosorbide-5-Nitrae-cyclohexylene is constituted2- can be replaced by-O- ,-S- or-NR-.R is carbon The alkyl or phenyl of atomicity 1~6.
It is preferred that Y1For-CH2CH2- ,-COO- or singly-bound, preferably Y2For-CH2CH2- or-CH2O-。
U2It is polymerizable group.U1For hydrogen atom or polymerizable group, preferred polymeric group.It is preferred that U1And U2It is poly- Conjunction property group.Polymerizable group is preferably polymerism group.Polymerism group refers to, can be drawn by photopolymerization described later Send out the group that living radical or acid of agent generation etc. participate in polymerisation.If using the polymerism with polymerism group Smectic shape liquid-crystal compounds, then can polymerize the polymerism smectic shape liquid-crystal compounds, in this point under conditions of more low temperature On be favourable.
U1And U2Polymerizable group each other can be different, but preferably congener group.
Polymerizable group can be enumerated, vinyl, vinyl epoxide, 1- chlorovinyls, isopropenyl, 4- ethenylphenyls, Acryloxy, methacryloxy, epoxy ethyl, oxetanylmethoxy etc..Wherein, preferably acryloxy, metering system Acyloxy, vinyl epoxide, epoxy ethyl and oxetanylmethoxy, more preferably acryloxy.
V1And V2Alkylidene can enumerate, methylene, ethylidene, 1,3- propylidene, 1,3- butylidenes, Isosorbide-5-Nitrae-butylidene, 1, The sub- myristyl and 1,20- of 5- pentylidene, 1,6- hexylidenes, 1,7- heptamethylenes, 1,8- octamethylenes, 1,10- decylenes, 1,14- Alkylene eicosyl etc..V1And V2It is preferred that the alkylidene of the alkylidene of carbon number 2~12, more preferably carbon number 6~12.
The substituent that alkylidene has can be enumerated, cyano group and halogen atom etc..It is preferred that alkylidene is unsubstituted, more preferably without taking Generation and the alkylidene of straight-chain.
W1And W2It is preferably singly-bound or-O- independently of one another.
Compound (2) can be enumerated, compound represented respectively by formula (2-1)~formula (2-24) etc..When related compound (2) when concrete example has Isosorbide-5-Nitrae-cyclohexylene, preferably Isosorbide-5-Nitrae-the cyclohexylene is trans body.
Polymerism smectic shape liquid-crystal compounds can be individually or after two or more mixing, for polarization film formation composition.
When polymerism smectic shape liquid-crystal compounds is used for into polarization film formation composition, polymerism smectic is tried to achieve in advance The phase transition temperature of shape liquid-crystal compounds, under the temperature conditionss less than the phase transition temperature, adjusts polarization film formation group Composition outside the polymerism smectic shape liquid-crystal compounds of compound, polymerize polymerism smectic shape liquid-crystal compounds.As can control The composition of the such polymerization temperature of system, can enumerate polymerization initiator described later, sensitizer and polymerization inhibitor etc..By suitably adjusting it Species and amount, can control the polymerization temperature of polymerism smectic shape liquid-crystal compounds.Separately, in polarization film formation composition During middle use polymerism smectic shape liquid-crystal compounds of more than two kinds, the polymerism smectic shape LCD compound of more than two kinds is tried to achieve After the phase transition temperature of the mixture of thing, polymerization temperature is controlled as described above.
Among the compound (2) of illustration, it is preferably selected from respectively by formula (2-2), formula (2-3), formula (2-4), formula (2-6), formula In the group that (2-7), formula (2-8), formula (2-13), formula (2-14), formula (2-15) and the compound shown in formula (2-24) are constituted extremely It is few a kind.
Polymerism smectic shape liquid-crystal compounds is preferably by mixing, or the phase interaction with polymerization initiator used at the same time With can be easily under the temperature conditionss less than phase transition temperature, you can fully keeping the feelings of senior smectic liquid crystal state Under condition, the compound of polymerization is allowed to.More specifically, polymerism smectic shape liquid-crystal compounds is preferably, by with polymerization initiator Interaction, below 70 DEG C, under preferably less than 60 DEG C of temperature conditionss, can fully keep senior smectic liquid crystal state and The compound of polymerization.
The polymerism smectic shape liquid-crystal compounds contained in above-mentioned polarization film formation composition can be independent one kind, Or it is a variety of but preferably a variety of.
The content ratio of polymerism smectic shape liquid-crystal compounds in above-mentioned polarization film formation composition, relative to this The solid constituent of polarization film formation composition, preferably 70~99.9 mass %, more preferably 90~99.9 mass %.Work as polymerization The content ratio of property smectic shape liquid-crystal compounds within the above range when, the orientation with polymerism smectic shape liquid-crystal compounds The tendency uprised.Herein, solid constituent refers to, is removed from the polarization film formation composition after the volatile ingredients such as solvent Composition total amount.Separately, when containing plural polymerizable smectic shape liquid-crystal compounds in the polarization film formation composition, its Total content ratio is within the above range.
<Solvent>
It can also contain solvent in polarization film formation composition.Generally, due to polymerism smectic shape liquid-crystal compounds Viscosity it is high, therefore by the way that coating can be made it easier to containing solvent, the result is that the situation that polarization film is easily formed is more.Solvent is excellent Choosing can be completely dissolved the solvent of polymerism smectic shape liquid-crystal compounds and azo system pigmen (1).Furthermore it is preferred that to polarization film The polymerisation of formation composition is inert solvent.
Solvent can be enumerated, methanol, ethanol, ethylene glycol, isopropanol, propane diols, Ethylene glycol methyl ether, ethylene glycol butyl ether and The alcoholic solvents such as propylene glycol monomethyl ether；Ethyl acetate, butyl acetate, Ethylene glycol methyl ether acetic acid esters, gamma-butyrolacton or propane diols The ester solvent such as methylether acetate and ethyl lactate；Acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-HEPTANONE and methyl tert-butyl The ketone solvents such as base ketone；The aliphatic hydrocarbon solvents such as pentane, hexane and heptane；The aromatic hydrocarbon solvents such as toluene and dimethylbenzene, acetonitrile etc. Nitrile solvent；The ether solvents such as tetrahydrofuran and dimethoxy-ethane；Chlorinated solvents such as chloroform and chlorobenzene etc..These solvents can independent one Plant or multiple combinations are used.
The content of solvent is relative to the total amount of above-mentioned polarization film formation composition, preferably 50~98 mass %.Change speech It, solid constituent preferably 2~50 mass % in polarization film formation composition.Solid constituent in more than 2 mass %, Tendency with slim polarization film for being more easy to obtain an object of the present invention.On the other hand, the solid constituent is in 50 matter When measuring below %, the viscosity of polarization film formation composition so that the thickness of polarization film is substantially homogeneous, thus has Have the tendency of the polarization film be not likely to produce it is uneven.In addition, related solid constituent can be according to can form aftermentioned polarization film Thickness determine.
<Polymerisation auxiliary agent>
Above-mentioned polarization film formation preferably comprises polymerization initiator with composition.The polymerization initiator is to trigger polymerism The compound of the polymerisation of smectic shape liquid-crystal compounds, based on the point of the polymerisation can be triggered under conditions of more low temperature, It is preferred that Photoepolymerizationinitiater initiater.Specifically, the effect that will be enabled through light produces the compound of living radical or acid as photopolymerization Initiator.Among the Photoepolymerizationinitiater initiater, the initiator of free radical is more preferably produced by the effect of light.
Above-mentioned polymerization initiator can be enumerated, for example benzoin compound, benzophenone cpd, benzene alkyl ketone compound, Acylphosphine oxide compound, triaizine compounds, salt compounded of iodine and sulfonium salt etc..
It is exemplified below the concrete example of the polymerization initiator.
Benzoin compound can be enumerated, for example benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Ether and benzoin isobutyl ether etc..
Benzophenone cpd can be enumerated, for example benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl hexichol first Ketone, 4- -4 '-methyldiphenyls of benzoyl thioether, 3,3 ', 4,4 '-four (t-butylperoxycarbonyl) benzophenone and 2,4,6- Tri-methyl benzophenone etc..
Benzene alkyl ketone compound can be enumerated, for example diethoxy acetophenone, 2- methyl -2- morpholinoes -1- (4- methyl thios Phenyl) -1- acetone, 2- benzyl -2- dimethylaminos -1- (4- morpholinyl phenyls) -1- butanone, 2- hydroxy-2-methyl -1- phenyl - 1- acetone, 1,2- diphenyl -2,2- dimethoxy -1- ethyl ketones, 2- hydroxy-2-methyls -1- (4- (2- hydroxyl-oxethyls) phenyl) - 1- acetone, 1- hydroxycyclohexylphenylketones and 2- hydroxy-2-methyls -1- (4- (1- methyl ethylenes) phenyl) -1- acetone it is low Polymers etc..
Acylphosphine oxide compound can be enumerated, TMDPO and two (2,4,6- tri- Methyl benzoyl) phenyl phosphine oxide etc..
Triaizine compounds can be enumerated, such as 2,4- bis- (trichloromethyl) -6- (4- methoxyphenyls) -1,3,5-triazines, 2, 4- bis- (trichloromethyl) -6- (4- methoxyl groups naphthyl) -1,3,5-triazines, 2,4- bis- (trichloromethyl) -6- (4- methoxy styrenes Base) -1,3,5-triazines, 2,4- bis- (trichloromethyl) -6- (2- (5- methylfuran -2- bases) vinyl) -1,3,5-triazines, 2,4- Two (trichloromethyl) -6- (2- (furans -2- bases) vinyl) -1,3,5-triazines, 2,4- bis- (trichloromethyl) -6- (2- (4- diethyls Base amino-2-methyl phenyl) vinyl) -1,3,5-triazines and 2,4- bis- (trichloromethyl) -6- (2- (3,4- dimethoxy benzenes Base) vinyl) -1,3,5-triazines etc..
The product easily bought from market can be used in polymerization initiator.Commercially available polymerization initiator can be enumerated, " イ Le ガ キ ュア(Irgacure)907”、“イルガキュア184”、“イルガキュア651”、“イルガキュア819”、“イ Le ガ キ ュ ア 250 ", " イ Le ガ キ ュ ア 369 " (チ バ ジ ヤ パ Application (strain))；" the Le BZ " of セ イ Network オ mono-, " セ イ Network The Le Z " of オ mono-, " the Le BEE " of セ イ Network オ mono- (Seiko chemistry (strain))；" (kayacure) BP100 " (Japanizations of カ ヤ キ ュ ア mono- Medicine (strain))；" UVI-6992 of カ ヤ キ ュ ア mono- " (ダ ウ societies system)；" SP-152 of ア デ カ オ プ ト マ mono- ", " ア デ カ オ プ ト The SP-170 of マ mono- " ((strain) ADEKA)；" TAZ-A ", " TAZ-PP " (the Japanese society of シ イ ベ Le ヘ グ Na one)；And " TAZ-104 " (three and ケ ミ カ Le society) etc..
When above-mentioned polarization film formation composition contains polymerization initiator, although its content can be according to the polarization film Formation is suitably adjusted with the species and its amount of the polymerism smectic shape liquid-crystal compounds contained in composition, but such as phase For the mass parts of total amount 100 of polymerism smectic shape liquid-crystal compounds, content preferably 0.1~30 mass parts of polymerization initiator The scope of scope, more preferably 0.5~10 mass parts, the scope of further preferred 0.5~8 mass parts.When polymerizing initiator Content within the range when, due to that can be allowed to polymerize in the case where not upsetting the orientation of polymerism smectic shape liquid-crystal compounds, Therefore can be polymerize in the case where the polymerism smectic shape liquid-crystal compounds keeps senior smectic liquid crystal state.
When above-mentioned polarization film formation composition contains polymerization initiator, in the polarization film formation composition Sensitizer can be contained.The preferred photosensitizing agent of sensitizer.The sensitizer can be enumerated, the xanthone such as xanthone and thioxanthones Compound (such as 2,4- diethyl thioxanthones, ITX etc.)；Anthracene and anthracene (for example, the two fourth oxygen containing alkoxy Base anthracene etc.) etc. anthracene compound；Phenothiazine and rubrene etc..
When above-mentioned polarization film formation composition contains polymerization initiator and sensitizer, it can further promote the polarization The polymerisation of the polymerism smectic shape liquid-crystal compounds contained in light film formation composition.Although related sensitizer makes Consumption can according to and polymerization initiator and polymerism smectic shape liquid-crystal compounds species and its amount be suitably adjusted, But for example relative to the mass parts of total amount 100 of polymerism smectic shape liquid-crystal compounds, the preferred scope of 0.1~30 mass parts, more It is preferred that the scope of 0.5~10 mass parts, the scope of further preferred 0.5~8 mass parts.
Though understand by making to contain sensitizer in above-mentioned polarization film formation composition, promote polymerism smectic shape The polymerisation of liquid-crystal compounds, but in order that the polymerisation is stably carried out, in the polarization film formation composition Polymerization inhibitor can moderately be contained.By containing polymerization inhibitor, the progress of the polymerisation of polymerism smectic shape liquid-crystal compounds can control Degree.
Above-mentioned polymerization inhibitor can be enumerated, and such as hydroquinones, hydroquinones containing alkoxy, catechol containing alkoxy are (for example, Butyl-catechol etc.), 1,2,3,-thrihydroxy-benzene, the free radical scavenger such as 2,2,6,6- tetramethyl -1- piperidines epoxide free radicals；Benzene sulphur Phenols；Betanaphthyl amine and betanaphthol class etc..
When above-mentioned polarization film formation composition contains polymerization inhibitor, although its content can be near according to the polymerism used The species and its amount of crystalline liquid-crystal compounds, and the usage amount etc. of sensitizer are suitably adjusted, but for example relative to poly- The mass parts of conjunction property smectic shape liquid-crystal compounds 100, the scope of content preferably 0.1~30 mass parts of polymerization inhibitor, more preferably 0.5~ The scope of 10 mass parts, the scope of further preferred 0.5~8 mass parts.When polymerization inhibitor content within the range when, due to can Make in the case of the orientation of the polymerism smectic shape liquid-crystal compounds contained in not upsetting the polarization film formation composition Polymerization, therefore the polymerism smectic shape liquid-crystal compounds can further, keeping senior smectic liquid crystal state well In the case of polymerize.
<Levelling agent (レ ベ リ Application グ drug)>
It is preferred that above-mentioned polarization film formation composition contains levelling agent.There is the levelling agent adjustment polarization film formation to use The mobility of composition, the function of making coated film obtained by coating polarization film formation composition more flat, can enumerate surface Activating agent etc..The levelling agent is further preferably from using polyacrylic acid ester compounds as the levelling agent of main composition and with fluorine-containing atomization Compound is at least one kind of for what is selected among the levelling agent of principal component.
Levelling agent using polyacrylic acid ester compounds as main composition can be enumerated, " BYK-350 ", " BYK-352 ", " BYK- 353 ", " BYK-354 ", " BYK-355 ", " BYK-358N ", " BYK-361N ", " BYK-380 ", " BYK-381 " and " BYK-392 " [BYK Chemie societies] etc..
It can be enumerated using fluorine-containing atomic compound as the levelling agent of principal component, it is " Mega-fac (メ ガ Off ア ッ Network) R-08 ", same " R-30 ", with " R-90 ", with " F-410 ", with " F-411 ", with " F-443 ", with " F-445 ", with " F-470 ", with " F-471 ", With " F-477 ", with " F-479 ", with " F-482 " and with " F-483 " [DIC (strain)]；" Surflon (the Off ロ Application of サ mono-) S-381 ", With " S-382 ", with " S-383 ", with " S-393 ", with " SC-101 ", with " SC-105 ", " KH-40 " and " SA-100 " [AGC セ イ ミ ケ ミ カ Le (strain)]；" E1830 ", " E5844 " [(strain) Daikin Fine Chemical (ダ イ キ Application Off ア イ Application ケ ミ カ Le) research institute]；" エ Off ト ッ プ EF301 ", same " EF303 ", same " EF351 " and same " EF352 " [Mitsubishi's マ テ リ ア Le electronization Into (strain)] etc..
When above-mentioned polarization film formation composition contains levelling agent, its content liquid-crystalizes relative to polymerism smectic shape More than the scope, further preferred 0.5 the mass parts more than mass parts of compound 100, preferably 0.3 mass parts below 5 mass parts 3 mass Scope below part.When levelling agent content within the above range when, then be easy to make polymerism smectic shape liquid-crystal compounds level Orientation, and having makes the polarization film to be formed become smoother tendency.If levelling agent liquid-crystalizes relative to polymerism smectic shape The content of compound exceedes above range, then with making obtained polarization film be easy to produce uneven tendency.Separately, the polarization Light film formation composition can contain levelling agent of more than two kinds.
<The forming method of this polarization film>
Then, the method for forming this polarization film with composition to being formed by above-mentioned polarization film is illustrated.Related In method, this is formed preferably by the way that the polarization film formation is coated on base material with composition, on preferably clear base material partially Shake light film.
<Transparent base>
Above-mentioned transparent base refers to there is the transparent base material that can pass through light, especially visible ray.The transparency refers to For the light in the range of 380~780nm of wavelength, characteristic of its transmitance more than 80%.In particular it relates to transparent base Material can be enumerated, glass baseplate, or plastics translucency piece and light transmissive film.Separately, the translucency piece or light transmissive film are constituted Plastics can be enumerated, the polyolefin such as polyethylene, polypropylene, norbornene-based polymer；Annular ethylene series resin；Polyethylene Alcohol；Polyethylene terephthalate；Polymethacrylates；Polyacrylate；Triafol T, cellulose diacetate and The cellulose esters such as cellulose acetate propionate；PEN；Makrolon；Polysulfones；Polyether sulfone；Polyether-ketone； The plastics such as polyphenylene sulfide and polyphenylene oxide.Among the concrete example of above transparent base, for preferred plastics translucency piece and thoroughly Photosensitiveness film, preferably plastics light transmissive film, i.e. polymeric membrane.Among the polymeric membrane, based on easily being bought from market, the transparency Excellent point, particularly preferred cellulose esters, annular ethylene series resin, polyethylene terephthalate or polymethacrylates The polymeric membrane of composition.When manufacturing this polarization film using the transparent base being related to, during based on carrying, taking care of the transparent base The breakages such as rupture, and maneuverable point are not susceptible to, support base material etc. can be attached on the transparent base.In addition, such as rear institute State, when manufacturing circular polarization light board by this polarization film, there is a situation where to assign the transparent base with phase difference.In this feelings Under condition, polymeric membrane is got out as transparent base, by carrying out stretch processing etc. to the polymeric membrane, the polymeric membrane is assigned Phase difference, is made after phase difference film, and the phase difference film is used as into transparent base.Separately, it is (high to assigning transparent base Molecular film) illustrated in the method for phase difference.
It is preferably fine based on the point for being easily controlled the phase difference value when assigning its phase difference among above-mentioned polymeric membrane The film (cellulose ester membrane, annular ethylene series resin film) that the plain ester of dimension or annular ethylene series resin are constituted.Below to this 2 kinds of high score Sub- film is described in detail.
Contained at least a portion hydroxyl can be by acetic acid in cellulose esters for constituting cellulose ester membrane, its cellulose Esterification.The cellulose ester membrane being made up of such cellulose esters can easily be bought from market.Commercially available three cellulose acetate membrane Have for example, " Off ジ タ Star Network film " (Fuji description Off イ Le system (strain))；" KC8UX2M ", " KC8UY " and " KC4UY " (U ニ カ ミ ノ Le タ オ プ ト (strain)) etc..Such commercially available three cellulose acetate membrane can directly or according to need assign phase difference after It is further used as transparent base.In addition, non-glare treated, hard conating process, antistatic can be implemented to the surface of ready transparent base After the surface treatment such as processing and antireflection process, it is re-used as transparent base 1 and uses.
When assigning polymeric membrane with phase difference, as described above, taking the method for polymeric membrane stretching etc..To modeling The polymeric membrane that material, i.e. thermoplastic resin are constituted, can carry out stretch processing, but based on the point for being easily controlled phase difference, it is excellent Select annular ethylene series resin film.The annular ethylene series resin for constituting annular ethylene series resin film refers to by such as ENB or many The resin that the polymer or copolymer (annular ethylene series resin) of the cyclic olefins such as ring norborneol alkene monomer are constituted, the ring-type alkene Hydrocarbon system resin can contain part open loop structure.In addition, can be also hydrogenated with to the annular ethylene series resin containing open loop structure.Enter One step, based on the point for substantially not damaging the transparency, or does not significantly increase hygroscopic point, the annular ethylene series resin can be example Such as, the copolymer of cyclic olefin and chain olefin or vinylation aromatic compound (styrene).In addition, for the ring-type alkene Hydrocarbon system resin, can import polar group to the intramolecular.
When annular ethylene series resin is cyclic olefin with chain olefin or the copolymerization of the aromatic compound with vinyl During thing, the chain olefin is ethene or propylene etc., in addition, vinylation aromatic compound be styrene, α-methylstyrene and Alkyl-substituted styrene etc..In such copolymer, come from the content ratio of the construction unit of cyclic olefin, relative to ring The general construction unit of shape olefin-based resin, in 50 moles of below %, such as scope in 15~50 moles of % degree.When ring-type alkene When hydrocarbon system resin is the terpolymer obtained by cyclic olefin and chain olefin with vinylation aromatic compound, for example, coming From general construction unit of the content ratio relative to the annular ethylene series resin of the construction unit in chain olefin, rubbed 5~80 Your % degree, comes from the content ratio of the construction unit of vinylation aromatic compound, in 5~80 moles of % degree. The annular ethylene series resin of such terpolymer has when manufacturing the annular ethylene series resin, relative can reduce high price ring The advantage of the usage amount of shape alkene.
The annular ethylene series resin of annular ethylene series resin film, which can be manufactured, easily to be bought from market.Commercially available ring-type alkene Hydrocarbon system resin can be enumerated, " Topas " [Ticona societies (Germany)]；" the ト Application of ア mono- " [JSR (strain)]；“ゼオノア(ZEONOR)” And " ゼ オ ネ Star Network ス (ZEONEX) " [Japanese ゼ オ Application (strain)]；" ア ペ Le " [Mitsui Chemicals (strain) system] etc..Can be by so Annular ethylene series resin is for example, by solvent casting process or film (cyclic olefin is made in film-forming method known to dissolving extrusion etc. Resin film).In addition, it is possible to use the annular ethylene series resin film sold with the form of film.Such commercially available ring-type alkene Hydrocarbon system resin film can be enumerated, such as " Na of エ ス シ mono- " and " SCA40 " [ponding chemical industry (strain)]；“ゼオノアフイル System " [オ プ テ ス (strain)]；" the ト Application Off イ Le system of ア mono- " [JSR (strain)] etc..
Then, the method for assigning polymeric membrane phase difference is briefly described bright.Polymeric membrane can be by known Drawing process assigns phase difference.For example, the roller (spool body) that polymeric membrane is wound into roller is got out, from the spool body Continuous uncoiling output film, heating furnace is transported to by the film that uncoiling is exported.The design temperature of heating furnace is the glass in polymeric membrane Change the scope of (DEG C)~[glass transition temperature+100] (DEG C) near transition temperature, near preferred glass transition temperature The scope of (DEG C)~[glass transition temperature+50] (DEG C).In the heating furnace, to film move ahead direction, or with preceding line direction When orthogonal direction is stretched, direction is carried in adjustment or tension force is allowed to tilt with any angle, carries out uniaxially or biaxially hot-drawn Stretch processing.The multiplying power of stretching is usually the scope of 1.1~6 times or so of scope, preferably 1.1~3.5 times or so.In addition, conduct The method stretched in incline direction, as long as axis of orientation is carried out inclined method along expected angle, i.e., without It is particularly limited to, can be using known drawing process.Such drawing process can be enumerated, for example Japanese Patent Laid-Open No. Sho 50-83482 Method described in number publication or Japanese Patent Laid-Open 2-113920 publications.
As transparent base in use, based on can practical operation degree weight point, and can ensure that sufficiently thoroughly The point of bright property, the thickness preferably thin person of polymeric membrane, if but it is excessively thin, decline with intensity, the trend of poor in processability.Therefore, The suitable thickness of these films is in such as substantially 5~300 μm, preferably 20~200 μm.This polarization film is inclined as circle described later Tabula rasa shake in use, the imagination of the mobile purposes based on the display device using the circular polarization light board, the thickness of particularly preferred film At substantially 20~100 μm.
Separately, when assigning film by stretching with phase difference, thickness and drawing of the thickness according to the film before stretching after stretching Multiplying power is stretched to determine.
<Alignment films>
On the base material used in the manufacture of this polarization film, alignment films are preferably formed with.Now, polarization film formation group Compound is coated in alignment films.It is therefore preferable that the alignment films have via coating of polarization film formation composition etc. without The solvent tolerance of the degree of dissolving.In addition it is also preferred that with the heating carried out for removing solvent or liquid crystal aligning Heat resistance.Orientation polymer can be used in the alignment films being related to.
Above-mentioned orientation polymer can be enumerated, such as polyamide or gelatin class, intramolecular with amido link in intramolecular The polyamic acid of polyimides and its hydrolysate with imide bond, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide Amine, poly- oxazole, polyethyleneimine, polystyrene, PVP, polyacrylic acid or polyacrylate etc. polymerize Thing.Wherein, preferred polyvinyl alcohol.These orientation polymer of formation alignment films can be used alone or two or more is used in mixed way.
Orientation polymer can be as being dissolved in the orientation polymer composition of solvent (containing the molten of orientation polymer Liquid), by being coated on base material, alignment films are formed on the substrate.The solvent that the orientation polymer composition is used is without spy It Zhi not limit, can specifically enumerate, water；Methanol, ethanol, ethylene glycol, isopropanol, propane diols, methyl cellosolve, butyl cellosolve and The alcoholic solvents such as propylene glycol monomethyl ether；Ethyl acetate, butyl acetate, Ethylene glycol methyl ether acetic acid esters, gamma-butyrolacton, propane diols The ester solvent such as methylether acetate and ethyl lactate；Acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and first The ketone solvents such as base isobutyl ketone；The aliphatic hydrocarbon solvents such as pentane, hexane and heptane；The aromatic hydrocarbon solvents such as toluene and dimethylbenzene； The nitrile solvent such as acetonitrile；The ether solvents such as tetrahydrofuran and dimethoxy-ethane；The chlorine such as chloroform and chlorobenzene substitution hydrocarbon solvent etc..These have Machine solvent be can be used alone or multiple combinations are used.
In addition it is used for the orientation polymer composition for forming alignment films, commercially available aligning film material can be used directly.City The aligning film material sold can be enumerated, サ Application エ バ mono- (registration mark, Nissan Chemical Industries (strain) system) and (registrations of オ プ ト マ mono- Trade mark, JSR (strain) systems) etc..
As the method that alignment films are formed on above-mentioned base material, such as on above-mentioned base material, it is coated with above-mentioned orientation polymerization Compositions or commercially available aligning film material, afterwards by annealing, can form alignment films on above-mentioned base material.It is obtained as described above Alignment films thickness in such as 10nm~10000nm scope, preferably 10nm~1000nm scope.
In order to assign anchorage force to above-mentioned alignment films, (rubbing manipulation) is preferably rubbed as needed.By assigning grappling Power, can be such that polymerism smectic shape liquid-crystal compounds is orientated along desired direction.
As the method that anchorage force is assigned by rubbing manipulation, can enumerate for example be ready to be wound with it is friction cloth, rotation Friction roll, alignment films formation will be formd on base material and is placed on the laminate of coated film on objective table, to rubbing for being rotating Wipe roller to transport, the method for thus making the friction roll of the alignment films formation coated film with being rotating be in contact.
In addition, it is possible to use so-called optical alignment film.Optical alignment film can also form light orientation induced layer, be polarized by irradiating Light (preferably polarised light UV) assigns anchorage force.When forming light orientation induced layer, first, it is ready to containing with photoreactivity base The polymer of group or the composition (being also referred to as " optical alignment film formation composition " below according to situation) of monomer and solvent.Light is anti- Answering property group refers to the group that liquid crystal aligning ability is produced by irradiation light (light irradiation).Specifically refer to send out by light irradiation As the induction orientation or isomerization reaction, dimerization reaction, photo-crosslinking, or photolysis reactionses of raw product molecule, draw Play the group of the light reaction of liquid crystal aligning ability.Among the photoreactive group, dimerization reaction or photo-crosslinking are utilized Group, based on orientation it is excellent, keep polarization film formation when smectic shape mesomorphic state point and it is preferred that.As can occur with The photoreactive group of upper reaction, preferably with unsaturated bond, especially have double bond group, particularly preferably have be selected from Among 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) At least one key group.
Photoreactive group with C=C keys can be enumerated, for example vinyl, polyalkenyl, stilbene base, benzene second The miscellaneous stilbene radicals of alkenyl pyridine radicals, class, chalcone base and cinnamoyl etc..Photoreactive group with C=N keys can be enumerated, and be had Aromatic series schiff bases and the isostructural group of aromatic series hydrazone.Photoreactive group with N=N keys can be enumerated, azobenzene, idol Quinoline base, heteroaromatic azo group, two azo groups are Ji formazan base etc., or to aoxidize group of the even oxygen benzene as basic structure. Photoreactive group with C=O keys can be enumerated, benzophenone base, cumarin base, anthraquinonyl and dimaleoyl imino etc..This A little groups can have alkyl, alkoxy, aryl, pi-allyl epoxide, cyano group, alkoxy carbonyl, hydroxyl, sulfonic group and alkyl halide The substituents such as base.
Wherein, can preferably occur the photoreactive group of light dimerization reaction, based on the polarizing light irradiation required for light orientation Amount is relatively fewer, and is easily obtained heat endurance or lasts the optical alignment film of excellent in stability, preferably cinnamoyl and chalcone Base.Further, as the polymer with photoreactive group, the distal portion of the particularly preferred polymer lateral chain, which has, is in The cinnamoyl of cinnamic acid structure sample.
The optical alignment film formation composition of solvent is dissolved in as polymer or monomer with photoreactive group, is led to Cross and be coated over the transparent substrate, light orientation induced layer (film) can be formed on the transparent base.Used for said composition Solvent be not particularly limited, above-mentioned orientation can be used according to polymer or the dissolubility of monomer with photoreactive group The solvent used in polymer composition.
Relative to optical alignment film formation composition, the concentration of polymer or monomer with photoreactive group, though can The thickness of optical alignment film suitably enters according to made from the polymer or the species of monomer with the photoreactive group or expection Row is adjusted, but is represented with solid component concentration, more preferably at least 0.2 mass %, particularly preferred 0.3~10 mass % model Enclose.In addition, in the range of the characteristic of optical alignment film is not substantially damaged, the optical alignment film formation composition can contain poly- second Enol or polyimides Polymer material or sensitizer.
As by above-mentioned orientation polymer or polymer or monomer with photoreactive group are coated on transparent base On method, can be or flexible using the rubbing method such as spin-coating method, extrusion, intaglio plate coating, die coating method, stick coating method and coating process Method known to print processes such as method etc..Separately, in the continuous manufacture by volume to volume form described later (Roll to Roll forms) When method implements the manufacture of this polarization film, the coating method is generally using the printing such as intaglio plate coating, die coating method or flexibility method Method.
Separately, rubbed or during polarizing light irradiation, if being sheltered (マ ス キ Application グ), differently- oriented directivity can be formed not Same multiple regions (pattern).
<The manufacture method of this polarization film>
In the alignment films formed on above-mentioned (transparent) base material, the polarization film formation of the coating present invention is obtained with composition Coated film.In the alignment films be coated with polarization film formation composition method (coating method) can enumerate, for example with saturating The method identical side illustrated when being coated with orientation polymer or polymer (monomer) with photoreactive group on bright base material Method.
Then, done under conditions of not polymerize by the above-mentioned polymerism smectic shape liquid-crystal compounds contained in the coated film Dry removing solvent, forms dry coationg.Drying means can be enumerated, and such as natural seasoning, aeration-drying method, heat drying and be subtracted Press seasoning etc..Now, preferably first make the mesomorphic state of polymerism smectic shape liquid-crystal composition that contains in the dry coationg into After nematic phase (nematic liquid crystal state), then the nematic Phase is set to be smectic phase.Carrying out as described above via nematic phase When forming smectic phase, for example, it can take following method：It is heated to the polymerism smectic shape liquid-crystal compounds contained in dry coationg More than the temperature for being mutually changed into nematic liquid crystal state, it is then cooled to the polymerism smectic shape liquid-crystal compounds and smectic phase liquid is presented The temperature of crystalline state.
Polymerism smectic shape liquid-crystal compounds in above-mentioned dry coationg is made is in smectic shape mesomorphic state, or makes the polymerization Property smectic shape liquid-crystal compounds when being rendered as smectic shape mesomorphic state via nematic liquid crystal state, by determining the polymerism used The phase transition temperature of smectic shape liquid-crystal compounds, can easily try to achieve the condition (heating condition) of control mesomorphic state.Determining should The condition determination of phase transition temperature is illustrated by embodiments herein.
When polymerizeing above-mentioned polymerism smectic shape liquid-crystal compounds, in order that it keeps good smectic liquid crystal shape State, as the polymerism smectic shape liquid-crystal compounds, is preferably used containing the nearly crystalline Compound of polymerizable liquid crystal of more than two kinds Polarization film formation composition.If using the content ratio that have adjusted the polymerism smectic shape liquid-crystal compounds of more than two kinds Polarization film formation composition, then via nematic phase formation smectic liquid crystal state after, can temporary formation supercooling State, has the advantages that to be easy to keep senior smectic liquid crystal state.
Then, the polymerization process of polymerism smectic shape liquid-crystal compounds is illustrated.Herein, to making above-mentioned polarization film Formation composition contains Photoepolymerizationinitiater initiater, and the mesomorphic state for making the polymerism smectic shape liquid-crystal compounds in dry coationg is in After smectic phase, the smectic liquid crystal state is kept, the method for the polymerism smectic shape liquid-crystal compounds photopolymerization is described in detail. In photopolymerization, as the light of irradiation dry coationg, can according to the species of the Photoepolymerizationinitiater initiater contained in the dry coationg, Or species (the photopolymerization that especially, the polymerism smectic shape liquid-crystal compounds has of polymerism smectic shape liquid-crystal compounds The species of group) and its amount, light is suitably selected from the group of visible ray, ultraviolet light and laser composition or passes through active electrons Shu Jinhang.Wherein, the point of the progress based on easily controllable polymerisation, or widely used device conduct in the field can be used The point of device involved by photopolymerization, preferably ultraviolet light.It is therefore preferable that selecting to contain in above-mentioned polarization film formation composition Polymerism smectic shape liquid-crystal compounds or Photoepolymerizationinitiater initiater species, so that photopolymerization can be carried out by ultraviolet light.In addition, , also can be by appropriate cooling means while irradiating ultraviolet light when being allowed to be polymerize, cool drying envelope is to control to gather Close temperature.If, can be in implementation polymerism smectic shape LCD compound under lower temperature by using such cooling means The polymerization of thing, even if then with above-mentioned transparent base using the relatively low thing of heat resistance, also can rightly shape cost polarisation beam The advantage of film.Separately, during photopolymerization, also this polarization film for foring pattern can be obtained by being sheltered or being developed.
By carrying out photopolymerization as described above, above-mentioned polymerism smectic shape liquid-crystal compounds is keeping smectic phase, preferably It is polymerize under the senior smectic liquid crystal state enumerated, forms this polarization film.Polymerism smectic shape liquid-crystal compounds This polarization film in the case where keeping the mesomorphic state of smectic phase obtained by polymerization, along with the effect of above-mentioned azo system pigmen (1), phase Than in existing host and guest's build polarization film, i.e. keep nematic liquid crystal state under make polymerism nematic liquid crystal compound etc. gather Polarization film obtained by conjunction, it has the advantages that polarised light performance will be significantly larger than the existing polarization film.Further, compare In the polarization film of only coating dichroism pigment or lysotropic liquid crystal, it has the advantages that excellent strength.
As above the scope that preferably less than more than 0.5 μm 5 μm of the thickness of the polarization film formed, further preferred 1 μm with Upper less than 5 μm.Accordingly it is contemplated that the thickness to the polarization film of acquisition determines the thickness of the coated film of this polarization film formation Degree.Separately, the thickness of this polarization film can be tried to achieve by interfering film thickness gauge or laser microscope or contact pin type film thickness gauge to determine.
In addition, this polarization film so formed, as described above, particularly preferably obtaining Bradley in X-ray diffraction measure The polarization film at lattice peak.As the polarization film for obtaining such bragg peak, can enumerate for example, display from hexagonal phase or This polarization film of the diffraction maximum of crystal phase.
In the manufacture of described above polarization film, it is made successively and possesses this polarization film/(light) alignment films/transparent The component of base material.The component can be directly used as the polarizer used in liquid crystal display device.If briefly describing the above-mentioned polarizer Manufacture method, the then process that its manufacture method includes following (1)~(5).
(1) process for possessing the laminate for there are above-mentioned alignment films over the transparent substrate is got out；
(2) in the above-mentioned alignment films of above-mentioned laminate, formation forms the film constituted with composition by above-mentioned polarization film Process；
(3) process that solvent is removed from above-mentioned film；
(4) the above-mentioned polymerism smectic shape liquid-crystal compounds contained in the film for making to eliminate above-mentioned solvent turns into smectic shape liquid The process of crystalline state；
(5) made by above-mentioned polymerism smectic shape liquid-crystal compounds in the case where keeping the form of above-mentioned smectic shape mesomorphic state Above-mentioned polymerism smectic shape liquid-crystal compounds polymerization, in the process that polarization film is formed in above-mentioned alignment films.
<The method for continuous production of this polarization film>
The manufacture method of this polarization film is illustrated generally above, but when commercially manufacturing this polarization film, it would be desirable to be able to The method for continuously manufacturing this polarization film.Such method for continuous production is the method for taking volume to volume form, according to circumstances will It is referred to as " this manufacture method ".Separately, in this manufacture method, by base material to be illustrated centered on the situation of transparent base.
This manufacture method is for example with following process：
Get out the process that transparent base is wound in the 1st roller obtained by the 1st core；
The process for continuously sending out the transparent base from the 1st roller；
Coating is containing polymer and the composition of solvent with above-mentioned photoreactive group, in continuous on the transparent base The process for forming the 1st coated film；
The solvent is removed by being dried from the 1st coated film, in forming the 1st dry coationg on the transparent base, is continuously obtained The process for obtaining the 1st laminate；
By carrying out polarised light UV irradiations to the 1st dry coationg, optical alignment film is formed, the 2nd laminate of continuous acquisition Process；
On the optical alignment film, the combination containing polymerism smectic shape liquid-crystal compounds, dichroism pigment and solvent is coated with Thing, in the process that the 2nd coated film is formed continuously on the optical alignment film；
By the polymerism smectic shape liquid-crystal compounds that contains in the 2nd coated film without polymerization under conditions of, 2nd coated film is dried, in the 2nd dry coationg of formation on the optical alignment film, the continuous process for obtaining the 3rd laminate；
The polymerism smectic shape liquid-crystal compounds contained in the 2nd dry coationg is set to turn into after smectic shape mesomorphic state, By keeping the smectic shape mesomorphic state, it polymerize the polymerism smectic shape liquid-crystal compounds, the continuous work for obtaining polarization film Sequence；
The polarization film continuously obtained is wound in the 2nd core, the process for obtaining the 2nd roller.Herein, reference picture 1, to this The major part of manufacture method is illustrated.
Transparent base be wound in the 1st roller 210 obtained by the 1st core 210A can from for example, in the market is readily available. As such transparent base that can be bought with roller form from market, among the transparent base enumerated, fibre can be enumerated Film that the plain ester of dimension, annular ethylene series resin, polyethylene terephthalate or polymethacrylates are constituted etc..In addition, Using this polarization film as circular polarization light board in use, the transparent base for imparting phase difference in advance also can be easy from the market Ground is obtained, and can be enumerated such as the phase retardation film that, cellulose esters or annular ethylene series resin are constituted.
Then, transparent base is exported from the above-mentioned uncoiling of 1st roller 210.The method of uncoiling output transparent base can be by as follows Carry out：Suitable whirligig is set to the core 210A of the 1st roller 210, the 1st roller 210 is revolved by the whirligig Turn.In addition, can also take the following form：On the direction for carrying transparent base from the 1st roller 210, suitable auxiliary rolling is set Cylinder 300, transparent base is exported by the whirligig uncoiling of the auxiliary cylinder 300.Further, it can also take the following form：It is logical Cross and whirligig is set to the 1st core 210A and auxiliary cylinder 300 simultaneously, assigning the same of the appropriate tension force of transparent base When, uncoiling output transparent base.
Transparent base from the above-mentioned uncoiling of 1st roller 210 output is when by apparatus for coating 211A, by the apparatus for coating 211A is coated with above-mentioned optical alignment film formation composition on its surface.In order to be coated with optical alignment film as continuous as described above Formation composition, apparatus for coating 211A is using print processes such as intaglio plate coating, die coating method, flexibility methods.
Film after apparatus for coating 211A, equivalent to above-mentioned transparent base and the laminate of the 1st coated film.It is thusly-formed The transparent base of the 1st coated film of (lamination) is moved to drying oven 212A, is heated by drying oven 212A, converts For the 1st laminate being made up of transparent base and the 1st dry coationg.As drying oven 212A, such as hot air type can be used to dry Stove etc..Drying oven 212A design temperature, is formed with composition according to by the apparatus for coating 211A above-mentioned optical alignment films being coated with Species of the solvent contained etc. is set.In addition drying oven 212A, which can take, is divided into suitable section, division it is multiple The different form of the design temperature of section, can also take the multiple drying ovens of arranged in series, each drying oven is set each other Operated for different temperature, while film is transported to the form of the plurality of drying oven successively.
Then, to the 1st laminate being formed continuously by heating furnace 212A, via polarised light UV irradiation unit 213A, The surface on surface or transparent base side to the 1st dry coationg side of the laminate carries out polarised light UV irradiations, and thus the 1st is dry Dry envelope is converted into light polarization light film.Now, the carrying direction D1 and the differently- oriented directivity D2 of the optical alignment film formed for making film are into big The angle of 45 ° of cause.Fig. 5 is irradiated between the differently- oriented directivity D2 of optical alignment film formed after polarised light UV the and carrying direction D1 of film The schematic diagram of relation.That is, Fig. 1 is shown, for the surface by the 1st laminate after polarised light UV irradiation units 213A, Observe film carrying direction D1 and optical alignment film differently- oriented directivity D2 when, substantially 45 ° of the angle formed between them.
As above the 1st laminate being formed continuously, then by apparatus for coating 211B, thus takes in the light of the 1st laminate It is coated with to film after polarization film formation composition, then by drying oven 212B, and then as the 2nd laminate or the 2nd layer The polymerism smectic shape liquid-crystal compounds contained in 2nd dry coationg of product body forms the laminate of smectic shape mesomorphic state. Drying oven 212B has the function of being dried from the above-mentioned polarization film formation composition being coated with optical alignment film and remove solvent While, also with the effect for giving the 2nd dry coationg thermal energy, so that the polymerism contained in above-mentioned 2nd dry coationg Smectic shape liquid-crystal compounds turns into smectic liquid crystal state.In addition, as described above, in order that polymerism smectic shape liquid-crystal compounds In smectic liquid crystal state, it is in nematic liquid crystal state that the polymerism smectic shape liquid-crystal compounds is first made for the time being, for this reason, it may be necessary to right Above-mentioned 1st laminate carries out multistage heat with different heating conditions.Therefore, drying oven 212B is such as to drying oven 212A explanation like that, is preferably made up of the multiple sections for setting different set temperature each other, or prepares multiple mutual Between the different drying oven of design temperature, be arranged in series the form of the plurality of drying oven.
Above-mentioned drying oven 212B film is have passed through, polarization film formation is fully removed with the solvent contained in composition, Polymerism smectic shape liquid-crystal compounds in 2nd dry coationg is moved to light in the case where keeping the form of smectic liquid crystal state Irradiation unit 213B.Light irradiation is carried out by light irradiation device 213B, the polymerism smectic shape liquid-crystal compounds is in holding State and photopolymerization is carried out under the form of mesomorphic state, this final polarization film is consecutively formed in alignment films.
As above this polarization film being formed continuously, is wound in the form containing transparent base and the laminate of alignment films 2nd core 220A, obtains the form of the 2nd roller 220.When this polarization film that winding is formed obtains 2 roller, it is possible to use Appropriate sept (サ of ス ペ mono-) carries out co-wound.
As described above, transparent base sequentially passes through 1 roller/apparatus for coating 211A/ drying oven 212A/ polarised lights in order U V irradiation unit 213A/ apparatus for coating 211B/ drying oven 212A/ light irradiation device 213A, on the optical alignment film of transparent base Polarization film is continuously made.
In addition, in this manufacture method shown in Fig. 1, though exemplified with the continuous manufacture from transparent base to this polarization film Method, but can also be made as follows：Such as transparent base sequentially passes through 1 roller/apparatus for coating 211A/ and dried in sequence Stove 212A/ polarised light UV irradiation unit 213A, the 1st laminate being formed continuously produces roller form in core 1st laminate, the 1st laminate is exported from the roller uncoiling, and the 1st laminate that uncoiling is exported passes through apparatus for coating in order 211B/ drying oven 212A/ light irradiation device 213A, are made this polarization film.
This polarization film obtained according to this manufacture method, its shape is membranaceous and is strip.By this polarization film During for liquid crystal display device described later etc., it can be cut into according to scale of the liquid crystal display device etc. after the size of needs again Use.
More than, centered on the form of the laminate of transparent base/optical alignment film/this polarization film, to this polarization film Composition and manufacture method be illustrated, but as described above, this polarization film can also from the laminate peel off optical alignment film Or transparent base or layer on the laminate beyond lamination transparent base/optical alignment film/this polarization film or film Form.As these layers and film, as described above, this polarization film can be further equipped with phase retardation film, it can also be further equipped with preventing Reflecting layer or brightness enhancement film.
In addition, by the way that transparent base is made into phase retardation film in itself, phase retardation film/optical alignment film/this polarised light can be obtained The circular polarization light board or Elliptical circular polarization light board of film form.For example, being used as phase difference in 1/4 wavelength plate obtained using uniaxial tension , can be with volume by the way that polarised light UV direction of illumination is set as into the carrying direction relative to transparent base into substantially 45 ° during film Circular polarization light board is made to the method for volume.1/4 wavelength plate used in the such circular polarization light board of manufacture, preferably with pair In the characteristic that phase difference value shortens and reduced with wavelength in the face of visible ray.
In addition, making the angle of the absorption axiss of its slow axis and polarization film as phase retardation film by using 1/2 wavelength plate It is set as the rectilinearly polarized light plate cylinder staggered, relative side further forms 1/4 ripple in the face with forming the polarization film Long slab, can obtain broadband circular polarization light board.
<The purposes of this polarization film>
This polarization film can be used for various display devices.Display device refers to the device with display element, and it includes hair Optical element or light-emitting device are used as light emitting source.Display device can be enumerated, and such as liquid crystal display device, organic electroluminescent (EL) show Showing device, inorganic EL (EL) display device, electron emission display (such as field-emission display device (FED), table Face field emission display device (SED)), Electronic Paper (use the display device of electronic ink or electrophoresis element, plasma display dress Put, (such as grating light valve (GLV) display device, the display with digital microlens device (DMD) are filled projection type image display apparatus Put) and piezoelectric ceramics display etc..Liquid crystal display device equally shows comprising transmissive liquid crystal display device, semi-transparent liquid crystal Showing device, reflection-type liquid-crystal display device, direct view liquid crystal display device and projection type liquid crystal display apparatus etc. it is any.These Display device can be the display device for showing two dimensional image or the 3 d display device for showing 3-D view.
This polarization film can particularly effectively be used for organic electroluminescent (EL) display device or inorganic EL (EL) The display device of display device.
Fig. 2 and Fig. 5 are (to be referred to as " this liquid crystal display dress below according to situation using the liquid crystal display device of this polarization film Put ") generalized schematic of 10 section constitution.Liquid crystal layer 17 is clamped by 2 plate base 14a and substrate 14b.
Fig. 8 and Figure 10 are the EL display devices (being referred to as " this EL display devices " below according to situation) using this polarization film Section constitution generalized schematic.
Figure 11 is the generalized schematic of the composition of the projection-type liquid crystal display device using this polarization film.
First, this liquid crystal display device shown in Fig. 2 10 is illustrated.
Colour filter 15 is configured with the substrate 14a side of liquid crystal layer 17.Colour filter 15 is configured at the picture with clamping liquid crystal layer 17 The opposite position of plain electrode 22, black matrix" 20 is configured at the opposite position in region between pixel electrode.Transparency electrode 16 is matched somebody with somebody It is placed in the side of liquid crystal layer 17, covering colour filter 15 and black matrix" 20.
Separately, there can be protection film layer (not shown) between colour filter 15 and transparency electrode 16.
In the substrate 14b side of liquid crystal layer 17, thin film transistor (TFT) 21 is configured with pixel electrode 22 by rule.Pixel electrode 22 is matched somebody with somebody It is placed in the position opposite with the colour filter 15 of clamping liquid crystal layer 17.Between thin film transistor (TFT) 21 and pixel electrode 22, it is configured with Interlayer dielectric 18 with connecting hole (not shown).
As substrate 14a and substrate 14b, glass substrate and plastic base are used.
The glass substrate and plastic base being related to, can be used and transparent base material cited in the manufacture of this polarization film Matter identical substrate.In addition, the transparent base 1 of this polarization film can hold a concurrent post substrate 14a and substrate 14b.The shape on manufacture substrate Into colour filter 15 or thin film transistor (TFT) 21 when, it is necessary in the case of high-temperature heating process, preferably glass substrate or quartz base plate.
Thin film transistor (TFT) can be according to substrate 14b material, using optimal morphology.Thin film transistor (TFT) 21 can be enumerated, in quartz High temperature polysilicon silicon transistor is formed on substrate, low-temperature polycrystalline silicon transistor, glass substrate or plastic base is formed on glass substrate Upper formation amorphous silicon transistor.In order that this liquid crystal display device smallerization, can also form driving IC on substrate 14b.
Liquid crystal layer 17 is configured between transparency electrode 16 and pixel electrode 22.In liquid crystal layer 17, in order that substrate 14a And the distance between substrate 14b keeps fixing, and is configured with sept 23.Separately, column spacer is shown in Fig. 2, but simultaneously unexpectedly Taste is defined to column by the sept, as long as the distance between substrate 14a and substrate 14b can be made to keep fixing, it is shaped as Arbitrarily.
, can be on the face contacted with liquid crystal layer 17 among the layer formed on substrate 14a and substrate 14b, being respectively configured makes The alignment films that liquid crystal is orientated to desired orientation.Separately, this polarization film can be configured inside liquid crystal cell, i.e. can with liquid crystal layer The side in 17 faces connected configures this polarization film.Such form hereinafter is referred to as " embedded ".This is embedded refer to it is aftermentioned.
Each component is according to substrate 14a, colour filter 15 and black matrix" 20, transparency electrode 16, liquid crystal layer 17, pixel electrode 22nd, interlayer dielectric 18 and thin film transistor (TFT) 21 and substrate 14b order carry out lamination successively.
Among such substrate 14a and substrate 14b that hold liquid crystal layer 17, it is provided with and is polarized on the outside of substrate 14b Device 12a and 12b, 1 polarizer of wherein at least contain this polarization film.
Further, preferably phase separation layer (for example, 1/4 wavelength plate or optical compensation films) 13a and 13b carries out lamination.It is polarized Among device 12a and 12b, by the way that this polarization film is configured at into polarizer 12b, this liquid crystal display device 10 can be assigned by incident light Be converted to the function of rectilinearly polarized light.Separately, according to the liquid-crystal compounds contained in the structure of liquid crystal display device, or liquid crystal layer 17 Species, can not also configure phase retardation film 13a and 13b, when transparent base be phase retardation film, use the circle containing this polarization film During polarization plate, due to can using the phase retardation film as phase separation layer, therefore can also omit the phase separation layer 13a in Fig. 2 and/or 13b.Also polarization film can be further set in the light emitting side (outside) of the polarizer containing this polarization film.
In addition, also can be in the outside of the polarizer containing this polarization film (when being further configured with this polarization film During polarization film, on the outside of it), it is configured to prevent the antireflection film that ambient light reflects.
As described above, in the polarizer 12a or 12b of Fig. 2 this liquid crystal display device 10, this polarization film can be used. By the way that this polarization film is arranged at into the polarizer 12a and/or 12b, with the slimming that can reach this liquid crystal display device 10 Effect.
When this polarization film is used for into polarizer 12a or 12b, its laminated order is not particularly limited.With void in reference picture 2 The A and the enlarged drawing of part B that coil goes out are described.
Fig. 3 is the section enlarged diagram of the part A in Fig. 2.Fig. 3 (A1) is shown, and is used as by the polarizer 100 During for polarizer 12a, from phase separation layer 13a sides, the setting of this polarization film 3, optical alignment film 2 and transparent base 1 is configured successively. In addition, Fig. 3 (A2) is shown from phase separation layer 13a sides, transparent base 1, optical alignment film 2 and this polarization film are configured successively 3 setting.
Fig. 4 is, the enlarged diagram of Fig. 2 part B.Fig. 4 (B1) is shown, and is used as using the polarizer 100 During inclined device 12b, from phase retardation film 13b sides, the setting of transparent base 1, optical alignment film 2 and this polarization film 3 is configured successively.Fig. 4 (B2) be shown, when using the polarizer 100 as polarizer 12b, from the 3b sides of phase retardation film 1, this polarization is configured successively The setting of light film 3, optical alignment film 2 and transparent base 1.
In polarizer 12b outside, the backlight module 19 as light emitting source is configured with.
Backlight module 19 includes light source, light conductor, reflecting plate, diffusion sheet and visual angle trimmer.Light source can be enumerated, electroluminescent hair Light, cold-cathode tube, thermionic-cathode tube, light emitting diode (LED), LASER Light Source and mercury lamp etc..In addition, can be according to the spies of these light sources Property selects the species of this polarization film.
When this liquid crystal display device 10 be transmissive liquid crystal display device when, from the light source in backlight module 19 send it is white Coloured light injects light conductor, is changed by reflecting plate after light path, is diffused by diffusion sheet.Diffusion light is adjusted by visual angle trimmer After with desired directive property, polarizer 12b is injected by backlight module 19.
Among the incident light of no polarization, only a certain rectilinearly polarized light passes through the polarizer 12b of liquid crystal panel.The straight line Polarised light is converted to circularly polarized light or Elliptical circularly polarized light by phase separation layer 13b, and substrate 14b, pixel electrode 22 are penetrated successively Deng arrival liquid crystal layer 17.
Herein, according to potential difference is whether there is between pixel electrode 22 and opposite transparency electrode 16, change and contain in liquid crystal layer 17 Liquid crystal molecule state of orientation, and then control from this liquid crystal display device 10 project light brightness.When liquid crystal layer 17 is straight When connecing the state of orientation for passing through polarised light, the polarised light passes through liquid crystal layer 17, transparency electrode 16, the light of certain particular range of wavelengths Polarizer 12a is reached through colour filter 15, the most bright color determined by colour filter is shown in liquid crystal display device.
On the contrary, when liquid crystal layer 17 is that switchable polarisation light is allowed to the state of orientation passed through, through liquid crystal layer 17, transparency electrode 16 and colour filter 15 light be polarized device 12a absorption.Thus, the pixel is shown as black.If the intermediate orientation of this 2 states State, then the brightness of the light projected from this liquid crystal display device 10 is also in the middle of the two, therefore during the pixel is shown as Secondary color.
When this liquid crystal display device 10 is transflective liquid crystal display device, preferably use on this polarization film further It is laminated with the thing (circular polarization light board) of 1/4 wavelength plate.Now, pixel electrode 22 has the through portion formed by transparent material, and The reflecting part formed by the material of reflected light, through portion display image in the same manner as above-mentioned transmissive liquid crystal display device.It is another Aspect, in reflecting part, ambient light injects liquid crystal display device, the work for 1/4 wavelength plate being further equipped with by this polarization film With, through this polarization film circularly polarized light by liquid crystal layer 17, reflected via pixel electrode 22, so that for showing.
Then, this polarization film of 5 pairs of reference picture use, embedded suitable liquid crystal display device (this liquid crystal display Device 24) illustrate.
This liquid crystal display device 24, by substrate 14a, polarizer 12a, phase retardation film 13a, colour filter 15 and black matrix" 20th, transparency electrode 16, liquid crystal layer 17, pixel electrode 22, interlayer dielectric 18 and thin film transistor (TFT) 21, phase retardation film 13b, rise Lamination is formed in sequence for inclined device 12b, substrate 14b and backlight module 19, in this composition, preferably uses the conduct of this polarization film Polarizer 12a.In this composition, this polarization film can also take transparent base 1, optical alignment film 2 and this polarization film 3 to configure successively Setting, so that the transparent base on the polarizer holds a concurrent post substrate 14a.By this composition, impart and possess this polarization film This liquid crystal display device 24 incident light is changed into the function of rectilinearly polarized light.Separately, it is identical with this liquid crystal display device 10, root According to the species of the liquid-crystal compounds contained in liquid crystal layer 17, phase separation layer 13a and 13b can not be also configured.
Then, 8 pairs of reference picture is illustrated using this EL display devices 30 of this polarization film.In this EL display devices During using this polarization film, this polarization film is first preferably made circular polarization light board and (is referred to as " this circularly polarized light below according to situation Plate ") after reuse.This circular polarization light board has 2 kinds of embodiments.Therefore, explanation this EL display devices 30 composition etc. it Before, 2 kinds of embodiments of this circular polarization light board are illustrated with initial reference to Fig. 6.
Fig. 6 (A) is the schematic cross-section of the 1st embodiment of this circular polarization light board 110.1st embodiment is, This circular polarization light board 110 of phase separation layer (phase retardation film) 4 is further set on the polarization film 3 in the polarizer 100.Fig. 6's (B) be this circular polarization light board 110 the 2nd embodiment schematic cross-section.2nd embodiment is this following circular polarization light board 110, it is used by using when imparting the transparent base 1 (phase retardation film 4) of phase difference in advance as the manufacture polarizer 100 Transparent base 1, transparent base 1 itself has the function as phase separation layer 4 concurrently.
Herein, the manufacture method on this circular polarization light board 110 is first illustrated.As above the 2nd of this circular polarization light board 110 , can be by using imparting phase difference in advance in this manufacture method of manufacture this polarization film 100 described in embodiment Transparent base 1, i.e. phase retardation film are manufactured as transparent base 1.In 1st embodiment of circular polarization light board 110, pass through Fitted on this polarization film being fabricated by by this manufacture method 3 phase retardation film, form phase separation layer 4.Separately, in basis This manufacture method, when manufacturing this polarization film 100 with the form of the 2nd roller 220, can take in the following manner：From the 2nd roller 220 uncoilings export this polarization film 100, are cut into after given size, and phase retardation film is fitted in this polarization film of the severing 100；But the 3rd roller of core is wound in by getting out phase retardation film, can be continuously manufactured by being shaped as membranaceous and be strip This circular polarization light board 110.
The method of 1st embodiment of the continuous manufacture circular polarization light board 110 of 7 pairs of reference picture is illustrated.The manufacture being related to Method is made up of following process：
While exporting this polarization film 100 from the continuous uncoiling of above-mentioned 2nd roller 220, from winding phase retardation film The process that the continuous uncoiling of 3rd roller 230 exports above-mentioned phase retardation film；
By set polarization film from this polarization film 100 that the above-mentioned uncoiling of 2nd roller 220 is exported, and from above-mentioned The above-mentioned phase retardation film of 3rd roller uncoiling output is continuously fitted the process for forming polarization plate 110；
This circular polarization light board 110 formed is wound in the 4th core 240A, the process for obtaining the 4th roller 240.
This circular polarization light board is preferred embodiment such as can enumerate following ＜ X1 ＞ and ＜ X2 ＞.
＜ X1 ＞ have this polarization film and λ/4 layer, and meet this circular polarization light board of the important document of following (A1) and (A2)
(A1) absorption axiss of this polarization film and substantially 45 ° of the slow axis angulation of above-mentioned λ/4 layer；
(A2) front retardation values determined under wavelength 550nm light, above-mentioned λ/4 layer 100~150nm scope with It is interior
＜ X2 ＞ have this polarization film, λ/2 layer and λ/4 layer successively, and meet following (B1)~(B4) all important documents Circular polarization light board
(B1) absorption axiss of above-mentioned polarization film and substantially 15 ° of the slow axis angulation of above-mentioned λ/2 layer；
(B2) slow axis of above-mentioned λ/2 layer and substantially 60 ° of the slow axis angulation of above-mentioned λ/4 layer；
(B3) above-mentioned λ/2 layer determined under wavelength 550nm light, the front retardation values of above-mentioned λ/2 layer 200~ 300nm scope；
(B4) above-mentioned λ/4 layer determined under wavelength 550nm light, the front retardation values of above-mentioned λ/4 layer 100~ 150nm scope
Though the manufacture method to the 1st embodiment of this circular polarization light board 110 is illustrated above, it is polarized in laminating During this polarization film 3 and phase retardation film in device 100, it is possible to use appropriate adhesive, via the bonding of adhesive formation Layer laminating this polarization film 3 and phase retardation film.
Then, this EL display devices that 8 pairs of reference picture possesses this circular polarization light board 110 are illustrated.
This EL display devices 30 are being formed with the substrate 33 of pixel electrode 35, lamination as light emitting source organic functions Layer 36 and cathode electrode 37 and be made.Circular polarization light board 31 is configured with the opposite side of clamping substrate 33, organic function layer 36, is made For related circular polarization light board 31, this circular polarization light board 110 is used.By applying positive voltage on pixel electrode 35, in negative electrode Apply negative voltage on electrode 37, the external dc electric current between pixel electrode 35 and cathode electrode 37, organic function layer 36 starts It is luminous.It is made up of as the organic function layer 36 of light emitting source electron supplying layer, luminescent layer and hole transporting layer etc..From organic functions The light that layer 36 is projected passes through pixel electrode 35, interlayer dielectric 34, substrate 33, circular polarization light board 31 (this circular polarization light board 110). Though the organic EL display with organic function layer 36 is illustrated, but it is also suitable for the inorganic EL with inorganic functional layer Display device.
When manufacturing this EL display devices 30, first, the thin film transistor (TFT) 40 of intended shape is formed on substrate 33.Then Interlayer dielectric 34 is formed, then with sputtering method formation pixel electrode 35, pattern is formed.Afterwards, lamination organic function layer 36.
Then, in the opposing face in the face for setting thin film transistor (TFT) 40 of substrate 33, (this circular polarization of circular polarization light board 31 is set Tabula rasa 110).
When using this circular polarization light board 110 as circular polarization light board 31, the C portion irised out in reference picture 8 with dotted line Enlarged drawing is illustrated to its laminated order.When using this circular polarization light board 110 as circular polarization light board 31, this circular polarization Phase separation layer 4 on tabula rasa 110 is configured at the side of substrate 33.Fig. 9 (C1) is the 1st embodiment of this circular polarization light board 110 The enlarged drawing used as circular polarization light board 31, Fig. 9 (C2) is the conduct circle of the 2nd embodiment of this circular polarization light board 110 The enlarged drawing that polarization plate 31 is used.
Then, the component beyond this polarization film 31 (circular polarization light board 110) of this EL display devices 30 is carried out simple Explanation.
Substrate 33 can be enumerated, sapphire glass substrate, quartz glass substrate, sodium calcium (ダ of ソ mono-) glass substrate and aluminum oxide Deng ceramic substrate；The metal substrates such as copper；Plastic base etc..
Though figure is not shown, heat conductivity film can be formed on substrate 33.Heat conductivity film can be enumerated, diamond thin (DLC etc.) etc..When pixel electrode 35 is reflection-type, light is projected from the direction opposite with substrate 33.Therefore, not only it can be used saturating Bright material, it is possible to use the non-transparent material such as stainless steel.Substrate can take single form, and can also take fitted multiple with adhesive Substrate is made the form of laminated substrate.In addition, these substrates are not limited to tabular, it is alternatively film.
As thin film transistor (TFT) 40, such as using polysilicon transistors.Thin film transistor (TFT) 40 is arranged at pixel electricity The end of pole 35, its size is 10~30 μm of degree.Separately, the size of pixel electrode 35 is the μ m 300 of 20 μ m 20 μm~300 μm degree.
On substrate 33, the cloth line electrode of thin film transistor (TFT) 40 is provided with.The resistance of cloth line electrode is low, with electric with pixel Pole 35 is electrically connected, and resistance value is suppressed into the function in low value, usually, and the cloth line electrode, which is used, contains Al, Al and transition metal Any one kind or two or more thing in (but not including Ti), Ti or titanium nitride (TiN).
Interlayer dielectric 34 is provided between thin film transistor (TFT) 40 and pixel electrode 35.Interlayer dielectric 34 can be by SiO2Formed or with SOG (ス ピ by sputtering or vacuum evaporation film forming Deng the inorganic based material such as silica, silicon nitride ン·オン·グラス；Spin-on-glass) tree such as silicon oxide layer, photoresist, polyimides and acrylic resin that is formed Any one of fat based material film etc., material with insulating properties.
On interlayer dielectric 34, rib 41 is formed.The edge that rib 41 is configured at pixel electrode 35 is (adjacent Between pixel).The material of rib 41 can be enumerated, acrylic resin and polyimide resin etc..The thickness of rib 41 preferably 1.0 Less than 3.5 μm more than μm, more preferably less than more than 1.5 μm 2.5 μm.
Then, to by the pixel electrode 35 as transparency electrode, the organic function layer 36 as light emitting source, cathode electrode 37 The EL element of composition is illustrated.Organic function layer 36 has hole transporting layer and luminescent layer at least each 1 layer, for example, in order Possess electron injection transfer layer, luminescent layer, hole transporting layer and hole injection layer.
Pixel electrode 35 can be enumerated, such as ITO (tin-doped indium oxide), IZO (mixing zinc indium oxide), IGZO, ZnO, SnO2And In2O3Deng particularly preferred ITO or IZO.As long as the thickness of pixel electrode 35 with can fully carry out the regulation of hole injection with On thickness, preferred 10~500nm degree.
Pixel electrode 35 can be by being deposited with (preferably sputtering method) formation.Sputter gas is not particularly limited, using Ar, He, Ne, The inert gases such as Kr and Xe, or their mixed gas.
As the constituent material of cathode electrode 37, can be used such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, The metallic elements such as In, Sn, Zn and Zr, but in view of improving the job stability of electrode, preferably use selected from illustration metallic element 2 kinds of compositions or 3 kinds of compositions alloy body.Alloy body preferably such as AgMg (Ag：1~20at%), A1Li (Li：0.3~ 14at%), InMg (Mg：50~80at%) and AlCa (Ca：5~20at%) etc..
Cathode electrode 37 can be formed by evaporation and sputtering method etc..It is preferred that the thickness of cathode electrode 37 is in more than 0.1nm, it is excellent Select 1~more than 500nm.
Hole injection layer has the function of making hole easily be injected from pixel electrode 35, and hole transporting layer has conveying hole And hinder the function of electronics, also referred to as electric charge injection layer and charge transport layer.
The thickness of the thickness of luminescent layer, the gross thickness of hole injection layer and hole transporting layer and electron injection transfer layer without It is particularly limited to, it is different because of forming method difference, it is preferably made substantially 5~100nm thickness.Hole injection layer or hole transporting layer In various organic compounds can be used.When forming hole injection transfer layer, luminescent layer and electron injection transfer layer, based on energy shape Into the point of homogeneous film, vacuum vapour deposition can be used.
It as the organic function layer 36 of light emitting source, can use, utilize the material for coming from singlet exciton luminous (fluorescence) Material, using coming from the material of Triplet exciton (phosphorescence), containing lighting (fluorescence) using coming from singlet exciton Material and using come from Triplet exciton (phosphorescence) material material, formed by organic matter material, containing by having The material and the material of the material formed by inorganic matter of the formation of machine thing, macromolecular material, low molecule material, contain macromolecular material With the material of low molecule material etc..It is however not limited to which this, has used organic work(as various materials known to EL element Ergosphere 36, can be applied to this EL display devices 30.
Drier 38 is configured between the space of cathode electrode 37 and cap 39.Because organic function layer 36 intolerant to It is wet.Moisture is absorbed by drier 38, the deterioration of organic function layer 36 is prevented.
Figure 10 is the skeleton diagram of the section constitution for the another way for representing this EL display devices 30.This EL display devices 30 With the encapsulating structure using thin-film package film 41, also emergent light can be obtained from the opposing face of array base palte.
As thin-film package film 41, being preferably used in evaporation on electrolytic capacitor film has the DLC of DLC (diamond-like-carbon) Film.DLC film has the excessively poor characteristic of moisture permeable, and its moisture-proof characteristic is high.In addition, also DLC film etc. can be directly deposited with The surface of cathode electrode 37 and formed.In addition, also can laminated multi-layer resin film and metallic film, formation thin-film package film 41.
There is provided a kind of polarized light film (this polarization film) of the present invention and possesses this polarization film as described above New display device (this liquid crystal display device and this EL display devices).
Finally to being illustrated using the projection-type liquid crystal display device of this polarization film.
Figure 11 is the generalized schematic of the projection-type liquid crystal display device using this polarization film.
As the polarizer 142 and/or the polarizer 143 of the projection-type liquid crystal display device, this polarization film is used.
The light shafts projected from the light source (such as, high-pressure sodium lamp) 111 as light emitting source, pass through the 1st lens array first 112nd, the 2nd lens array 113, polarization light conversion element 114, compound lens 115, thus homogeneous by the brightness of reflective strand cross-sectional Change, carry out polarization photochemical.
Specifically, the light shafts projected from light source 111, the 1st rectangular lens array is formed as via micro lens 112a Row 112 are divided into the small light shafts of multi beam.The 2nd lens array 113 and compound lens 115 are configured, so that divided light Beam can be respectively to 3 liquid crystal panels 140R, 140G, 140B as lighting object entirety be irradiated, thus, each liquid crystal surface The surface of plate light incident side can integrally obtain homogeneous illumination.
Polarization light conversion element 114 is made up of light beam separation array, is configured at the 2nd lens array 113 and compound saturating Between mirror 115.Thus, the random polarised light in light source can be converted to the polarised light with specific polarization light direction in advance, had There is to reduce the light loss in the light incident side polarizer described later, improve picture brightness.
As described above, brightness is homogenized and is polarized photochemical light, via speculum 122, pass sequentially through for dividing From for the trichromatic dichronic mirrors 121,123,132 of RGB, red passage, green passage, blue channel are separated into, liquid crystal surface is injected respectively Plate 140R, 140G, 140B.
In liquid crystal panel 140R, 140G, 140B, the polarizer 142 is configured with its light incident side respectively, exiting side has been configured with Inclined device 143.In the polarizer 142, the polarizer 143, this polarization film can be used.
The polarizer 142 and the polarizer 143 of each light paths of RGB are configured at, makes that respective absorption axiss are orthogonal to be configured.Configuration In each liquid crystal panel 140R, 140G, 140B of each light path, turn with the polarized light state of each pixel will be controlled according to picture signal It is changed to the function of light quantity.
This polarization film 100, can usefully conduct by species of the selection suitable for the dichroism pigment of corresponding passage Durability in each light path of blue channel, green passage and red passage excellent polarization film.
According to liquid crystal panel 140R, 140G, 140B view data, make incident light for each pixel with different transmitances Through the optical imagery being thus made is synthesized via cross colour splitting prism 150, and by projecting lens 170, amplification projects to projection On screen 180.
Electronic Paper can be enumerated, and the device that such molecule is shown is orientated by optical anisotropy and dye molecule； Moved by electrophoresis, particle, crystal grain rotates the device that the particle of (particle returns translocation), phase change etc is shown；Pass through film The device that one end moves to be shown；The device shown by color development/phase change of molecule；Pass through the light of molecule Absorb the device shown；Device for being combined generation self-luminous with hole by electronics to be indicated etc..More specifically, can Enumerate microcapsule-type electrophoresis, horizontal motion electrophoresis, vertically-moving electrophoresis, spherical twist ball type, magnetic twist ball type, cylinder Twist ball type, charged toner, electronics powder fluid, magnetophoresis type, magnetic heat seeking, electrowetting, light scattering (transparent/gonorrhoea change), Cholesteric liquid crystal/optical conductive layer, cholesteric liquid crystal, bistability nematic liquid crystal, Ferroelectric liquid Crystals, dichroism pigment dispersed liquid crystal Type, movable film, the colour changing according to leuco dye, photochromic, electrochromism, electro-deposition, flexible organic EL etc..Electronic Paper is not only The personal use of text or image is can be applied to, advertisement is applied also for and shows (label) etc..According to this polarization film, it can reduce The thickness of Electronic Paper.
It is used as 3 d display device, it is thus proposed that for example micro- polarization film (μ Pol) formula like that replaces the poor film of out of phase The method (Japanese Patent Laid-Open 2002-185983 publications) of arrangement, but the optical film of the present invention is used as polarization film When, due to pattern can be readily formed by printing, ink-jet, photoetching etc., therefore the manufacturing process of display device can be shortened, and be not required to Want phase retardation film.
Embodiment
The present invention is illustrated in further detail by the following examples." % " and " part " in example is if without especially saying It is bright, as quality % and mass parts.
In the present embodiment, following polymerism smectic shape liquid-crystal compounds is used.
Compound (2-6) (compound shown in following formula (2-6))
Compound (2-6) passes through Lub et al.Recl.Trav.Chim.Pays-Bas, 115,321-328 (1996) institute The method synthesis stated.
(measure of phase transition temperature)
The phase transition temperature of compound (2-6) is carried out by trying to achieve the phase transition temperature for the film being made up of compound (2-6) Confirm.Its operation is as follows.
On the glass substrate for foring alignment films, the film being made up of compound (2-6) is formed, while heating, is used Polarization microscope (BX-51, Olympus society system), phase transition temperature is confirmed by observation structure (テ Network ス チ ヤ mono-). The film that compound (2-6) is constituted is warming up to after 120 DEG C, during cooling, and it is nematic to confirm phase in version at 112 DEG C Phase, phase in version is that phase in version is smectic B at smectic C, 94 DEG C at 110 DEG C.
Compound (2-8) (compound shown in following formula (2-8))
Compound (2-8) is synthesized with reference to the synthesis of above-mentioned compound (2-6).
(measure of phase transition temperature)
Identical method is determined according to the phase transition temperature of compound (2-6), to compound (2-8) phase transition temperature Confirmed.Compound (2-8) is warming up to after 140 DEG C, during cooling, it is nematic to confirm phase in version at 131 DEG C Phase, phase in version is that phase in version is smectic B at smectic C, 68 DEG C at 80 DEG C.
Embodiment 1
(preparation of polarization film formation composition)
The following composition of mixing, stirs 1 hour at 80 DEG C, is derived from polarization film formation composition.
Polymerism smectic shape liquid-crystal compounds：75 parts of compound (2-6)
25 parts of compound (2-8)
Azo system pigmen (1)：2.5 parts of compound (1-8)
The pigment of D10 described in Japanese Patent Laid-Open 8-278409
Polymerization initiator：2- dimethylamino -2- benzyls -1- (4- morpholinyl phenyls) -1- butanone (イ Le ガ キ ュ ア 369： Ciba Co., Ltd (チ バ ス ぺ シ ヤ Le テ イ ケ ミ カ Le ズ societies) makes)
6 parts
Levelling agent：Polyacrylic acid ester compounds (BYK-361N：BYK-Chemie societies system) 1.2 parts
Solvent：250 parts of cyclopentanone
(measure of phase transition temperature)
By compound (2-6) and compound (2-8) with 75 parts of mass ratio：25 parts of ratio is mixed.
It is identical with the situation of compound (2-6) and compound (2-8), the phase for the mixture being formulated is tried to achieve as described above Transition temperature.The mixture is warming up to after 140 DEG C, during cooling, it is nematic phase to confirm phase in version at 115 DEG C, Phase in version is smectic C at 105 DEG C, and phase in version is smectic B at 75 DEG C.
(manufacture and evaluation of this polarization film)
1. form alignment films
Transparent base is used as using glass substrate.
By spin-coating method by polyvinyl alcohol (the fully saponified type of polyvinyl alcohol 1000, Wako Pure Chemical Industries, Ltd.'s system) The 2 mass % aqueous solution (orientation polymer composition) are coated on the glass substrate, after drying, and form thickness 100nm film. Then, friction treatment formation alignment films are implemented by the surface of the film to acquisition.Friction treatment uses semi-automatic rubbing device (business The name of an article：LQ-008 types, Joyo Engineering Co., Ltd.'s system), pass through cloth (trade name：YA-20-RW, Ji Chuan Chemical Co., Ltd system), Carried out under conditions of pressure is away from 0.15mm, rotating speed 500rpm, 16.7mm/s.By the friction treatment, obtain in glass substrate On be formed with the laminates 1 of alignment films.
2. form polarization film
Above-mentioned polarization film formation is coated on composition in the alignment films of laminate 1 by spin-coating method, at 120 DEG C Heat drying is quickly cooled to room temperature after 3 minutes in heating plate, and dry coationg is formed in above-mentioned alignment films.In the drying quilt In film, the mesomorphic state of polymerism smectic shape liquid-crystal compounds is smectic B.Then, by using UV irradiation units (SPOT CURE SP-7：ウ シ オ Electric Co., Ltd system), with light exposure 2400mJ/cm2(365nm benchmark) carries out purple to dry coationg Outside line is irradiated, and the polymerism smectic shape liquid-crystal compounds contained in the dry coationg keeps mesomorphic state and polymerize, by the drying Envelope is formed as polarization film.Pass through the polarised light of laser microscope (Olympus Co., Ltd OLS3000) measure now The thickness of film, is 1.7 μm.
3.X ray diffraction determinations
To the polarization film of the laminate 2 of acquisition, using X-ray diffraction device X ' Pert PRO MPD, (Spectris is public Take charge of (ス ぺ Network ト リ ス Co., Ltd.) system) carry out X-ray diffraction measure.Cu will be used as target, in x-ray tube current 40mA, X The X-ray produced under conditions of ray tube voltage 45kV (tries to achieve polarization in advance by fixed 1/2 ° of divergent slit along frictional direction The frictional direction of alignment films under light film) it is incident, with the scope of θ=4.0~40.0 ° of sweep limits 2, θ=0.01671 ° of step width 2 Be scanned, measure as a result, obtaining the sharp diffraction of half-peak breadth (FWHM)=about 0.312 ° near 2 θ=20.08 ° Peak.In addition, also having obtained identical result from perpendicular to frictional direction incidence.Asked by the position at peak and obtain lattice period (order Cycle) (d) be aboutUnderstand to form the structure for reflecting senior smectic phase.
4. the measure of dichroic ratio
In order to confirm the serviceability of this polarizer, dichroic ratio is determined by following.
Use the folding that the subsidiary polarizer is provided with spectrophotometer (Shimadzu Corporation UV-3150) The device of device, absorbance (A of the maximum absorption wavelength in transmission direction of principal axis is determined by dijection collimation method1) and absorb direction of principal axis suction Luminosity (A2).The reference side of the folder is provided with the mesh screen (メ ッ シ ュ) of light quantity reduction 50%.From the axis of homology side of measure To absorbance (A1) and absorb direction of principal axis absorbance (A2) value calculate ratio (A2/A 1), it is used as dichroic ratio.As a result see Table.Dichroic ratio is higher, more useful as polarization film.Absorb the absorbance (A of direction of principal axis2) maximum absorption wavelength, and The measurement result of dichroic ratio under the wavelength is shown in Table 1.
Embodiment 2~9 and comparative example 1~3, reference example 1~4 change the species of azo system pigmen (1), Qi Tayu Embodiment 1 makes polarization film in the same manner, determines the absorbance (A for absorbing direction of principal axis2) maximum absorption wavelength λ MAX and should Dichroic ratio under wavelength.It the results are shown in Table 1.
【Table 1】
Embodiment 10
Replace compound (2-6) as polymerism smectic shape liquid-crystal compounds using compound (2-14), use compound (2-24) replaces compound (2-8), other to form polarization film same as Example 1ly, and two under its λ MAX=518nm Color ratio is 36.
Embodiment 11
Replace compound (2-6) as polymerism smectic shape liquid-crystal compounds using compound (2-14), use compound (2-24) replaces compound (2-8), other to form polarization film same as Example 2ly, two colors under its λ MAX=392nm Property ratio be 22.
Embodiment 12
Replace compound (2-6) as polymerism smectic shape liquid-crystal compounds using compound (2-14), use compound (2-24) replaces compound (2-8), other to form polarization film same as Example 3ly, two colors under its λ MAX=536nm Property ratio be 40.
Embodiment 13
(preparation of polarization film formation composition)
Following compositions are mixed, in being stirred 1 hour at 80 DEG C, polarization film formation composition are obtained.
Polymerism smectic shape liquid-crystal compounds：75 parts of compound (2-6)
25 parts of compound (2-8)
Azo system pigmen (1)：2.5 parts of compound (1-8)
Polymerization initiator：2- dimethylamino -2- benzyls -1- (4- morpholinyl phenyls) -1- butanone (イ Le ガ キ ュ ア 369： Ciba Co., Ltd system) 6 parts
Levelling agent：Polyacrylic acid ester compounds (BYK-361N：BYK-Chemie societies system) 1.2 parts
Solvent：250 parts of cyclopentanone
(optical alignment film is made on phase retardation film)
Use phase retardation film (monadic stretching membrane WRF-S (modified polycarbonate system resin), phase difference value 137.1nm, thickness 50 μm, Supreme Being people's chemical conversion (strain) system) as transparent base, the light orientation polymer 5% for being coated with following formula (3) by stick coating method is dissolved in Solution (optical alignment film formation composition) obtained by cyclopentanone, is dried at 120 DEG C, obtains dry coationg.In dry coationg On, optical alignment film is obtained with the direction irradiation polarised light UV that the slow axis relative to the phase retardation film is at 45 °.Polarised light UV processing makes With UV irradiation units (SPOT CURE SP-7：ウ シ オ Electric Co., Ltd system), the intensity determined under wavelength 365nm is Carried out under conditions of 100mJ.
(making of circular polarization light board)
Above-mentioned polarization film formation is coated on optical alignment film with composition by stick coating method, dried with 120 DEG C dry After case heat drying 1 minute, room temperature is cooled to.In the dry coationg, the liquid of contained polymerism smectic shape liquid-crystal compounds Crystalline state is smectic B.Then, by using UV irradiation units (SPOT CURE SP-7：ウ シ オ Electric Co., Ltd system), With light exposure 2400mJ/cm2(365nm benchmark) carries out ultraviolet irradiation to forming the layer formed with composition by polarization film, The polymerism smectic shape liquid-crystal compounds contained in the dry coationg is set to keep the liquid of above-mentioned polymerism smectic shape liquid-crystal compounds Crystalline state and polymerize, polarization film is formed as by the dry coationg.Pass through laser microscope (society of Olympus Co., Ltd system OLS3000 the thickness of polarization film now) is determined, is 1.6 μm.
<The measure of optical characteristics>
To the circular polarization light board by above-mentioned acquisition, determine wavelength 450.9nm, 498.6nm, 549.4nm, 587.7nm, Ellipticity under 627.8nm, confirms all wavelength and is almost circularly polarized light.
450.9nm=a/b=0.841
498.6nm=a/b=0.889
549.4nm=a/b=0.968
587.7nm=a/b=0.924
627.8nm=a/b=0.852
Utilization possibility in industry
This polarization film is non-on manufacture liquid crystal display device, (organic) EL display devices and projection-type liquid crystal display device Chang Youyong.

Claims (7)

1. a kind of circular polarization light board, successively with polarization film, λ/2 layer and λ/4 layer, and meet following important document (B1), (B2), And (B4) (B3)：
(B1) absorption axiss of the polarization film and the slow axis angulation of λ/2 layer are 15 °；
(B2) slow axis of λ/2 layer and the slow axis angulation of λ/4 layer are 60 °；
(B3) λ/2 layer determined under wavelength 550nm light, the front retardation values of λ/2 layer is 200~300nm's Scope；
(B4) λ/4 layer determined under wavelength 550nm light, the front retardation values of λ/4 layer is 100~150nm's Scope；
The polarization film is as there is the polyazo shown in absorption, following formulas (1) containing the wave-length coverage in 400~800nm Be at least one kind of of pigment and
The composition of polymerism smectic shape liquid-crystal compounds is formed；
The polarization film obtains bragg peak in X-ray diffraction measure；
In formula (1),
N is 1 or 2,
Ar1And Ar3The group selected from group shown below is represented independently of one another；
Ar2Represent the group selected from group shown below；
A1And A2The group selected from group shown below is represented independently of one another；
M is 0~10 integer, and when there is 2 m in same group, this 2 m are identical or different each other.
2. a kind of circular polarization light board, with polarization film and λ/4 layer, and meets following important document (A1) and (A2)：
(A1) absorption axiss of the polarization film and the slow axis angulation of λ/4 layer are 45 °；
(A2) scope of the front retardation value of λ/4 layer determined under wavelength 550nm light in 100~150nm；
The polarization film is as there is the polyazo shown in absorption, following formulas (1) containing the wave-length coverage in 400~800nm Be at least one kind of of pigment and
The composition of polymerism smectic shape liquid-crystal compounds is formed；
The polarization film obtains bragg peak in X-ray diffraction measure；
In formula (1),
N is 1 or 2,
Ar1、Ar2And Ar3Represented group is one kind in following 3 kinds combinations：
A1Represent the group selected from group shown below；
M is 0~10 integer, and when there is 2 m in same group, this 2 m are identical or different each other.
3. circular polarization light board according to claim 1 or 2, wherein, the thickness of the polarization film is more than 1 μm, 5 μm with Under.
4. a kind of organic EL display, possesses the circular polarization light board and organic EL element described in claim 1 or 2.
5. a kind of polarization film, as having how even shown in absorption, following formulas (1) containing the wave-length coverage in 400~800nm Nitrogen system pigment at least one kind of and
The composition of polymerism smectic shape liquid-crystal compounds is formed；
The polarization film obtains bragg peak in X-ray diffraction measure；
In formula (1),
N is 1 or 2,
Ar1、Ar2And Ar3Represented group is one kind in following three kinds combinations：
A1Represent the group selected from group shown below；
M is 0~10 integer, and when there is 2 m in same group, this 2 m are identical or different each other.
6. a kind of manufacture method of the polarizer, the polarizer possesses polarization film described in claim 5, alignment films and thoroughly successively Bright base material, its manufacture method has following process：
The process for possessing the laminate of the alignment films on the transparent base is got out,
In the alignment films of the laminate, formed containing polymerism smectic shape liquid-crystal compounds, 400~800nm's The process that wave-length coverage has the film of polyazo system pigment shown in the above-mentioned formula (1) of absorption, polymerization initiator and solvent,
The process that the solvent is removed from the film of upper process formation,
The polymerism smectic shape liquid-crystal compounds contained in the film for making to eliminate the solvent turns into smectic shape mesomorphic state Process,
By the polymerism smectic shape liquid-crystal compounds in the case where keeping the form of the smectic shape mesomorphic state, make the polymerization Property the polymerization of smectic shape liquid-crystal compounds, in the process that polarization film is formed in the alignment films.
7. a kind of liquid crystal display device, possesses the polarization film described in claim 5.
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Families Citing this family (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102223121B1 (en) * 2013-08-09 2021-03-05 스미또모 가가꾸 가부시키가이샤 Process for producing long retardation film
KR20150093591A (en) 2014-02-07 2015-08-18 스미또모 가가꾸 가부시키가이샤 Process for producing long polarizing film
JP6299367B2 (en) * 2014-04-18 2018-03-28 住友化学株式会社 Pattern polarizing film manufacturing method
JP2015212823A (en) * 2014-04-18 2015-11-26 住友化学株式会社 Patterned polarizing film
KR102426386B1 (en) * 2014-04-18 2022-07-27 스미또모 가가꾸 가부시키가이샤 Patterned polarizing film and its production process
JP6728581B2 (en) 2014-06-25 2020-07-22 住友化学株式会社 Light-absorption anisotropic film, three-dimensional light-absorption anisotropic film, and method for producing the same
KR20230093526A (en) * 2014-10-17 2023-06-27 스미또모 가가꾸 가부시끼가이샤 Compound and composition
JP6428202B2 (en) * 2014-11-28 2018-11-28 住友化学株式会社 Optical laminate
CN105448251B (en) * 2014-12-09 2018-08-03 苏州汉朗光电有限公司 A kind of frequency amplitude variation driving method for smectic liquid crystal screen
CN105742319B (en) * 2014-12-26 2019-10-25 三星电子株式会社 Anti-reflective film and organic light emitting apparatus including the anti-reflective film
JP6586276B2 (en) * 2015-02-20 2019-10-02 住友化学株式会社 Compound and composition containing the same
JP6444763B2 (en) * 2015-02-20 2018-12-26 住友化学株式会社 Compound and composition containing the same
JP6718657B2 (en) * 2015-02-27 2020-07-08 住友化学株式会社 Composition
JP6538383B2 (en) * 2015-03-16 2019-07-03 住友化学株式会社 Polarizer and circular polarizer
JP6483486B2 (en) 2015-03-16 2019-03-13 住友化学株式会社 Polarizing plate and circularly polarizing plate
US10557978B2 (en) * 2015-07-24 2020-02-11 Sumitomo Chemical Company, Limited Composition, optical film including composition, and method of producing optical film
CN106978196B (en) * 2015-10-29 2022-02-15 住友化学株式会社 Composition and polarizing film
KR102182484B1 (en) * 2016-03-08 2020-11-24 후지필름 가부시키가이샤 Colored composition, dichroic dye compound, light-absorbing anisotropic film, laminate and image display device
JP7025702B2 (en) * 2016-03-31 2022-02-25 日産化学株式会社 Orientation layer forming composition
KR102263428B1 (en) * 2016-03-31 2021-06-11 닛산 가가쿠 가부시키가이샤 Polarizing layer forming composition
JP6718735B2 (en) 2016-04-26 2020-07-08 住友化学株式会社 Optical film
JP6771304B2 (en) * 2016-04-26 2020-10-21 住友化学株式会社 The composition and the optical film containing the composition
KR102652054B1 (en) 2016-07-21 2024-03-27 스미또모 가가꾸 가부시끼가이샤 Elliptical polarizing plate
KR102253504B1 (en) * 2016-11-29 2021-05-18 주식회사 엘지화학 Polarizing Plate
KR102253502B1 (en) * 2016-11-29 2021-05-18 주식회사 엘지화학 Polarizing Plate
JP2019032491A (en) * 2017-08-09 2019-02-28 株式会社ジャパンディスプレイ Display device and vehicle room mirror
JP6497457B2 (en) * 2018-02-27 2019-04-10 住友化学株式会社 Pattern polarizing film manufacturing method
JP7265389B2 (en) * 2018-03-29 2023-04-26 住友化学株式会社 Composition and polarizing film
CN111989599B (en) * 2018-04-27 2022-05-13 日本瑞翁株式会社 Broadband wavelength film, method for producing same, and method for producing circularly polarizing film
WO2019221137A1 (en) * 2018-05-14 2019-11-21 コニカミノルタ株式会社 Optical film, retardation film, polarizing plate and liquid crystal display device
JP7029529B2 (en) * 2018-05-25 2022-03-03 富士フイルム株式会社 Polarizer and image display device
JP7008831B2 (en) 2018-08-28 2022-01-25 富士フイルム株式会社 Laminates and image display devices
JP6741743B2 (en) * 2018-12-12 2020-08-19 富士フイルム株式会社 Liquid crystal composition, light absorption anisotropic film, laminate and image display device
WO2020129729A1 (en) * 2018-12-21 2020-06-25 富士フイルム株式会社 Liquid crystal composition, method for producing polymer liquid crystalline compound, light absorption anisotropic film, multilayer body and image display device
WO2020162119A1 (en) 2019-02-08 2020-08-13 東洋紡株式会社 Polyester film and use thereof
US11934226B2 (en) 2019-02-08 2024-03-19 Toyobo Co., Ltd. Foldable display and portable terminal device
JP6945586B2 (en) 2019-04-17 2021-10-06 住友化学株式会社 Laminated body and image display device
JP7435448B2 (en) 2019-05-28 2024-02-21 東洋紡株式会社 Laminated film and its uses
US11926720B2 (en) 2019-05-28 2024-03-12 Toyobo Co., Ltd. Polyester film and application therefor
KR20220016132A (en) 2019-05-28 2022-02-08 도요보 가부시키가이샤 Polyester film, laminated film and its use
EP3978967A4 (en) 2019-05-30 2023-07-12 Toyobo Co., Ltd. Foldable display
JPWO2020241312A1 (en) 2019-05-30 2020-12-03
WO2021106798A1 (en) * 2019-11-29 2021-06-03 日本化薬株式会社 Polarized light-emitting element, polarized light-emitting plate, and display device
JP6853902B2 (en) * 2020-01-29 2021-03-31 住友化学株式会社 Composition
CN112068357B (en) * 2020-09-25 2022-06-03 厦门天马微电子有限公司 Display panel and display device
JPWO2022270222A1 (en) 2021-06-21 2022-12-29

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2638930B2 (en) * 1987-06-04 1997-08-06 三菱化学株式会社 Liquid crystal composition
JP3687130B2 (en) * 1995-04-07 2005-08-24 住友化学株式会社 Alignment dye film, production method thereof, polarizing element and liquid crystal display device
JP2002151251A (en) * 2000-11-09 2002-05-24 Sharp Corp Luminous element
JP2002162519A (en) * 2000-11-24 2002-06-07 Teijin Ltd Circular polarized film and display device using the same
JP3807503B2 (en) * 2003-05-29 2006-08-09 セイコーエプソン株式会社 Liquid crystal display device and electronic device
EP2159611B1 (en) 2003-11-06 2018-01-03 Sumitomo Chemical Company, Limited Polymerizable liquid crystal and oriented polymer film
JP2006126551A (en) * 2004-10-29 2006-05-18 Hitachi Displays Ltd Liquid crystal display
WO2006123803A1 (en) * 2005-05-19 2006-11-23 Canon Kabushiki Kaisha Liquid crystal display device
JP4937252B2 (en) * 2005-06-27 2012-05-23 住友化学株式会社 Dichroic guest-host polarizer
JP2007249030A (en) * 2006-03-17 2007-09-27 Fujifilm Corp Polarized light conversion film and its manufacturing method, polarizing element, and liquid crystal display device
US8039067B2 (en) * 2006-05-18 2011-10-18 Fujifilm Corporation Cellulose acylate film and method for producing same, and retardation film, polarizer and liquid crystal display device comprising the film
US8927070B2 (en) * 2008-09-30 2015-01-06 Fujifilm Corporation Dichroic dye composition, light absorption anisotropic film, and polarizing element
JP2010210886A (en) * 2009-03-10 2010-09-24 Sumitomo Chemical Co Ltd Display device
JP2011048311A (en) * 2009-08-28 2011-03-10 Fujifilm Corp Dichroic dye, light-absorbing anisotropic film, polarizer and method for producing the same, and display device

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