CN103173227B - Form the compositions used by polarization film and polarization film - Google Patents
Form the compositions used by polarization film and polarization film Download PDFInfo
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- CN103173227B CN103173227B CN201210552907.XA CN201210552907A CN103173227B CN 103173227 B CN103173227 B CN 103173227B CN 201210552907 A CN201210552907 A CN 201210552907A CN 103173227 B CN103173227 B CN 103173227B
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- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
-
- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Abstract
It is an object of the invention to provide a kind of polarization film that can manufacture and form slim and that the there is heigh clarity compositions used by polarization film and formed by the compositions formed used by this polarization film.The solution of the present invention is to provide containing polymerizable liquid crystal compound, polymerism non-liquid crystal compound, dichroism pigment, Photoepolymerizationinitiater initiater and solvent, and meet following (A) and (B) essential condition forms the compositions used by polarization film and the polarization film formed by the compositions formed used by this polarization film.(A) polymerizable liquid crystal compound and polymerism non-liquid crystal compound all contain polymerizable group;(B) in the coated film obtained by the compositions formed used by polarization film, contained polymerizable liquid crystal compound does not haves phase-separated state, but shows nematic liquid crystal phase and smectic liquid crystal phase.
Description
Technical field
The present invention relates to form the compositions used by polarization film and by the compositions system formed used by this polarization film
The polarization film produced and manufacture method etc. thereof.
Background technology
Liquid crystal indicator in recent years, the requirement to its filming is more and more higher, meanwhile, also requires that this liquid crystal
Polarizer used in showing device is more slim material.In order to realize more slim polarizer, begin one's study containing polymerization
Property liquid-crystal compounds compositions institute film forming replace polyvinyl alcohol institute film forming through iodine staining in the past to apply as polarization film
In liquid crystal indicator.
The polarization film that compositions containing polymerizable liquid crystal compound is formed, such as, patent documentation 1 is disclosed only by gathering
The polarization film that conjunction property smectic liquid crystal compound, dichroism pigment, Photoepolymerizationinitiater initiater are formed with Inhibitors, meanwhile, specially
Profit document 2 in disclose only by polymerizable liquid crystal compound, dichroism pigment, polymerization initiator, inhibitor, gelating agent and
The polarization film that solvent is formed.
Prior art
Patent documentation
Patent documentation 1: No. 4719156 publications of Japanese Patent No.
Patent documentation 2: Japan Patent spy's table 2008-547062 publication
Summary of the invention
The problem that invention is to be solved
But, to polarization film, it is desirable to its more slimming and highly transparent.
It is an object of the invention to provide a kind of group that can manufacture used by slim and that there is heigh clarity polarization film
Compound and the polarization film formed by the compositions formed used by this polarization film.
Solve the means of problem
The present invention includes following invention,
[1] a kind of compositions formed used by polarization film, it is characterised in that containing polymerizable liquid crystal compound, polymerization
Property non-liquid crystal compound, dichroism pigment, polymerization initiator and solvent, meet following (A) essential condition and (B) be necessary
Condition.
(A) polymerizable liquid crystal compound and polymerism non-liquid crystal compound all contain polymerizable group;
(B) in the coated film obtained by the compositions formed used by polarization film, contained polymerizable liquid crystal compound will not go out
Existing phase-separated state, but present nematic liquid crystal phase and smectic liquid crystal phase.
(these (A) and (B) essential condition, respectively in hereinafter referred to as " (essential condition A) and " (essential condition B) ".)
[2] compositions used by polarization film of the formation described in basis [1], polymerizable liquid crystal compound is shown in formula (1)
Compound.
U1-V1-W1-X1-Y1-X2-Y2-X3-W2-V2-U2 (1)
(in formula, X1、X2And X3Separately represent the Isosorbide-5-Nitrae-phenylene that can contain substituted radical or can contain
Hexamethylene-Isosorbide-5-Nitrae-the diyl of substituted group.But, X1、X2And X3In at least one be can containing substituted radical Isosorbide-5-Nitrae-
Phenylene.Constitute-the CH of hexamethylene-Isosorbide-5-Nitrae-diyl2-can be replaced by-O-,-S-or-NR-.R represents carbon number 1 ~ 6
Alkyl or phenyl.Y1And Y2Separately expression-CH2CH2-、-CH2O-,-COO-,-OCOO-, singly-bound ,-N=N-,-CRa
=CRb-,-C ≡ C-or-CRa=N-。RaAnd RbSeparately represent hydrogen atom or the alkyl of carbon number 1 ~ 4.U1Table
Show hydrogen atom or polymerism base.U2Represent polymerism base.W1And W2Represent independently of each other singly-bound ,-O-,-S-,-COO-or
Person-OCOO-.V1And V2Represent the alkylidene of the carbon number 1 ~ 20 that can contain substituent group independently of each other, constitute this alkylene
-the CH of base2-can be replaced by-O-,-S-or-NH-.
[3] compositions used by polarization film of the formation described in basis [1] or [2], its polymerism non-liquid crystal compound
For monofunctional acrylate or polyfunctional acrylic ester.
[4] compositions used by polarization film of the formation described in any one of basis [1] ~ [3], its polymerizable liquid crystal compound
The polymerizable group that the polymerizable group contained and polymerism non-liquid crystal compound contain is separately for acryloxy
(CH2=CHCOO-) or methacryloxy (CH2=C(CH3)COO-)。
[5] compositions used by polarization film of the formation described in any one of basis [1] ~ [4], its polymerizable liquid crystal compound
The polymerizable group that the polymerizable group contained contains with polymerism non-liquid crystal compound is identical.
[6] compositions used by polarization film of the formation described in any one of basis [1] ~ [5], its polymerizable liquid crystal compound
Intramolecular contains 1 ~ 2 polymerizable group, and polymerism non-liquid crystal compound molecule is contained within 2 ~ 6 polymerizable groups.
[7] compositions used by polarization film of the formation described in any one of basis [1] ~ [6], its polymerism non-liquid crystal chemical combination
The content of thing, relative to polymerizable liquid crystal compound 100 mass parts, is more than 3 mass parts, below 10 mass parts.
[8] containing following (I), the manufacture method of the polarization film of (II) and (III) operation.
(I) compositions used by polarization film that formed described in any one of [1] ~ [7] is coated on base material or base material
In the alignment films of upper formation, remove solvent and form the operation of coated film;
(II) polymerizable liquid crystal compound contained in the coated film formed in (I) is made to become the work of smectic liquid crystal phase state
Sequence;
(III), in coated film that formed in (II), that polymerizable liquid crystal compound is smectic liquid crystal phase state, polymerization is made
Property liquid-crystal compounds and polymerism non-liquid crystal compound copolymerization operation;
[9] according to the manufacture method of the polarization film described in [8], its base material is the transparent base implementing orientation process.
[10] according to the manufacture method of the polarization film described in [8] or [9], wherein, (II) operation comprises, heat treated
Until the operation (I-of polymerizable liquid crystal compound display nematic liquid crystal phase state contained in the coated film formed in (I) operation
1), cool down with by middle for operation (I-1) coated film that this polymerizable liquid crystal compound is nematic liquid crystal phase state formed, until should
The operation (I-2) of polymerizable liquid crystal compound display smectic liquid crystal phase.
[11] a kind of polarization film, by the manufacture method manufacture described in any one of [8] ~ [10].
[12] according to the polarization film described in [11], its X-ray diffraction measures display bragg peak.
[13] a kind of display device, containing the polarization film described in [11] or [12].
The effect of invention
The compositions used by formation polarization film according to the present invention, it is possible to produce the slim and polarization of high transparent
Light film.
Accompanying drawing explanation
Fig. 1 shows the key of the method for continuous production (volume to volume (Roll to Roll) form) of the polarization film of the present invention
The schematic diagram of part.
Fig. 2 shows the schematic diagram of the section constitution of the polariscopic liquid crystal indicator using the polarization film containing the present invention.
Fig. 3 shows the schematic diagram of the polariscopic layer order of the polarization film containing the present invention arranged in liquid crystal indicator.
Fig. 4 shows the schematic diagram of the polariscopic layer order of the polarization film containing the present invention arranged in liquid crystal indicator.
Fig. 5 shows the composition of the polariscopic liquid crystal indicator (embedded) using the polarization film containing the present invention
Schematic diagram.
Fig. 6 contains the schematic cross-section of the circular polarization light board of the polarization film of the present invention.
Fig. 7 contains the schematic diagram of the method for continuous production of the circular polarization light board of the polarization film of the present invention.
Fig. 8 shows the schematic diagram of the composition of the EL display device of the circular polarization light board using the polarization film containing the present invention.
Fig. 9 shows the schematic diagram of the layer order of the circular polarization light board of the polarization film containing the present invention arranged in EL display device.
Figure 10 shows the schematic diagram of the composition of the EL display device of the circular polarization light board using the polarization film containing the present invention.
Figure 11 shows the composition of the polariscopic projection-type liquid crystal display device using the polarization film containing the present invention
Schematic diagram.
The explanation of symbol
1 transparent base
2 optical alignment films
3 polarization films
4 phase separation layers
100 polarization films
210 the 1st cylinder 210A core
220 the 2nd cylinder 220A core
230 the 3rd cylinder 230A core
240 the 4th cylinder 240A core
211A, 211B apparatus for coating
212A, 212B drying oven
213A polarized light UV irradiation unit
213B light irradiation device
300 auxiliary cylinders
10 liquid crystal indicators
11 antireflection layers
12a, 12b polarization film
13a, 13b phase retardation film
14a, 14b base material
15 color 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 indicators
30 EL display devices
31 circular polarization light board
33 base materials
34 interlayer dielectrics
35 pixel electrodes
36 luminescent layers
37 cathode electrodes
38 desiccant
39 caps
40 thin film transistor (TFT)s
41 ribs
42 thin film sealing films
110 circular polarization light board
111 light sources
112 the 1st lens arras
112a lens
113 the 2nd lens arras
114 polarized light conversion elements
115 compound lenses
121,123,132 dichroic mirrors
122 reflecting mirrors
140R, 140G, 140B liquid crystal panel
142,143 polarizeies
150 cross colour splitting prisms
170 projecting lens
180 projection screens
It is embodied as form
<forming the compositions used by polarization film>
The present invention forms the compositions used by polarization film (the most sometimes referred to as " this compositions ".), containing polymerization
Property liquid-crystal compounds, polymerism non-liquid crystal compound, dichroism pigment, polymerization initiator, solvent.Passed through by this compositions
The polarization film that aftermentioned manufacture method is formed is (following, sometimes referred to as " this polarization film ".), can manufacture and be applicable not only to liquid
Crystal device, the circular polarization light board applying also for organic EL display is (following, sometimes referred to as " this circular polarization light board ".)
First, this compositions is illustrated.
<polymerizable liquid crystal compound>
The polymerizable liquid crystal compound of the present invention contains polymerizable group, and the coated film formed by this compositions will not
Phase-separated state occurs, is the liquid-crystal compounds with the characteristic being shown as nematic liquid crystal phase and smectic liquid crystal phase.
By following manner, the coated film formed by this compositions, confirms whether it meets (essential condition B).At glass baseplate
Upper this compositions of coating, this compositions of coating is not polymerized at polymerizable liquid crystal compound and polymerism non-liquid crystal compound
Under the conditions of implement heat treated and/or reduced pressure treatment, remove solvent.Then, the coated film that heating glass substrates is formed,
Confirm whether the polymerizable liquid crystal compound contained in this coated film is separated, if display nematic liquid crystal phase.Afterwards,
Slowly cool down the coated film of heating, confirm whether the polymerizable liquid crystal compound contained in this coated film is separated, be
No display smectic liquid crystal phase.The texture being identified through such as micropolariscope of nematic liquid crystal phase and smectic liquid crystal phase is seen
Examine, X-ray diffraction measures or Differential Scanning Calorimeter measures and carries out.By the most various microscopical surface observations or transmissometer
Nephelometric turbidity unit measure confirm its whether formed separated.
The smectic liquid crystal that polymerizable liquid crystal compound shows preferred high order smectic phase mutually.High order smectic phase referred to herein has
Smectic B, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase and near
Brilliant L phase, wherein, preferably smectic B, smectic F phase and smectic I phase.The smectic liquid crystal that polymerizable liquid crystal compound shows is mutually
During these high order smectic phases, it is possible to produce higher polarization film of ordered orientation degree.Meanwhile, above-mentioned ordered orientation Du Genggao
This polarization film obtain from hexagonal phase (hexatic) or the Bradley that crystallizes equal higher order structure in X-ray diffraction measures
Lattice peak.
As polymerizable liquid crystal compound, it is preferably 40 ~ 200 by the temperature of nematic liquid crystal phase phase in version to smectic liquid crystal phase
DEG C compound, the compound of more preferably 60 ~ 140 DEG C.
As preferred polymerizable liquid crystal compound, such as, for example there are the compound shown in formula (1) (hereinafter sometimes referred to
" compound (1) ").
U1-V1-W1-X1-Y1-X2-Y2-X3-W2-V2-U2 (1)
[in formula (1), X1、X2And X3Separately representing can be containing the Isosorbide-5-Nitrae-phenylene of substituted radical or permissible
Hexamethylene-Isosorbide-5-Nitrae-diyl containing substituted radical.But, X1、X2And X3In at least 1 be can containing substituted radical 1,
4-phenylene.Constitute-the CH of hexamethylene-Isosorbide-5-Nitrae-diyl2-, can be replaced by-O-,-S-or-NR-.R represent carbon number 1 ~
The alkyl of 6 or phenyl.
Y1And Y2Separately expression-CH2CH2-、-CH2O-,-COO-,-OCOO-, singly-bound ,-N=N-,-CRa=
CRb-,-C ≡ C-or-CRa=N-。RaAnd RbSeparately represent hydrogen atom or the alkyl of carbon number 1 ~ 4.
U1Represent hydrogen atom or polymerizable group.
U2Represent polymerizable group.
W1And W2Separately represent singly-bound ,-O-,-S-,-COO-or-OCOO-.
V1And V2Separately represent the alkylidene of the carbon number 1 ~ 20 that can contain substituted radical, constitute this Asia
-the CH of alkyl2-can be replaced by-O-,-S-or-NH-.
In compound (1), X1、X2And X3In, preferably at least 2 is can be containing the Isosorbide-5-Nitrae-phenylene of substituent group.
Can be containing the Isosorbide-5-Nitrae-phenylene of substituted radical, preferably without substituted radical.Can be containing the ring of substituted radical
Hexane-Isosorbide-5-Nitrae-diyl preferably can contain the anti-of substituted radical containing the trans-cyclohexane-Isosorbide-5-Nitrae-diyl of substituted radical
Formula-preferred unsubstituted group of hexamethylene-Isosorbide-5-Nitrae-diyl.
Can containing substituted radical Isosorbide-5-Nitrae-phenylene or can containing substituted radical hexamethylene-Isosorbide-5-Nitrae-diyl appoint
Meaning substituted radical such as example there are the alkyl of the carbon numbers 1 ~ 4 such as methyl, ethyl and butyl;Cyano group;Halogen atom etc..
The Y of compound (1)1Preferably-CH2CH2-,-COO-or singly-bound, Y2Preferably-CH2CH2-or-CH2O-。
U2It it is polymerizable group.U1It is hydrogen atom or polymerizable group, preferred polymeric group.Preferably U1And U2All
For polymerizable group, likewise it is preferred that be optical polymerism group.Optical polymerism group herein refers to by absorbing luminous energy participation
The group of polymerization.Even if the polymerizable liquid crystal compound containing optical polymerism group can also be polymerized under more cryogenic conditions,
It is favourable on this point.As optical polymerism group, preferably free radical polymerizable group.Free-radical polymerised group refers to
Enough living radicals by being produced by polymerization initiator described later participate in the group of polyreaction.
In compound (1), U1And U2Polymerizable group can be each different, but the most identical.As polymerism base
Group, such as, for example there are vinyl, ethyleneoxy, 1-chlorovinyl, isopropenyl, 4-vinyl phenyl, acryloxy, methyl-prop
Alkene acyloxy, Oxyranyle and oxetanylmethoxy etc..Wherein, preferably acryloxy, methacryloxy and second
Alkenyloxy group, more preferably acryloxy and methacryloxy.
As V1And V2Alkylidene, such as example there are methylene, ethylidene, trimethylene, 1,3-butylidene, 1,
4-butylidene, 1,5-pentylidene, 1,6-hexylidene, 1,7-heptamethylene, 1,8-are octylene, 1,10-decylene, 1,14-sub-14
Alkyl and 1,20-alkylene eicosyl etc..V1And V2The preferably alkylidene of carbon number 2 ~ 12, more preferably carbon number 6 ~ 12
Alkylidene.
As such as can for example there are containing substituted radical arbitrary in the alkylidene of the carbon number 1 ~ 20 of substituted radical
Cyano group and halogen atom etc., but the preferred unsubstituted group of this alkylidene, the most unsubstituted group and the alkylene of straight-chain
Base.
W1And W2Separately preferred singly-bound or-O-.
As the concrete example of compound (1), such as, for example there are the compound etc. that formula (1-1) ~ formula (1-23) represents respectively.This
Time in the concrete example of the compound (1) of sample containing hexamethylene-Isosorbide-5-Nitrae-diyl, its preferred trans body of hexamethylene-Isosorbide-5-Nitrae-diyl.
Polymerizable liquid crystal compound can individually or mix two or more in this compositions.Mix for two or more
Time, preferably at least a kind is compound (1), and more preferably two or more is compound (1).Mix 2 kinds of polymerizable liquid crystals
Mixed proportion during compound is usually 1:99 ~ 50:50, preferably 5:95 ~ 50:50, more preferably 10:90 ~ 50:50.
The polymerization temperature of this compositions is generally below the temperature that polymerizable liquid crystal compound phase in version is smectic phase.Permissible
The polymerization temperature of this compositions is controlled by adjusting the ingredient of this compositions.Obtain polymerizable liquid crystal chemical combination the most in advance
Phase transition is the temperature of smectic phase, adjusts the composition outside polymerizable liquid crystal compound, makes this compositions can be less than its phase
It is polymerized under the temperature conditions of transition temperature.Time in this compositions containing polymerizable liquid crystal compound of more than two kinds, obtain these 2 kinds
The temperature that mixture phase in version is smectic phase of above polymerizable liquid crystal compound, is controlled as described above.
In the compound (1) illustrated, preferred formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1-
8), the compound that formula (1-13), formula (1-14) and formula (1-15) represent.These compounds are by the polymerizable liquid crystal with other
Compound or the interaction of polymerism non-liquid crystal compound, can be easily below smectic phase temperature at phase in version
Under temperature conditions, i.e. it is adequately retained under the mesomorphic state of high order smectic phase and is polymerized.
The content ratio of the polymerizable liquid crystal compound in this compositions, relative to solid constituent 100 matter of this compositions
Amount part, generally in 70 ~ 99.5 mass parts, preferably 80 ~ 99 mass parts, more preferably 80 ~ 94 mass parts, the most preferably 80 ~ 90
Mass parts.The content ratio of compound (1) within the above range time, latter compounds (2) to tend to orientation high, therefore excellent
Choosing.Solid constituent herein is to remove the total amount of composition after solvent in the present compositions.
Polymerizable liquid crystal compound passes through such as, Lub et al.Recl.Trav.Chim.Pays-Bas, and 115,321-
328 (1996), or the known method manufacture described in Japanese Patent No. 4719156 etc..
<polymerism non-liquid crystal compound>
The polymerism non-liquid crystal compound of the present invention is it is meant that containing polymerizable group, even and if during variations in temperature also
Do not have the compound of the mesomorphic state being between solid and liquid.
Polymerism non-liquid crystal compound preferably (i) will not colored by themselves (absorption to visible ray), (ii) have with
The intermiscibility that polymerizable liquid crystal compound mixes equably, and, (iii) will not hinder the liquid that polymerizable liquid crystal compound shows
The formation of crystalline state.
As polymerism non-liquid crystal compound, such as, for example there are monofunctional acrylate and polyfunctional acrylic ester.Single
Sense means containing 1 polymerizable group, multifunctional means containing multiple polymerizable groups.From polymerizable liquid crystal compound
Can be carried out continuously with the polyreaction of polymerism non-liquid crystal compound and set out, preferably polyfunctional acrylic ester.The non-liquid of polymerism
The quantity of the polymerizable group that crystallization compound contains, preferably 1 to 6, more preferably 2 to 6.
Polymerizable group contained by polymerizable group contained by preferred polymeric liquid-crystal compounds and polymerism non-liquid crystal compound
Identical.
It addition, by the compound of at least one selected in polymerizable liquid crystal compound and polymerism non-liquid crystal compound
During containing plural polymerizable group, at least 1 polymerizable group that preferred polymeric liquid-crystal compounds contains, liquid non-with polymerism
At least 1 polymerizable group that crystallization compound contains is identical.
As polymerism non-liquid crystal compound preferably, for example there are and there is above-mentioned (i), (ii) and the feature of (iii),
Intramolecular contains 1 to 6, preferably 2 monofunctional acrylate to 6 polymerizable groups and polyfunctional acrylic ester.
It addition, because above-mentioned monofunctional acrylate and polyfunctional acrylic ester are non-liquid crystal liquid crystal property, preferably without mesomorphic structure.
Meanwhile, the nematic liquid crystal phase of contained polymerizable liquid crystal compound and near in without interference with the coated film obtained by this compositions
In the range of brilliant liquid crystalline phase, intramolecular can contain urethane structure, amino structure, epoxy construction, ethylene glycol structure and polyester
Structure.
Polymerism non-liquid crystal compound can be used alone or mix two or more in this compositions.
Monofunctional acrylate is that its intramolecular contains one by acryloxy (CH2=CH-COO-) and metering system
Acyloxy (CH2=C(CH3)-COO-) and in groups in select group (following, be sometimes designated as (methyl) acryloxy.) change
Compound.When polymerism non-liquid crystal compound is monofunctional acrylate, preferred polymeric liquid-crystal compounds also contains (methyl) third
Alkene acyloxy.
As the monofunctional acrylate containing 1 (methyl) acryloxy, for example there are (methyl) acrylic acid carbon atom
The Arrcostab of several 4 to 16, the β carboxyalkyl ester of (methyl) acrylic acid carbon number 2 to 14, (methyl) acrylic acid carbon number 2
Alkyl-substituted phenyl ester to 14, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group Polyethylene Glycol (methyl) acrylic acid
Ester and (methyl) isobornyl acrylate etc..
Polyfunctional acrylic ester, it is common that its intramolecular contains 2 compounds to 6 methacryloxies.Polymerism
When non-liquid crystal compound is polyfunctional acrylic ester, preferred polymeric liquid-crystal compounds also contains (methyl) acryloyl group epoxide.
As 2 functional acrylates containing 2 (methyl) acryloxies, such as, for example there are 1,3 butylene glycol two (first
Base) acrylate;1,3 butylene glycol (methyl) acrylate;1,6-hexanediol two (methyl) acrylate;Ethylene glycol bisthioglycolate (first
Base) acrylate;Diethylene glycol two (methyl) acrylate;Neopentyl glycol two (methyl) acrylate;Triethylene glycol two (first
Base) acrylate;TEG two (methyl) acrylate;Polyethyleneglycol diacrylate;Double (acryloxies of bisphenol-A
Ethyl) ether;Ethoxylated bisphenol A bis-(methyl) acrylate;Ethoxylated neopentylglycol two (methyl) acrylate;Ethyoxyl
Change neopentyl glycol two (methyl) acrylate and 3-methyl pentanediol two (methyl) acrylate etc..
As the polyfunctional acrylic ester containing 3 to 6 (methyl) acryloxies, for example there are trimethylolpropane tris
(methyl) acrylate;Tetramethylolmethane three (methyl) acrylate;Three (2-ethoxy) isocyanuric acid ester three (methyl) acrylic acid
Ester;Ethoxylated trimethylolpropane three (methyl) acrylate;Propoxylation trimethylolpropane tris (methyl) acrylate;
Tetramethylolmethane four (methyl) acrylate;Dipentaerythritol five (methyl) acrylate;Dipentaerythritol six (methyl) acrylic acid
Ester;Tripentaerythritol four (methyl) acrylate;Tripentaerythritol five (methyl) acrylate;Tripentaerythritol six (methyl) third
Olefin(e) acid ester;Tripentaerythritol seven (methyl) acrylate;Tripentaerythritol eight (methyl) acrylate;
Tetramethylolmethane three (methyl) acrylate and the reactant of anhydride;Dipentaerythritol five (methyl) acrylate and acid
The reactant of acid anhydride;
Tripentaerythritol seven (methyl) acrylate and the reactant of anhydride;
Caprolactone modification trimethylolpropane tris (methyl) acrylate;Caprolactone modification tetramethylolmethane three (methyl) propylene
Acid esters;Caprolactone modification three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate;Caprolactone modification tetramethylolmethane four
(methyl) acrylate;Caprolactone modification dipentaerythritol five (methyl) acrylate;Caprolactone modification dipentaerythritol six (first
Base) acrylate;Caprolactone modification tripentaerythritol four (methyl) acrylate;Caprolactone modification tripentaerythritol five (methyl)
Acrylate;Caprolactone modification tripentaerythritol six (methyl) acrylate;Caprolactone modification tripentaerythritol seven (methyl) third
Olefin(e) acid ester;Caprolactone modification tripentaerythritol eight (methyl) acrylate;Caprolactone modification tetramethylolmethane three (methyl) acrylic acid
Ester and the reactant of anhydride;Caprolactone modification dipentaerythritol five (methyl) acrylate and the reactant of anhydride, with in Radix Chloranthi Serrati
Ester modified tripentaerythritol seven (methyl) acrylate and anhydride etc..It addition, the polyfunctional acrylic ester of above-mentioned expression is concrete
In example, (methyl) acrylate means acrylate or methacrylate.Meanwhile, caprolactone modification mean from
Between alcohol position and (methyl) acryloxy of (methyl) acrylate compounds, introduce the open loop body of caprolactone or open
Cyclopolymer.
Such polyfunctional acrylic ester can use commercial goods.As such commercial goods, such as, for example there are A-
DOD-N、A-HD-N、A-NOD-N、APG-100、APG-200、APG-400、A-GLY-9E、A-GLY-20E、A-TMM-3、A-
TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, HD-N, NOD-N, NPG, TMPT (Xin Zhong village chemistry strain formula meeting
Society's system), " ARONIX M-220 ", with " M-325 ", with " M-240 ", with " M-270 " " M-309 " together " M-310 " together, with " M-
321 ", with " M-350 ", with " M-360 ", with " M-305 ", with " M-306 ", with " M-450 ", with " M-451 ", with " M-408 ", with
" M-400 ", same " M-402 ", same " M-403 ", same " M-404 ", same " M-405 ", same " M-406 " (Toagosei Co., Ltd
System), " EBECRYL11 " " 145 " together, with " 150 ", with " 40 ", with " 140 ", same " 180 ", DPGDA, HDDA, TPGDA, HPNDA,
PETIA, PETRA, TMPTA, TMPEOTA, DPHA, EBECRYL series (DAICEL CYTEC(ダ ィ セ Le サ ィ テ ッ Network) strain
Formula commercial firm system) etc..
As preferred polyfunctional acrylic ester, such as, for example there are the chemical combination that following formula (4-1) ~ (4-14) is respectively shown in
Thing.
The content of the polymerism non-liquid crystal compound in this compositions, relative to the gross mass of this compositions, usually 0.1
~ 20 mass %, preferably 1 ~ 10 mass %, more preferably 3 ~ 7 mass %.More preferably relative to solid constituent 100 mass of this compositions
Part is 0.1 ~ 19 mass parts, the most preferably 1 ~ 15 mass parts, particularly preferred 4 ~ 10 mass parts.Further, relative to poly-
Conjunction property liquid-crystal compounds 100 weight portion, more than particularly preferred 3 mass parts, below 10 mass parts.Polymerism non-liquid crystal compound
Content if within the above range, can in the coated film obtained by this compositions the taking of contained polymerizable liquid crystal compound
In the case of tropism not multilated, make polymerizable component (polymerizable liquid crystal compound and the non-liquid of polymerism in this compositions
Crystallization compound) copolymerization, so preferably.Although it is respective also with polymerizable liquid crystal compound and polymerism non-liquid crystal compound
Kind is different and different, but when the content of polymerism non-liquid crystal compound is more more than above-mentioned scope, this polarization film saturating
Bright property has the tendency of decline, so the most preferred.
<dichroism pigment>
Dichroism pigment is the character that the absorbance with molecular long axis direction is different from the absorbance of short-axis direction
Pigment.If having above-mentioned character, dichroism pigment can be dyestuff, it is also possible to be pigment, can also be multipleization simultaneously
The mixture of compound.
As above-mentioned dichroism pigment, preferably 300 ~ 700nm scope has maximum absorption wavelength (λ MAX).As this
The dichroism pigment of sample, such as, for example there are acridine pigment, piperazine pigment, anthocyanidin, naphthalene pigment, azopigment and anthraquinone
Pigment etc., wherein preferred azopigment.As azopigment, such as, for example there are monoazo pigment, bisazo pigment, trisazo-color
Element, four azopigments and azopigment etc., preferably bisazo pigment and trisazo-pigment.
As azopigment, such as, for example there are the compound (hereinafter sometimes referred to " compound (2) ") shown in formula (2).
A1(-N=N-A2)p-N=N-A3 (2)
[in formula (2), A1And A3Separately represent the phenyl that can contain substituted radical, substituted radical can be contained
Naphthyl or can be containing 1 valency heterocyclic radical of substituted radical.A2Expression can containing substituted radical to phenylene, Ke Yihan
Naphthalene-Isosorbide-5-Nitrae-the diyl of substituted group or can be containing the divalent heterocyclic radical of substituted radical.P represents the integer of 1 ~ 4.P be 2 with
On integer time, multiple A2Can be identical, it is also possible to different.]
As the heterocyclic radical of 1 valency, such as, for example there are by quinoline, thiazole, benzothiazole, thieno thiazole, imidazoles, benzo miaow
The heterocyclic compounds such as azoles, azoles and benzothiazole remove the group of 1 hydrogen atom.2 hydrogen atoms are removed from heterocyclic compound
Group be divalent heterocyclic radical, the concrete example of this heterocyclic compound is described above.
As A1And A3In phenyl, naphthyl and the heterocyclic radical of 1 valency and A2In to phenylene, naphthalene-Isosorbide-5-Nitrae-diyl
And the substituted radical that the heterocyclic radical of divalent arbitrarily contains, such as example there are the alkyl of carbon number 1 ~ 4;Methoxyl group, ethyoxyl
And the alkoxyl of the carbon number 1 ~ 4 such as butoxy;The fluoro-alkyl of the carbon numbers such as trifluoromethyl 1 ~ 4;Cyano group;Nitro;Halogen
Element atom;(substituted-amino refers to have 1 or 2 for the replacement such as amino, diethylamino and pyrrolidinyl or unsubstituted amino
The amino of the alkyl of individual carbon number 1 ~ 6, or 2 replace alkyl and be bound to each other to form the ammonia of alkylidene of carbon number 2 ~ 8
Base.Unsubstituted amino is-NH2-.) it addition, carbon number 1 ~ 6 alkyl concrete example and compound (1) phenylene etc. arbitrarily
The substituent group institute illustrated example having is identical.
In compound (2), the compound that preferably following formula (2-1) ~ formula (2-6) is respectively shown in.
[in formula (2-1) ~ (2-6), B1~B20Separately represent hydrogen atom, the alkyl of carbon number 1 ~ 6, carbon number
(definition of substituted-amino and unsubstituted amino is with above-mentioned for alkoxyl, cyano group, nitro, replacement or the unsubstituted amino of 1 ~ 4
Equally), chlorine atom or trifluoromethyl.
N1 ~ n4 separately represents the integer of 0 ~ 3.
When n1 is more than 2, multiple B2Can the most identical can also be each different,
When n2 is more than 2, multiple B6Can the most identical can also be each different,
When n3 is more than 2, multiple B9Can the most identical can also be each different,
When n4 is more than 2, multiple B14Can the most identical can also be each different.]
As above-mentioned anthraquinone pigment, the compound that preferred formula (2-7) represents.
[in formula (2-7), R1~R8Separately represent hydrogen atom ,-Rx、-NH2、-NHRx、-NRx 2、-SRxOr halogen is former
Son.
RxRepresent alkyl or the aryl of carbon number 6 ~ 12 of carbon number 1 ~ 4.]
As above-mentioned piperazine pigment, the compound that preferred formula (2-8) represents.
[in formula (2-8), R9~R15Separately represent hydrogen atom ,-Rx、-NH2、-NHRx、-NRx 2、-SRxOr halogen
Atom.RxRepresent alkyl or the aryl of carbon number 6 ~ 12 of carbon number 1 ~ 4.]
As above-mentioned acridine pigment, the compound that preferred formula (2-9) represents.
[in formula (2-9), R16~R23Separately represent hydrogen atom ,-Rx、-NH2、-NHRx、-NRx 2、-SRxOr halogen
Atom.RxRepresent alkyl or the aryl of carbon number 6 ~ 12 of carbon number 1 ~ 4.]
In formula (2-7), formula (2-8) and formula (2-9), as RxThe alkyl of the carbon number 1 ~ 4 represented, such as, for example there are
Methyl, ethyl, propyl group, butyl, amyl group and hexyl etc., as the aryl of carbon number 6 ~ 12, such as, for example there are phenyl, toluene
Base, xylyl and naphthyl etc..
As above-mentioned anthocyanidin, compound that preferred formula (2-10) represents and the compound that formula (2-11) represents.
[in formula (2-10), D1And D2The base that separately any one of expression (2-10a) ~ formula (2-10d) represents
Group.
N5 represents the integer of 1 ~ 3.]
[in formula (2-11), D3And D4The separately group shown in expression (2-11a) ~ any one of formula (2-11h).
N6 represents the integer of 1 ~ 3.]
The content of dichroism pigment in this compositions, relative to content 100 mass parts of polymerizable liquid crystal compound, excellent
Select more than 0.1 mass parts, below 30 mass parts, more than more preferably 0.1 mass parts, below 20 mass parts, further preferred 0.1 matter
More than amount part, below 10 mass parts, more than particularly preferred 0.1 mass parts, below 5 mass parts.The content of dichroism pigment is such as
Fruit within the range, can the orientation not multilated of contained polymerizable liquid crystal compound in the coated film obtained by this compositions
In the case of, make this polymerizable liquid crystal compound and polymerism non-liquid crystal compound polymerization, so preferably.Dichroism pigment
Content is too much, probably can hinder the orientation of polymerizable liquid crystal compound.Accordingly it is also possible to the content of dichroism pigment is determined
For making polymerizable liquid crystal compound be maintained in the range of mesomorphic state.
Dichroism pigment can use commercially available material.
<polymerization initiator>
This compositions contains polymerization initiator.This polymerization initiator is the polymerization that can cause polymerizable liquid crystal compound etc.
The compound of reaction.As polymerization initiator, the Photoepolymerizationinitiater initiater of living radical preferably can be produced by the effect of light.
Photoepolymerizationinitiater initiater, such as, for example there are Benzoinum compound, benzophenone cpd, benzene alkyl ketone compound, acyl
Base phosphine oxide compound, triaizine compounds, iodine salt and sulfonium salt etc..
Benzoinum compound, such as, for example there are Benzoinum, Benzoinum methyl ether, Benzoinum ethylether, benzoin isobutyl propyl group
Ether, benzoin isobutyl butyl ether etc..
Benzophenone cpd, such as, for example there are benzophenone, o-benzoyl base benzoic acid methyl ester, 4-phenyl hexichol first
Ketone, 4-benzoyl-4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6-front threes
Base benzophenone etc..
Benzene alkyl ketone compound, such as, for example there are diethoxy acetophenone, 2-methyl-2-morpholine-1-(4-methylthio phenyl
Base) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl
Propane-1-ketone, 1,2-diphenyl-2,2-dimethoxy-ethane-1-ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl)
Phenyl] propane-1-ketone, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl)
The oligomer etc. of propane-1-ketone.
Acylphosphine oxide compound, such as example there are 2,4,6-trimethylbenzoyl diphenyl phosphine oxides and double (2,4,
6-trimethylbenzoyl) phenyl phosphine oxide etc..
Triaizine compounds, such as, for example there are 2, double (trichloromethyl)-6-(4-the methoxyphenyl)-1,3,5-triazines of 4-, 2,
Double (trichloromethyl)-6-(4-methoxyl group the naphthyl)-1,3,5-triazines of 4-, 2, double (trichloromethyl)-6-(the 4-methoxy styrene of 4-
Base)-1,3,5-triazines, 2, double (trichloromethyl)-6-(2-(5-methylfuran-2-base) the vinyl)-1,3,5-triazines of 4-, 2,4-
Double (trichloromethyl)-6-(2-(furan-2-base) vinyl)-1,3,5-triazines, 2, double (trichloromethyl)-6-(2-(the 4-diethyl of 4-
Base amino-2-methyl phenyl) vinyl)-1,3,5-triazines, 2, double (trichloromethyl)-6-(2-(3,4-Dimethoxyphenyl) of 4-
Vinyl)-1,3,5-triazines etc..
Polymerization initiator can use commercial goods.As commercially available polymerization initiator, such as, for example there are " ィ Le ガ キ ュ
ァ(Irgacure)907”、“ィルガキュァ184”、“ィルガキュァ651”、“ィルガキュァ819”、“ィルガキ
ュ ァ 250 ", " ィ Le ガ キ ュ ァ 369 " (チ バ ジ ャ パ Application (strain));" セ ィ Network ォ mono-Le BZ ", " セ ィ Network ォ mono-Le Z ",
" セ ィ Network ォ mono-Le BEE " (Seiko chemistry (strain));" カ ャ キ ュ ァ mono-(kayacure) BP100 " (Japan's chemical medicine (strain));
" カ ャ キ ュ ァ mono-UVI-6992 " (ダ ゥ society system);" ァ デ カ ォ プ ト マ mono-SP-152 ", " ァ デ カ ォ プ ト マ mono-SP-
170 " ((strain) ADEKA);" TAZ-A ", " TAZ-PP " (Japan シ ィ ベ Le ヘ グ Na one society);And " TAZ-104 " (three and ケ ミ カ
Le society) etc..
In this compositions, the content of polymerization initiator suitably can be adjusted according to the kind of polymerizable liquid crystal compound and amount thereof
Joint, is commonly angled relative to content 100 mass parts of polymerizable liquid crystal compound, is 0.1 ~ 30 mass parts.Preferably 0.5 ~ 10 mass parts,
More preferably 0.5 ~ 8 mass parts.The content of polymerization initiator, can be in the coating obtained by this compositions if within the range
In film in the case of the orientation not multilated of contained polymerizable liquid crystal compound, make polymerizable liquid crystal compound and the non-liquid of polymerism
Crystallization compound copolymerization, so preferably.
<solvent>
This compositions contains solvent.It is preferably able to be completely dissolved polymerizable liquid crystal compound, the non-liquid of polymerism as solvent
Crystallization compound and the solvent of dichroism pigment.Likewise it is preferred that show inert solvent when this compositions polyreaction.
As solvent, such as, for example there are, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, Ethylene glycol methyl ether, second two
The alcoholic solvents such as alcohol butyl ether and propylene glycol monomethyl ether;Ethyl acetate, butyl acetate, Ethylene glycol methyl ether acetas, γ-fourth
Lactone or the ester solvent such as methyl proxitol acetate and ethyl lactate;Acetone, methyl ethyl ketone, Ketocyclopentane, hexamethylene
The ketone solvents such as ketone, 2-heptanone and methyl iso-butyl ketone (MIBK);The aliphatic hydrocarbon solvents such as pentane, hexane and normal heptane;Toluene and
The nitrile solvents such as aromatic hydrocarbon solvents, acetonitrile such as dimethylbenzene;The ether solvents such as oxolane and dimethoxy-ethane;Chloroform and chlorine
The chlorinated solvents etc. such as benzene.These solvents can be used alone, it is also possible to multiple combinations are also used.
The content of solvent is relative to total amount preferably 50 ~ 98 mass % of this compositions.In other words, consolidating in this compositions
Body composition preferably 2 ~ 50 mass %.When solid constituent is more than 2 mass %, it is intended to be easier to obtain this polarization film, so excellent
Choosing.During it addition, this solid constituent is below 50 mass %, owing to the viscosity of this compositions is low, the thickness of this polarization film is the most equal
One, have in this polarization film and be difficult to that uneven tendency occurs, so preferably.Meanwhile, such solid constituent, according to make
The thickness of this polarization film made determines.
This compositions can such as example there are control polymerism containing the composition outside mentioned component as such composition
The polyreaction auxiliary agent of the polyreaction of liquid-crystal compounds etc..
<polyreaction auxiliary agent>
This compositions can contain sensitizer further.As sensitizer, preferably photosensitizer.As this sensitizer,
Such as example there are the xanthone based compound such as xanthone and thiaxanthone (such as 2,4-diethyl thioxanthone, 2-isopropyl thiophene
Ton ketone etc.), the anthracene compound such as anthracene and the anthracene (such as, dibutoxy anthracene etc.) containing alkoxyl;Phenothiazine and rubrene etc..
When this compositions contains sensitizer, can more promote the polymerizable liquid crystal compound contained in this compositions and gather
The polyreaction of conjunction property non-liquid crystal compound.The usage amount of such sensitizer, relative to the total amount of polymerizable liquid crystal compound
100 mass parts, preferably 0.1 ~ 30 mass parts, more preferably 0.5 ~ 10 mass parts, further preferred 0.5 ~ 8 mass parts.
In order to make polyreaction stably carry out, this compositions appropriateness can contain polymerization inhibitor.By containing polymerization inhibitor, can control
The polyreaction of polymerizable liquid crystal compound processed and polymerism non-liquid crystal compound carry out degree.
As above-mentioned polymerization inhibitor, such as, for example there are containing hydroquinone and the hydroquinone containing alkoxyl, catechu containing alkoxyl
Phenol (such as butyl catechol etc.), pyrogallic acid, the free radical such as 2,2,6,6-tetramethyls-piperidino epoxide free radical is caught
Catch agent, phenylmercaptan. class, betanaphthyl amine and betanaphthol class etc..
Time in this compositions containing polymerization inhibitor, its content relative to polymerizable liquid crystal compound 100 mass parts, preferably 0.1 ~
30 mass parts, more preferably 0.5 ~ 10 mass parts, further preferred 0.5 ~ 8 mass parts.The content of polymerization inhibitor is if in this scope
In, the situation of the orientation of the polymerizable liquid crystal compound that can contain in not upsetting the compositions formed used by this polarization film
Under be polymerized, therefore this polymerizable liquid crystal compound can more fully be maintained at mesomorphic state and is polymerized.
<levelling agent>
This compositions preferably comprises levelling agent.The mobility of this levelling agent this compositions of adjustable, has and makes to be coated with this
The function that coated film that compositions obtains is more smooth, such as, for example there are surfactant etc..This levelling agent is further preferred, with poly-
Acrylate compounds be main constituent levelling agent and with the compound containing fluorine atom as main constituent levelling agent institute in groups
At least one of middle selection.It addition, polyacrylic acid ester compounds herein is without polymerizable group.
Polyacrylic acid ester compounds is the levelling agent of main constituent, such as, for example there are " BYK-350 ", " BYK-352 ", " BYK-
353 ", " BYK-354 ", " BYK-355 ", " BYK-358N ", " BYK-361N ", " BYK-380 ", " BYK-381 " and " BYK-
392 " [BYK Chemie society] etc..
As containing the fluorine atom compound levelling agent as main constituent, such as example there are " Mega-fac (メ ガ Off ァ ッ
Network) R-08 ", with " 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 (サ mono-Off
ロ Application) S-381 ", with " S-382 ", with " S-383 ", with " S-393 ", with " SC-101 ", with " SC-105 ", " KH-40 " and
" SA-100 " [AGC セ ィ ミ ケ ミ カ Le (strain)];" E1830 ", " E5844 " [(strain) Daikin Fine Chemical (ダ ィ キ Application
Off ァ ィ Application ケ ミ カ Le) institute];" ェ Off ト ッ プ EF301 ", with " EF303 ", with " EF351 " and with " EF352 " [Rhizoma Sparganii
マ テ リ ァ Le electronics chemical conversion (strain)] etc..
Time in this compositions containing levelling agent, its content relative to polymerizable liquid crystal compound 100 mass parts, preferably 0.3
More than mass parts, below 5 mass parts, more than further preferred 0.5 mass parts, below 3 mass parts.The content of levelling agent is above-mentioned
In the range of, polymerizable liquid crystal compound can be made the most parallel-oriented, and tend to make this polarization film obtained more flat
Sliding, so preferably.Relative to polymerizable liquid crystal compound, when the content of levelling agent exceedes above-mentioned scope, this polarized light obtained
Film easily occurs uneven, so the most preferred.It addition, this compositions can contain two or more levelling agent.
<forming method of this polarization film>
Then, illustrate for the method being formed this polarization film by this compositions.First, this compositions is coated in
In the alignment films formed on base material or on base material.In the alignment films that preferred coated is formed on base material.The most saturating as base material
Bright base material.
<transparent base>
Transparent base refers to the base material with the transparency of the degree that can pass through light, especially visible ray.This transparency is
Relative to the light in the range of wavelength 380 ~ 780nm, its transmitance characteristic more than 80%.This transparent base of concrete conduct,
Such as example there are glass baseplate or plastic basis material.It addition, as the plastics of composition plastic basis material, such as example there are polyethylene, gather
The polyolefin such as propylene, norbornene-based polymer;Annular ethylene series resin;Polyvinyl alcohol;Polyethylene terephthalate;Poly-
Methacrylate;Polyacrylate;The fibers such as Triafol T, cellulose diacetate and cellulose acetate propionate
Element ester;PEN;Merlon;Polysulfones;Polyether sulfone;Polyether-ketone;The plastics such as polyphenylene sulfide and polyphenylene oxide.Its
In, from easily being bought and transparency significantly, particularly preferred cellulose esters, annular ethylene series resin, poly-carbon by market
Acid esters, polyethylene terephthalate or polymethacrylates.Such transparent base is used when manufacturing this polarization film
Material, be difficult to cause when transport, this transparent base of keeping breakage, easily operated from the viewpoint of, this transparent base can paste
Attached support base material etc..Meanwhile, as described later, this polarization film when manufacturing circular polarization light board, plastic basis material phase place is sometimes given
Difference property.At this point it is possible to give plastic basis material phase contrast by stretch processing.It addition, explanation gives transparent base phase place subsequently
The method of difference property.
Cellulose esters is at least some of thing formed through acid esterification of institute's hydroxyl in cellulose.Such cellulose
Formed by ester, cellulose ester membrane the most easily buys.Commercially available three cellulose acetate membrane has such as, " Off ジ タ ッ Network film "
(Fuji's description Off ィ Le system (strain));" KC8UX2M ", " KC8UY " and " KC4UY " (U ニ カ ミ ノ Le タ ォ プ ト (strain)) etc..This
The three cellulose acetate membrane that sample is commercially available, can be further used as transparent base after giving phase contrast directly or according to needs.With
Time, the transparent substrate surface formed can be implemented non-glare treated, hard coat process, antistatic process or antireflection and process
It is re-used as transparent base on surface after processing to use.
Annular ethylene series resin refers to by the polymerization of the cyclic olefins such as such as norborene or multi-ring norborneol dilute system monomer
Thing or the thing of copolymer (annular ethylene series resin) composition, this annular ethylene series resin can partly contain open loop structure.With
Time, the annular ethylene series resin containing ring opening moiety can be hydrogenated.Further, this annular ethylene series resin, from inconspicuous
Affect increase hygroscopicity transparent, inconspicuous to set out, can be cyclic olefin and chain olefin or vinylation aromatic compound
The copolymer of (styrene etc.).Its intramolecular of this annular ethylene series resin can introduce polar group simultaneously.
When annular ethylene series resin is cyclic olefin and chain olefin or the copolymerization of the aromatic compound containing vinyl
During thing, this chain olefin is ethylene or propylene etc., simultaneously vinylation aromatic compound be styrene, α-methyl styrene and
Alkyl-substituted styrene etc..In such copolymer, derive from the content ratio of construction unit of cyclic olefin relative to ring-type
The full construction unit of olefin-based resin, at 50 moles of below %, in the scope of such as 15 ~ 50 moles of about %.Work as cycloolefin
When resin is the terpolymer that cyclic olefin obtains with vinylation aromatic compound with chain olefin, such as, from chain
The content ratio of the construction unit of alkene, is come at 5 ~ 80 moles of about % relative to the full construction unit of this annular ethylene series resin
It is 5 ~ 80 moles of about % from the content ratio of the construction unit of vinylation aromatic compound.The ring of such terpolymer
Shape olefin-based resin, when manufacturing this annular ethylene series resin, has the advantage that the usage amount of high price cyclic olefin is fewer.
Annular ethylene series resin the most commercially buys.As commercially available annular ethylene series resin, such as, for example there are
" Topas " [Ticona society (German)];" ァ mono-ト Application " [JSR (strain)];" ゼ ォ ノ ァ (ZEONOR) " and " ゼ ォ ネ ッ Network ス
(ZEONEX) " [Japan ゼ ォ Application (strain)];" ァ ペ Le " [Mitsui Chemicals (strain) system] etc..Such annular ethylene series resin example
Masking mode as known to by solvent casting process or extrusion by melting etc. prepares film (annular ethylene series resin film).Meanwhile, also
The annular ethylene series resin film of commercially available film-forming state can be used.Such as lift as such commercially available annular ethylene series resin film
Example has " ェ ス シ mono-Na " and " SCA40 " [hydrops chemical industry (strain)];“ゼォノァフィルム”[ォプテス
(strain)];" ァ mono-ト Application Off ィ Le system " [JSR (strain)] etc..
Then, the method for the phase contrast of simple declaration imparting plastic basis material.Plastic basis material, by known drawing process
Its phase contrast can be given.Such as, getting out plastic basis material and be wound into the cylinder (spool body) of cylinder, plastic basis material is continuous
Ground exports from such spool body uncoiling, and the plastic basis material that uncoiling exports is transported to heating furnace.The design temperature of heating furnace exists
Near the glass transition temperature of plastic basis material in the range of (DEG C) ~ [glass transition temperature+100] (DEG C), preferably vitrification
The scope of (DEG C) ~ [glass transition temperature+50] (DEG C) near transition temperature.In this heating furnace, toward the advance side of plastic basis material
To or during the stretching of vertical with advance side direction, adjust carriage direction or tension force, be allowed to tilt with arbitrary angle, carry out list
The hot-stretch of axle or twin shaft processes.Stretching multiplying power generally in the range of about 1.1 ~ 6 times, preferably about 1.1 ~ 3.5 times
Scope.Meanwhile, as the method stretched at incline direction, if the side continuously axis of orientation tilted with desired angle
Method is i.e. not particularly limited, and can use known drawing process.Such drawing process can enumerate such as Japanese Patent Laid-Open
The method that clear 50-83482 publication or Japanese Patent Laid-Open 2-113920 publication are recorded.
The thickness of transparent base, from having the weight of energy practical operation degree and may insure that it has the sufficient transparency
Set out, the thinnest, but excessive thin meeting tend to intensity decline, machinability low.The suitable thickness of glass baseplate is such as 100
About ~ 3000 μm, preferably 100 ~ 1000 μm.The suitable thickness of plastic basis material about such as 5 ~ 300 μm, preferably 20 ~ 200 μm.
When this polarization film is used as aftermentioned circular polarization light board, transparent when using especially as the circular polarization light board of mobile machine purposes
Base material thickness, the thinnest, when using glass baseplate, preferred thickness is about 100 ~ 500 μm, thickness when using plastic basis material
About preferably 20 ~ 100 μm.It addition, when giving plastic basis material phase contrast by stretching, before the thickness after stretching is by stretching
Thickness and stretching ratio determine.
<alignment films>
On the base material used when manufacturing this polarization film, it is preferably formed as alignment films.Now, this compositions is coated in orientation
On film.So this alignment films preferably has is coated with this compositions without the solvent resistance dissolved.The most preferably removing solvent
With make the heat treated of liquid crystal aligning has thermostability.As such alignment films, it is possible to use orientation polymer shape
Become.
As above-mentioned orientation polymer, such as there can be exemplified intramolecular have the polyamide of amido link or gelatin class,
Intramolecular has polyimides and hydrolysate i.e. polyamic acid, polyvinyl alcohol, the alkyl-modified polyvinyl alcohol of imide bond, gathers
Acrylamide, polyazole, polymine, polystyrene, polyvinyl pyrrolidone, polyacrylic acid or polyacrylate etc.
Polymer.Wherein, preferably polyethylene alcohol.Formed alignment films these orientation polymer can be used alone, it is also possible to 2 kinds with
On be used in mixed way.
Orientation polymer, as the orientation polymer composition dissolved in a solvent (containing orientation polymer
Solution), by being coated on base material, alignment films can be formed on the substrate.As this solvent, such as, for example there are, water;First
The alcoholic solvents such as alcohol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether;
Ethyl acetate, butyl acetate, ethylene glycol, methylether acetate, gamma-butyrolacton, methyl proxitol acetate and lactic acid second
The ester solvents such as ester;The ketone such as acetone, methyl ethyl ketone, Ketocyclopentane, Ketohexamethylene, methyl amyl ketone and methyl iso-butyl ketone (MIBK) are molten
Agent;The aliphatic hydrocarbon solvents such as pentane, hexane and heptane;The nitrile solvents such as the aromatic hydrocarbon solvents such as toluene and dimethylbenzene, acetonitrile;
The ether solvents such as oxolane and dimethoxy-ethane;The chlorine such as chloroform and chlorobenzene replaces hydrocarbon solvent etc..These organic solvents can
To be used alone, it is also possible to multiple be applied in combination.
Simultaneously in order to form alignment films, as orientation polymer composition, it is possible to use commercially available aligning film material.As
At marketed aligning film material, such as example there are サ Application ェ バ mono-(registered trade mark, Nissan Chemical Industries (strain) is made) or
ォ プ ト マ mono-(registered trade mark, JSR (strain)) etc..
As the method forming alignment films on above-mentioned base material, such as example there are be coated with on above-mentioned base material above-mentioned orientation gather
Polymer composition or commercially available aligning film material, then, by annealing, can form alignment films on above-mentioned base material.Such
The thickness of the alignment films arrived is such as in the scope of the scope of 10nm ~ 10000nm, preferably 10nm ~ 1000nm.
In order to above-mentioned alignment films being given orientation anchorage force, the most preferably carry out rub (friction).By giving
Orientation anchorage force can make polymerizable liquid crystal compound be orientated with desired direction.
As the method giving orientation anchorage force by friction, such as, for example there are the rotation getting out be wound with friction cloth
Friction roll, on base material formed alignment films formation coated film laminate be placed on platform, be transported to the friction being rotating
Cylinder, makes the method that this alignment films formation coated film contacts with the friction roll being rotating.
At the same time it can also be use so-called optical alignment film.Optical alignment film refers to, generally passing through will be containing having photoreactivity
The compositions (following sometimes referred to as " formation compositions used by light redirecting layer ") of the polymer of group or monomer and solvent
It is coated on base material, base material is formed light orientation and lures aliquation, irradiated by polarized light (preferably polarized light UV) and give light and be orientated
Lure aliquation to be orientated anchorage force, thus be formed with the alignment films of light redirecting layer.Photoreactive group is the irradiation (illumination by light
Penetrate) and produce the group of liquid crystal aligning ability.Concrete, it is to be irradiated by light to occur the induction of product molecule to be orientated or different
Structure reaction, dimerization reaction, photo-crosslinking, or photolysis reactions are such, cause the base of the photoreaction of liquid crystal aligning ability
Group.In this photoreactive group, there is dimerization reaction or photo-crosslinking, have excellent orientation and form polarization film
Time be maintained at smectic liquid crystal state, so preferably.As there is the above photoreactive group reacted, preferably comprise unsaturated bond
Particularly double bond, particularly preferably containing by carbon-to-carbon double bond (C=C key), carbon-to-nitrogen double bond (C=N key), nitrogen-nitrogen double bond (N=N
Key) and carbon-oxygen double bond (C=O key) in groups at least one group of selecting.
As the photoreactive group containing C=C key, such as, for example there are vinyl, polyene-based, base, stibazole
The miscellaneous base of base, class, chalcone derivative base and cinnamoyl etc..As the photoreactive group containing C=N key such as example there are containing
Aromatic series Schiff's base and the isostructure group of aromatic series hydrazone.As the photoreactive group containing N=N key, such as, for example there are idol
Pyridyl, azo naphthyl, heteroaromatic azo group, bisazo base and methyl etc. or with azoxybenzide. etc. for basic structure
The group made.As the photoreactive group containing C=O, such as, for example there are benzophenone base, coumarin base, anthraquinonyl and horse
Carry out imide etc..These groups can contain alkyl, alkoxyl, aryl, allyloxy, cyano group, alkoxy carbonyl group, hydroxyl, sulphur
The substituted radical such as acidic group and halogenated alkyl.
Wherein, the photoreactive group of light dimerization reaction, preferably cinnamoyl and chalcone derivative base preferably can occur, because
The polarizing light irradiation amount necessary when its light is orientated is fewer, and, it is readily obtained heat stability and time stability is excellent
Light redirecting layer.Furthermore, it is understood that as the terminal part of the polymer containing photoreactive group, particularly preferably this polymer lateral chain
Point there is the cinnamoyl constituting cinnamic acid structure.
As the solvent of the compositions formed used by light redirecting layer, preferably dissolve the polymer with photoreactive group with
And the solvent of monomer, as this solvent, such as, for example there are the solvent for above-mentioned orientation polymer composition.
Relative to the compositions formed used by light redirecting layer, the polymer containing photoreactive group or the concentration of monomer
Can enter according to the thickness of the polymer containing this photoreactive group or the kind of monomer and optical alignment film to be manufactured
Row suitably regulation, but when representing with solid component concentration, preferably at least 0.2 mass %, the model of particularly preferred 0.3 ~ 10 mass %
Enclose.Meanwhile, in the range of the characteristic of inconspicuous infringement optical alignment film, said composition can comprise polyvinyl alcohol or polyimides
Deng macromolecular material or photosensitizer.
As the method that the compositions formed used by light redirecting layer is coated on base material, can use spin-coating method, squeezing and pressing method,
The rubbing methods such as rotogravure application method, mould cladding process, bar type cladding process and applicator method, or the print process such as flexo method etc. is known
Method.During it addition, manufacture this polarization film, when implementing continuous print manufacture method by aftermentioned volume to volume form, this coating process
Generally use the print processes such as rotogravure application method, mould cladding process or flexo method.
It addition, carry out rubbing or during polarizing light irradiation, if covered, multiple regions that differently-oriented directivity is different can be formed
(pattern).
<manufacture method of this polarization film>
In the alignment films formed on above-mentioned base material or on base material, apply this compositions and remove solvent, obtaining coated film.
As coating method (coating process), such as, for example there are and by the compositions used by orientation polymer or formation light redirecting layer
The method that the method that is coated on base material is identical.
Then, by not gathering at the polymerizable liquid crystal compound contained by coated film and polymerism non-liquid crystal compound
Remove solvent under conditions of conjunction, form coated film.As the method for removing, such as, for example there are natural seasoning, aeration-drying method, add
Heated drying and hypobaric drying method etc..Afterwards, contained polymerizable liquid crystal compound display smectic liquid crystal phase in this coated film is made.
Now, preferably by the characteristic of this polymerizable liquid crystal compound, first make its mesomorphic state display nematic liquid crystal mutually after, then make this to
Row liquid crystal phase transition is smectic liquid crystal phase.The transformation of liquid crystalline phase as mentioned above, uses first by the polymerism contained by coated film
Liquid-crystal compounds is heated to showing the temperature of more than nematic liquid crystal phase temperature, then is cooled to show by this polymerizable liquid crystal compound
The methods such as the temperature showing smectic liquid crystal phase.
Polymerizable liquid crystal compound display smectic liquid crystal phase or the temperature of nematic liquid crystal phase in above-mentioned coated film, such as front institute
State, try to achieve beforehand through the texture of this compositions is observed.
When polymerizable liquid crystal compound and polymerism non-liquid crystal compound polymerization, in order to make polymerizable liquid crystal compound intact
Be maintained at smectic liquid crystal phase, as this polymerizable liquid crystal compound, be preferably used containing polymerizable liquid crystal chemical combination of more than two kinds
This compositions of thing.This compositions using the content ratio that have adjusted this polymerizable liquid crystal compound of more than two kinds has such
Advantage, its via nematic liquid crystal formed mutually smectic liquid crystal mutually after, even if at a temperature of original display crystallization mutually, it is also possible to temporarily
Supercooled state can be in, thus be easily maintained at the mesomorphic state of high order smectic phase.Containing 2 kinds of polymerizable liquid crystal chemical combination
During thing, the content ratio of 2 kinds of polymerizable liquid crystal compounds is usual at 1:99 ~ 50:50, and preferably 5:95 ~ 50:50, more preferably 10:90 ~
50:50。
Then the polymerization process of polymerizable liquid crystal compound and polymerism non-liquid crystal compound is illustrated.
Polymerizable liquid crystal compound in coated film become smectic liquid crystal mutually after, be maintained at this smectic liquid crystal phase, one
Limit, by irradiation energy in coated film, makes polymerizable liquid crystal compound and polymerism non-liquid crystal compound polymerization.Due to this
Compositions contains polymerization initiator, preferably can irradiate the energy making polymerization initiator activate, and preferred energy such as example there are light.Make
For irradiating light, according to the kind of polymerization initiator contained in this coated film, or polymerizable liquid crystal compound and the non-liquid of polymerism
The kind (especially with the kind being polymerized base of this polymerizable liquid crystal compound) of crystallization compound and amount thereof, suitably visible
Light, ultraviolet light and laser institute are middle in groups to be selected light or is carried out by active electron beam.Wherein, from being easily controlled polyreaction
Carrying out or polymerization in the device that relates to be the most widely used setting out, preferably ultraviolet light.It is therefore preferable that select in advance
Select polymerizable liquid crystal compound, polymerism non-liquid crystal compound and the kind of polymerization initiator contained in this compositions, with
Can be polymerized by ultraviolet light.Simultaneously when polymerization, ultraviolet irradiates simultaneously can also be cold by suitable chiller
But coated film is to control polymerization temperature.If by using such cooling way, it is possible to carry out polymerism liquid at lower temperatures
Crystallization compound and the polymerization of polymerism non-liquid crystal compound, even if the material then having above-mentioned base material to use thermostability relatively low also may be used
With the advantage being suitably formed this polarization film.It addition, during polymerization, by covering or developing, it is also possible to obtain patterned partially
Shake light film.
By above-mentioned etc polymerization, the high order that above-mentioned polymerizable liquid crystal compound is maintained at smectic phase, the most illustrates
Under the mesomorphic state of smectic phase, polymerization forms this polarization film.Polymerizable liquid crystal compound is maintained at the mesomorphic state of smectic phase and gathers
Close this polarization film obtained, along with the effect of above-mentioned dichroism pigment, i.e. protect with conventional host and guest's build polarization film
Hold the polarization film making the polymerizations such as polymerizable liquid crystal compound obtain at nematic mesomorphic state to compare, have polarization property more
High advantage.Compare with the polarization film only applying dichroism pigment or lysotropic liquid crystal further, have intensity higher excellent
Point.
The thickness of this polarization film so formed preferably scope below 10 μm more than 0.5 μm, further preferred 1 μm
Below above 5 μm.Therefore, formed used by this polarization film the thickness of coated film, be this polarization film considering to obtain
Determine after thickness.It addition, the thickness of this polarization film, it is through interfering film thickness gauge or laser microscope or contact pin type film thickness gauge
Measure.
The transparency can pass through the assessment of turbidity (Haze) value.Preferably turbidity value is below 5%, and more preferably less than 2%.
Meanwhile, this polarization film so formed is as it has been described above, particularly preferably X-ray diffraction obtains bragg peak in measuring
's.As obtaining this polarization film of such bragg peak, include, for example display and derive from hexagonal phase or crystallization phase
This polarization film of diffraction maximum.
<method for continuous production of this polarization film>
Above the manufacture method of this polarization film is provided a brief description, when business manufactures this polarization film, it is desirable to
It it is the method that can manufacture this polarization film with continuous print.Such method for continuous production is the method using volume to volume form, root
It is referred to as according to occasion " this manufacture method ".It addition, this manufacture method illustrates centered by the base material situation as transparent base.
This manufacture method comprises such as,
Prepare transparent base and be wound on the operation of the 1st cylinder of gained in the 1st core,
The operation of transparent base is sent continuously by the 1st cylinder,
Operation over the transparent substrate is applied continuously by forming the compositions used by above-mentioned light redirecting layer,
Remove the solvent in the compositions used by formation light redirecting layer of coating, be formed continuously the first painting over the transparent substrate
The operation of cloth film,
By this coated film being carried out polarized light UV irradiation, being formed continuously light redirecting layer, forming the operation of optical alignment film,
On this optical alignment film, the operation of this compositions of continuously coating,
It is coated with by being dried under conditions of not being polymerized at polymerizable liquid crystal compound and polymerism non-liquid crystal compound
This compositions of cloth, is formed continuously the operation of the second coated film on this optical alignment film,
The mesomorphic state making in this coated film contained polymerizable liquid crystal compound become smectic liquid crystal mutually after, be maintained at
Smectic liquid crystal phase, by making polymerizable liquid crystal compound be polymerized, is continuously available the operation of polarization film,
The laminate containing transparent base, optical alignment film and polarization film being continuously available is wound around the 2nd core,
Operation to the 2nd cylinder.
This manufacture method is illustrated with reference to Fig. 1 at this.
The 1st cylinder 210 that transparent base winds around the 1st core 210A such as, can easily purchase in market.As
The transparent base bought by market with the form of such cylinder, such as example there are in the transparent base having been illustrated that by
Cellulose esters, annular ethylene series resin, Merlon, polyethylene terephthalate or polymethacrylates institute film forming
Deng.Meanwhile, when this polarization film uses as circular polarization light board, the transparent base imparting phase contrast in advance also easily exists
Market buys, such as, for example there are by cellulose esters, Merlon or the become phase retardation film of annular ethylene series resin etc..
Then, above-mentioned 1st cylinder 210 transparent base is sent.The method sending transparent base is at the 1st cylinder 210
Core 210A in suitable rotary apparatus is set, by this rotary apparatus rotate the 1st cylinder 210.In addition it is also possible to the 1st
Cylinder 210 sends the direction of transparent base, arranges suitable auxiliary cylinder 300, is sent by the rotary apparatus of this auxiliary cylinder 300
Go out transparent base.It is further possible to the 1st core 210A and auxiliary cylinder 300 are arranged rotary apparatus simultaneously, sending
Transparent base gives the tension force of its appropriateness simultaneously.
The transparent base sent by above-mentioned 1st cylinder 210, through apparatus for coating 211A, by this apparatus for coating 211A
Coating in its surface forms the compositions used by light redirecting layer.Continuous print coating described above forms the group used by light redirecting layer
This apparatus for coating 211A of compound, it is common that the printing dress of the coatings such as rotogravure application method, mould cladding process, flexo method can be carried out
Put.
Through the film of apparatus for coating 211A, carry it to drying oven 212A, heated by this drying oven 212A, from
Applied said composition removes solvent, is formed continuously the first coated film over the transparent substrate.As drying oven 212A such as
Hot air type drying oven etc. can be used.The design temperature of drying oven 212A, the formation light according to being coated with by apparatus for coating 211A is taken
In the compositions used by layer, the solvent-laden kind of institute etc. determine.Drying oven 212A can be divided into multiple region simultaneously, draws
Point multiple regions each can set different temperature, it is also possible to multiple drying ovens of configuration series connection, its respective design temperature
Can be different.
Through the first coated film that heating furnace 212A is formed continuously, continuously through polarized light UV irradiation unit 213A, can
The surface of the surface of the first coated film or transparent base side is irradiated by through polarized light UV, forms light redirecting layer, form light
Alignment films.
The base material being so formed continuously and the laminate of optical alignment film, then pass through through apparatus for coating 211B, by this group
After compound is coated on optical alignment film, by polymerizable liquid crystal compound contained in drying oven 212B, shape cost composition
Present the second coated film of smectic liquid crystal phase.Drying oven 212B is except for removing in this compositions being coated with on optical alignment film
Solvent, is additionally operable to give this compositions thermal energy, makes contained polymerizable liquid crystal compound in this compositions be turned mutually by nematic liquid crystal
Become smectic liquid crystal phase.In order to make polymerizable liquid crystal compound be smectic liquid crystal phase by nematic liquid crystal phase in version, drying oven 212B
Multistage heat treated can be carried out.That is, drying oven 212B can be divided into multiple region in the same manner as drying oven 212A, draws
Point multiple regions each set different temperature, it is also possible to multiple drying ovens of configuration series connection, its each design temperature different.
Via the film of above-mentioned drying oven 212B, solvent contained in this compositions is fully removed, poly-in the second coated film
Conjunction property liquid-crystal compounds is maintained at smectic liquid crystal phase, is transported to light irradiation device 213B.Light by this light irradiation device 213B
Irradiate, make polymerizable liquid crystal compound be maintained at smectic liquid crystal phase, together with polymerism non-liquid crystal compound by photopolymerization even
Continue on optical alignment film, form this polarization film.
This polarization film being so formed continuously is as comprising the laminate of transparent base and optical alignment film around volume 2
Core 220A winds, and obtains the form of the 2nd cylinder 220.When obtaining 2 cylinder being wound with this polarization film formed, can be suitable
Sept is used to wind together.
Irradiate as it has been described above, transparent base sequentially passes through 1 cylinder/apparatus for coating 211A/ drying oven 212A/ polarized light UV
Device 213A/ apparatus for coating 211B/ drying oven 212B/ light irradiation device 213B, on optical alignment film over the transparent substrate continuously
Manufacture this polarization film.
Meanwhile, this manufacture method display of Fig. 1 is from the method for continuous production of transparent base to this polarization film but it also may
Such as, transparent base is made to pass sequentially through 1 cylinder/apparatus for coating 211A/ drying oven 212A/ polarized light UV irradiation unit 213A,
The laminate of the base material being formed continuously and optical alignment film is centered around in core, by this laminate with the form manufacture of cylinder, this layer
Long-pending body is sent by this cylinder, and this laminate sent passes sequentially through apparatus for coating 211B/ drying oven 212B/ light irradiation device
213B, produces this polarization film.
This polarization film obtained by this manufacture method, it is shaped as membranaceous and is strip.This this polarization film is used
When aftermentioned liquid crystal indicator etc., desired size can be cut into use according to the scale etc. of this liquid crystal indicator.
Above, to this polarization film centered by the form of the laminate of transparent base/optical alignment film/this polarization film
Constitute and manufacture method illustrates, but as the laminate containing this polarization film, can peel off from such laminate
Optical alignment film or transparent base, it is also possible to be to be laminated with the layer outside transparent base/optical alignment film/this polarization film or film
Form.As these layers and film, as it was previously stated, this polarization film can contain phase retardation film further, it is possible to further
Ground is containing anti-reflection layer or brightness enhancement film.
Meanwhile, can be by transparent base self as phase retardation film, it is thus achieved that phase retardation film/optical alignment film/this polarized light
The circular polarization light board of the form of film or elliptical polarization tabula rasa.Such as use 1/4 wavelength plate that uniaxial tension obtains as phase place
During difference film, by setting the direction of illumination of the polarized light UV carriage direction relative to transparent base as substantially 45 °, can be right by rolling up
Volume mode manufactures circular polarization light board.As 1/4 wavelength plate that used when manufacturing above-mentioned circular polarization light board, preferably have for can
The characteristic that the interior phase difference value of meeting light shortens along with wavelength and diminishes.
Meanwhile, by using 1/2 wavelength plate as phase retardation film, its slow axis of the setting absorption axle with polarization film is made
The linear polarization plate cylinder that angle staggers, forms 1/4 wavelength further in the side relative with the face forming this polarization film
Plate, can obtain broadband circular polarization light board.
<purposes of this polarization film>
This polarization film may be used in various display device.Display device is the device containing display element,
Contain the light-emitting component as luminous source or light-emitting device.As display device, such as, for example there are liquid crystal indicator, have
Organic electro luminescent (EL) display device, inorganic EL (EL) display device, electron emission display (such as field emission
Display device (FED), surface field emission display (SED)), Electronic Paper (use the display dress of e-inks or electrophoresis element
Put, plasm display device, projection type image display apparatus (such as grating light valve (GLV) display device, containing numeral lenticule set
The display device of standby (DMD)) and piezoelectric ceramics display etc..Liquid crystal indicator include transmissive liquid crystal display device, half
Transmissive liquid crystal display device, reflection-type liquid-crystal display device, direct view liquid crystal display device and projection type liquid crystal's display dress
Any one put etc..These display devices can be the display device showing 2 dimension images, it is also possible to is to show standing of 3 d image
Body display device.
This polarization film can show in particularly organic electroluminescent (EL) display device or inorganic EL (EL)
The display device of showing device effectively uses.
Fig. 2 and Fig. 5 is to represent that the liquid crystal indicator using this polarization film (is referred to as " this liquid below according to occasion
Crystal device ".) 10 the generalized schematic of section constitution.Liquid crystal layer 17 is clipped between 2 plate substrate 14a and base material 14b.
Figure 10 is that the EL display device representing and using this polarization film (is referred to as below according to occasion that " this EL shows dress
Put ") the generalized schematic of section constitution.
Figure 11 is the generalized schematic of the composition representing the projection-type liquid crystal display device using this polarization film.
First this liquid crystal indicator 10 shown Fig. 2 illustrates.
Liquid crystal layer 17 side of base material 14a is configured with color filter 15.Color filter 15 is arranged in and clamps the pixel of liquid crystal layer 17
On the position that electrode 22 is relative, black matrix" 20 is arranged on the position relative with the border between pixel electrode.Transparency electrode 16
It is configured at liquid crystal layer 17 side, to cover color filter 15 and black matrix" 20.It addition, can between color filter 15 and transparency electrode 16
With containing protecting film layer (not shown in the diagram).
Liquid crystal layer 17 side of base material 14b, is configured with thin film transistor (TFT) 21 and pixel electrode 22 regularly.Pixel electrode 22
Clip liquid crystal layer 17, be arranged in the position relative with color filter 15.It is configured with between thin film transistor (TFT) 21 and pixel electrode 22 and contains
There is the interlayer dielectric 18 of connecting hole (not shown in the diagram).
As base material 14a and base material 14b, use glass baseplate and plastic basis material.Such glass baseplate or plastics
Base material, uses and the material of the identical material of Exemplary materials of the transparent base of use when manufacturing this polarization film.Meanwhile, this polarization
The transparent base of light film can double as base material 14a and base material 14b.Manufacture the color filter 15 and thin film transistor (TFT) formed on base material
When 21, need the preferred glass baseplate of occasion or the quartz substrate of high-temperature heating operation.
Thin film transistor (TFT) uses most suitable material according to the material of base material 14b.As thin film transistor (TFT) 21, such as, illustrate
There is low-temperature polycrystalline silicon transistor, the glass baseplate formed on the high temperature polysilicon silicon transistor formed in quartz substrate, glass baseplate
Or the amorphous silicon transistor formed on plastic basis material.For making this liquid crystal indicator smaller, can on base material 14b shape
The driving IC of Cheng Gan.
Liquid crystal layer 17 it is configured with between transparency electrode 16 and pixel electrode 22.In order to make between base material 14a and base material 14b
Maintain a certain distance, liquid crystal layer 17 is configured with sept 23.Though it addition, illustrate column spacer in Fig. 2, this sept is also
Being not limited to column, as long as certain distance can be made to keep between base material 14a and base material 14b, shape can be any.
The face contacted with liquid crystal layer 17 in the layer that base material 14a and base material 14b are formed, can be respectively configured can make liquid crystal with
The oriented layer of desired direction orientation.It addition, this polarization film can be placed in inside liquid crystal cell, i.e. connecing with liquid crystal layer 17
Contacting surface side configures this polarization film.Such form is referred to as " embedded (in cell) formula ".
Each component is with base material 14a, color filter 15 and black matrix" 20, transparency electrode 16, liquid crystal layer 17, pixel electrode
22, interlayer dielectric 18 and thin film transistor (TFT) 21 and the sequential laminating of base material 14b.
In such base material 14a and base material 14b accompanying liquid crystal layer 17,14a and the outside of base material 14b, it is provided with
Polarizer 12a and 12b, the polarizer that at least a part of which is 1 comprises this polarization film.
Further, it is preferable to lamination phase separation layer (such as 1/4 wavelength plate or optical compensation films) 13a and 13b.Polarizer
In 12a and 12b, by being inserted by this polarization film in polarizer 12b, this liquid crystal indicator 10 can be given by incident illumination
It is transformed to the function of rectilinearly polarized light.It addition, according to liquid-crystal compounds contained in the structure of liquid crystal indicator or liquid crystal layer 17
Kind, phase retardation film 13a and 13b can not be configured, when transparent base is phase retardation film, use containing this polarization film
During (ellipse) circular polarization light board, owing to this phase retardation film as phase separation layer, therefore can also omit the phase separation layer of Fig. 2
13a and/or 13b.Polariscopic smooth emitting side (outside) containing this polarization film can arrange polarized light further
Film.
Meanwhile, polariscopic outside containing this polarization film (when this polarization film is provided with polarization film further,
Outside it), for preventing the reflection of exterior light from can arrange antireflection film.
As it has been described above, polarizer 12a or 12b of this liquid crystal indicator of Fig. 2 10 can use this polarization film.
By being arranged in polarizer 12a and/or 12b by this polarization film, it is finally reached this liquid crystal display dress
Put the effect of 10 further slimmings.
When this polarization film is in polarizer 12a or 12b, its laminated order is not particularly limited.To this with reference to Fig. 2
A that dotted line surrounds and the expanded view explanation of part B.
Fig. 3 is the enlarged cross section schematic diagram of the part A of Fig. 2.(A1) display polarizer 100 of Fig. 3 makes as polarizer 12a
Used time, arrange by the order of this polarization film 3, optical alignment film 2 and transparent base 1 in phase separation layer 13a side.Meanwhile, Fig. 3
(A2) the order setting of transparent base 1, optical alignment film 2 and this polarization film 3 is pressed in display in phase separation layer 13a side.
Fig. 4 is the expansion schematic diagram of the part B of Fig. 2.(B1) display polarizer 100 of Fig. 4 uses as polarizer 12b
Time, the order pressing transparent base 1, optical alignment film 2 and this polarization film 3 in phase retardation film 13b side is arranged.Meanwhile, Fig. 4
(B2) display polarizer 100 is when using as polarizer 12b, press in phase separation layer 13b side this polarization film 3, optical alignment film 2 with
And the order of transparent base 1 is arranged.
The outside of polarizer 12b, is provided with the backlight module 19 as luminous source.Backlight module 19 is containing light source, leaded light
Body, reflecting plate, diffusion sheet and visual angle tab.As light source, such as example there are electroluminescent, cold-cathode tube, hot cathode tube,
Light emitting diode (LED), laser light source and mercury lamp etc..Meanwhile, light source characteristic can be compareed, select the kind of this polarization film
Class.
When this liquid crystal indicator 10 is transmissive liquid crystal display device, white with produce from light source in backlight module 19
Coloured light incidence light conductor, is reflected plate conversion light path and spreads in diffusion sheet.Diffusion light is adjusted to expectation by visual angle tab
Directivity, by backlight module 19 incident polarization mirror 12b.
As the incident illumination of no polarization, the polarizer 12b of only a certain rectilinearly polarized light permeate crystal panel.This straight line
Polarized light is transformed to circularly polarized light or elliptically polarized light by phase separation layer 13b, successively through base material 14b, pixel electrode 22
Deng arrival liquid crystal layer 17.
According to the presence or absence of potential difference between the transparency electrode 16 relative with pixel electrode 22 herein, contained in liquid crystal layer 17
The state of orientation change of liquid crystal molecule, controls the brightness of the light penetrated by this liquid crystal indicator 10.When liquid crystal layer 17 is at polarization
When light is directed through its state of orientation, this polarized light permeate crystal layer 17, transparency electrode 16, the light of certain particular range of wavelengths
Arriving polarizer 12a through color filter 15, liquid crystal indicator can show the color high-high brightness that color filter determines.
On the contrary, when liquid crystal layer 17 is when changing the state of orientation that polarized light passes it through, permeate crystal layer 17, transparent electrical
The light of pole 16 and color filter 15 is absorbed in polarizer 12a.By this, this pixel display black.In these 2 states
Between state of orientation time, this liquid crystal indicator 10 brightness of the light penetrated is also above-mentioned in the middle of both, and the most now pixel shows
Show Neutral colour.
When this liquid crystal indicator 10 is transflective liquid crystal display device, the polarization photosphere of this polarization film is preferably used
The side thing (circular polarization light board) that lamination 1/4 wavelength plate is become further.Now, pixel electrode 22 is formed containing transparent material
Transmissive portions, the reflecting part that light reflecting material is formed, display image as above-mentioned transmissive liquid crystal display device in transmissive portions.
On the other hand, at reflecting part, exterior light is injected in liquid crystal indicator, 1/4 ripple being had further by this polarization film
The effect of long slab, the circularly polarized light through this polarization film passes through liquid crystal layer 17, reflects through pixel electrode 22, thus be used for showing
Show.
Then, this EL display device 30 to this polarization film of use, illustrate with reference to Fig. 8.In this EL display device
When using this polarization film, preferably this polarization film is made circular polarization light board (be sometimes referred to as below " this circularly polarized light
Plate ".) use afterwards.This circular polarization light board generally has 2 embodiments.Therefore, the composition etc. of this EL display device 30 is being carried out
Before explanation, 2 embodiments to this circular polarization light board, illustrate with reference to Fig. 6.
(A) of Fig. 6 represents the schematic cross-section of the 1st embodiment of this circular polarization light board 110.1st embodiment is
Polarizer 100 arranges on this polarization film 3 this circular polarization light board 110 of phase separation layer (phase retardation film) 4 further.Fig. 6
(B) represent the schematic cross-section of the 2nd embodiment of this circular polarization light board 110.2nd embodiment is as manufacturing partially
The transparent base used during galvanometer 100, uses the transparent base 1 (phase retardation film 4) imparting phase contrast in advance, the most transparent
Base material 1 is this circular polarization light board 110 self having both and having the function as phase separation layer 4.
Herein, the manufacture method of this circular polarization light board 110 is illustrated.2nd embodiment of circular polarization light board 110 is such as
Upper described, manufacture in this manufacture method of this polarization film 100, the transparent of phase contrast can be had been assigned in advance by using
Base material 1, i.e. phase retardation film manufacture as transparent base.1st embodiment of circular polarization light board 110, by this manufacture
Laminating phase retardation film on this polarization film that method B is fabricated by 3, forms phase separation layer 4.It addition, by this manufacturer
Method B, when manufacturing this polarization film 100 with the form of the 2nd cylinder 220, can be exported this polarized light by the 2nd cylinder 220 uncoiling
Film 100, after being cut to the size of regulation, phase retardation film that this polarization film after cutting 100 is fitted;But can also be ready to
The 3rd cylinder that phase retardation film winds around core, manufactures continuously and is shaped as membranaceous and this circular polarization light board 110 of strip.
Method for continuous production to the 1st embodiment of circular polarization light board 110, illustrates with reference to Fig. 7.Such manufacture
Method is made up of following operation:
This polarization film 100 is being exported simultaneously, by wrapped around the 3rd of phase retardation film by the above-mentioned 2nd continuous uncoiling of cylinder 220
The continuous uncoiling of cylinder 230 exports the operation of above-mentioned phase retardation film,
The polarization photosphere that this polarization film 100 of above-mentioned 2nd cylinder 220 uncoiling output is provided with is rolled with by the above-mentioned 3rd
Cylinder winds off the above-mentioned phase retardation film of output and fits continuously, forms the operation of this circular polarization light board 110,
This circular polarization light board 110 formed, around entering the 4th core 240A, obtains the operation of the 4th cylinder 240.
Above the manufacture method of the 1st embodiment of this circular polarization light board 110 is described, the basis in polarizer 100
When polarization film 3 is fitted with phase retardation film, it is possible to use suitable binding agent, by the adhesive layer formed by this binding agent, will
This polarization film 3 is fitted with phase retardation film.
Then this EL display device containing this circular polarization light board 110 is illustrated with reference to Fig. 8.
This EL display device 30 is on the base material 33 forming pixel electrode 35, by the organic function layer 36 as luminous source
And cathode electrode 37 lamination is formed.In the side relative with the organic function layer 36 accompanying base material 33, it is configured with circularly polarized light
Plate 31, such circular polarization light board 31 uses this circular polarization light board 110.By pixel electrode 35 being applied positive voltage, negative electrode electricity
Pole 37 applies to be passed through between negative voltage, pixel electrode 35 and cathode electrode 37 DC current, and organic function layer 36 is luminous.As
The organic function layer 36 of luminous source is made up of electron supplying layer, luminescent layer and hole transporting layer.Penetrated by organic function layer 36
The light gone out, through pixel electrode 35, interlayer dielectric 34, base material 33, circular polarization light board 31 (this circular polarization light board 110).Although
It is the explanation that the organic EL display containing organic function layer 36 is carried out, is also applied for the inorganic EL containing inorganic functional layer
Display device.
Manufacture this EL display device 30, on base material 33, first form the thin film transistor (TFT) 40 of desired shape.Make afterwards
Interlayer dielectric 34 film forming, then makes pixel electrode 35 film forming with sputtering method, forms pattern, and then, lamination becomes organic function layer
36。
Then, at the reverse side of the one side being provided with thin film transistor (TFT) 40 of base material 33, circular polarization light board 31 (this circular polarization is set
Tabula rasa 110).
When this circular polarization light board 110 uses as circular polarization light board 31, to its laminated order with reference to the dotted line of Fig. 8
The expanded view of C portion illustrates.When this circular polarization light board 110 uses as circular polarization light board 31, this this circular polarization light board 110
Middle phase separation layer 4 is arranged in base material 33 side.(C1) of Fig. 9 is that the 1st embodiment of this circular polarization light board 110 is as circularly polarized light
The expanded view that plate 31 uses, (C2) of Fig. 9 is that the 2nd embodiment of this circular polarization light board 110 uses as circular polarization light board 31
Expanded view.
Then the component outside this polarization film 31 (circular polarization light board 110) of this EL display device 30 is carried out briefly
Bright.
As base material 33, such as, for example there are sapphire glass base material, quartz glass base material, soda glass base material and oxidation
The ceramic base materials such as aluminum;The metal bases such as copper;Plastic basis material etc..Although it is not shown in the figure that heat biography can be formed on base material 33
The property led film.As heat conductivity film, such as, for example there are diamond thin (DLC etc.) etc..When pixel electrode 35 is reflection-type, light to
The direction outgoing reverse with base material 33.Therefore transparent material it is not only, it is possible to use the non-permeable material such as rustless steel.Base material can
Be a separately formed, it is also possible to be the lamination base material multiple base materials binded with adhesive.Meanwhile, these base materials do not limit
In tabular, it is also possible to be film.
Polysilicon transistors etc. such as can be used as thin film transistor (TFT) 40.Thin film transistor (TFT) 40 is arranged at pixel electrode 35
End, its size is about 10 ~ 30 μm.It addition, the size of pixel electrode 35 is left in 20 μ m 20 μm ~ 300 μ m 300 μm
Right.
Thin film transistor (TFT) 40 distribution electrode it is provided with on base material 33.The resistance of distribution electrode is low, itself and pixel electrode 35 electricity
Have the function of suppression resistance value after connection, general this distribution electrode use containing Al, Al and transition metal (removing Ti),
In Ti or titanium nitride (TiN) any a kind or of more than two kinds.
Interlayer dielectric 34 is set between thin film transistor (TFT) 40 and pixel electrode 35.Interlayer dielectric 34 can be SiO2Deng oxygen
The inorganic material such as SiClx, silicon nitride is through sputtering or the material of vacuum evaporation film forming, use SOG (ス ピ Application オ Application グ ラ ス;Rotation
Painting formula glass method) film etc. of the resin system material such as silicon oxide layer, photoresist, polyimides and acrylic resin of being formed has
Any one of the material of insulating properties.
Rib 41 is formed on interlayer dielectric 34.Rib 41 is configured at the periphery (adjacent pixels of pixel electrode 35
Between).As the material of rib 41, such as, for example there are acrylic resin and polyimide resin etc..The thickness of rib 41
More than preferably 1.0 μm, below 3.5 μm, more than more preferably 1.5 μm, below 2.5 μm.
Then to the pixel electrode 35 as transparency electrode, the organic function layer 36 as luminous source and cathode electrode 37 shape
The EL element become illustrates.Organic function layer 36 each at least contains hole transporting layer and the luminescent layer of 1 layer, the most successively
Transfer layer, luminescent layer, hole transporting layer and hole injection layer is injected containing electronics.
As pixel electrode 35, such as example there are ITO (Indium sesquioxide. of doped tin), IZO (Indium sesquioxide. of doping zinc),
IGZO、ZnO、SnO2And In2O3Deng, particularly preferred ITO or IZO.The thickness of pixel electrode 35, as long as fully note hole
The thickness entered, preferably about 10 ~ 500nm.
Pixel electrode 35 can pass through vapour deposition method (preferably sputtering method) and be formed.As sputter gas, it is not particularly limited, can make
By the noble gases such as Ar, He, Ne, Kr and Xe or the mixed gas of these gases.
As the constituent material of cathode electrode 37 can use K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn,
The metallic elements such as Zn and Zr, in order to improve the job stability of electrode, are preferably used by illustrating 2 kinds of one-tenth of selection in metallic element
Divide or the alloy body of 3 kinds of compositions.As alloy body, the most such as Ag Mg (Ag:1 ~ 20at%), Al Li (Li:0.3 ~
14at%), In Mg (Mg:50 ~ 80at%) and Al Ca (Ca:5 ~ 20at%) etc..
Cathode electrode 37 is formed by vapour deposition method and sputtering method.The thickness of cathode electrode 37 at more than 0.1nm, preferably 1 ~
More than 500nm.
Hole injection layer has to be made to be injected hole by pixel electrode 35 and becomes easy function, and hole transporting layer has conveying
The function in hole and the function of obstruction electronics, referred to as electric charge injection layer or charge transport layer.
Thickness, the hole injection layer of luminescent layer is merged thickness and the thickness of electronics injection transfer layer with hole transporting layer
Degree is not particularly limited, though can be different according to forming method, but preferably about 5 ~ 100nm.Hole injection layer or cavity conveying
Layer can use various organic compound.When forming hole injection transfer layer, luminescent layer and electronics injection transfer layer, from permissible
The point forming homogenizing thin film considers, it is possible to use vacuum vapour deposition.
Organic function layer 36 as luminous source, it is possible to use utilize the material of luminescence (fluorescence) of singlet exciton, profit
With the material of the luminescence (phosphorescence) of triplet excitons, containing utilize singlet exciton luminescence (fluorescence) material with utilize three lines
The material of the material of the luminescence (phosphorescence) of state exciton, the material formed by Organic substance, containing the material formed by Organic substance
With the material of material formed by inorganic matter, macromolecular material, low molecule material, containing macromolecular material and low molecule material
Material etc..But it is not limited to this, uses the organic function layer 36 as various material known to used by EL element
May be used in this EL display device 30.
Space between cathode electrode 37 and cap 39 is configured with desiccant 38, because organic function layer 36 is weak to
Wet.Absorb moisture by desiccant 38 and be possible to prevent the deterioration of organic function layer 36.
Figure 10 represents the skeleton diagram of the section constitution of other modes of this EL display device 30.This this EL display device 30 has
There is the closed construction employing thin film sealing film 41, it is also possible to obtained emergent light by the reverse side of array base material.
As thin film sealing film 41, being preferably used on the film of electrochemical capacitor evaporation has the DLC film of DLC (diamond like carbon).
DLC film has and is very difficult to by the characteristic of moisture penetration, and moisture-proof characteristic is higher.Meanwhile, DLC film etc. directly can be deposited with at electrode
The surface of 37 is formed.It is also possible to resin film and metallic film multilamellar lamination form thin film sealer 41.
As mentioned above, it is provided that a kind of polarization film (this polarization film) with novelty that the present invention relates to, Yi Jihan
There is the display device (this liquid crystal indicator and this EL display device) with novelty of this polarization film.
Finally, the projection-type liquid crystal display device using this polarization film is illustrated.
Figure 11 is the skeleton diagram representing the projection-type liquid crystal display device using this polarization film.
Polarizer 142 and/or the polarizer 143 of this projection-type liquid crystal display device use this polarization film.
As luminous source light source (such as high voltage mercury lamp) by 111 injection light shafts, first pass around the 1st lens arra
112, the 2nd lens arra 113, polarized light conversion element 114, compound lens 115, it is achieved the brightness in Reflect light line area of beam equal
One change is photochemical with polarization.
Specifically, light source 111 light shafts penetrated, be formed as the 1st rectangular lens arra by lenticule 112a
112 are divided into multiple small light shafts.Configure the 2nd lens arra 113 and compound lens 115, so that divided light
Bundle irradiates the entirety of 3 liquid crystal panels 140R, 140G, 140B as lighting object, therefore, each liquid crystal panel light incident side respectively
Surface is integrally formed the most homogeneous illumination.
Polarization 114 is made up of polarized beam separation array, is arranged in the 2nd lens arra 113 saturating with compound
Between mirror 115.Thus, the random polarized light from light source can be converted to the polarized light with specific polarization light direction in advance,
Reduce in the polariscopic light loss of aftermentioned light incident side, it is achieved improve the effect of picture brightness.
Brightness homogenization as above and polarize photochemical light, via reflecting mirror 122, pass sequentially through dichroic mirror 121,
123,132 3 primary colors of RGB are separated, separate to red channel, green channel, blue channel, be incident to liquid crystal panel respectively
140R、140G、140B。
In liquid crystal panel 140R, 140G, 140B, being configured with polarizer 142 at its light incident side respectively, exiting side is configured with partially
Galvanometer 143.This polarizer 142, polarizer 143 can use this polarization film.
The polarizer 142 configured in each light path of RGB and polarizer 143, be configured to respective absorption axle orthogonal.Each light path
Each liquid crystal panel 140R, 140G, 140B of middle configuration, is had the polarized light state of each pixel controlled by picture signal
It is transformed to the function of light quantity.
This polarization film 100 is by selecting to be suitable for the kind of dichroism pigment of respective channel, as blue channel, green
The polarization film that in chrominance channel and red channel, in arbitrary light path, durability is all excellent is all useful.
According to the view data of liquid crystal panel 140R, 140G, 140B, enter according to the absorbance transmission different with each pixel
Penetrate the optical image that light is made, synthesize in cross colour splitting prism 150, by projecting lens 170, projection screen 180 amplifies and throws
Shadow.
As Electronic Paper, can enumerate and be orientated, by optical anisotropy and dye molecule, the dress that such molecule carries out showing
Put;Moved by electrophoresis, particle, crystal grain rotates, the particle of phase change etc carries out the device that shows;Entered by one end of film
The mobile device carrying out showing of row;The device shown is carried out by the color development/phase change of molecule;It is absorbed into by the light of molecule
The device of row display;Be combined with hole by electronics and be produced from the device etc. that luminescence is indicated.More specifically, can enumerate micro-
Capsule-type electrophoresis, horizontal motion electrophoresis, vertically-moving electrophoresis, spherical twist ball type, magnetic twist ball type, cylinder reverse ball
Type, charged toner, electronic powder fluid, magnetophoresis type, magnetic heat seeking, electrowetting, light scattering (transparent/nebulousurine change), cholesteric liquid
Crystalline substance/optical conductive layer, cholesteric liquid crystal, bistability nematic liquid crystal, Ferroelectric liquid Crystals, dichromatic pigment liquid crystal decentralized, can
Dynamic film, according to the colour changing of leuco dye, photochromic, electrochromism, electro-deposition, flexible organic EL etc..Electronic Paper not only can be answered
For text or the personal use of image, apply also for advertisement and show (label) etc..According to this polarization film, electronics can be reduced
The thickness of paper.
As 3 d display device, micro-polarized light of motion the most (Japanese Patent Laid-Open 2002-185983 publication)
The method of alternately arranged different phase retardation film as film (μ Pol), when the blooming of the present invention uses as polarization film,
Pattern can be readily formed by printing, ink-jet, photoetching technique etc., it is therefore possible to shorten the manufacturing process of display device, and not
Need phase retardation film again.
Embodiment
Hereinafter, described in detail the present invention further by embodiment.In following embodiment " % " and " part ", as long as
Record the most especially, represent quality % and mass parts.
In the present embodiment, use following polymerizable liquid crystal compound.
Compound (1-6) (compound that following formula (1-6) represents)
Compound (1-6) is by Lub et al.Recl.Trav.Chim.Pays-Bas, 115,321-328 (1996)
The method synthesis recorded.
(mensuration of phase transition temperature)
The phase transition temperature of compound (1-6), is by obtaining the phase transition temperature by compound (1-6) institute film forming and true
Fixed, its operation is as follows.
In the alignment films formed on glass baseplate, being formed by film formed by compound (1-6), limit is heated, and limit is by polarization
The texture of light microscope (BX-51, Olympus society system) is observed and is determined phase transition temperature.By compound (1-6) institute film forming, can be true
After fixed its is warming up to 120 DEG C, during cooling, it is changed into nematic phase 112 DEG C of phases, is changed into smectic C 110 DEG C of phases,
94 DEG C of phases are changed into smectic B.
Compound (1-7) (compound that following formula (1-7) represents)
Compound (1-7) synthesizes with reference to the synthesis of above-claimed cpd (1-6).
(mensuration of phase transition temperature)
Mensuration mode as the phase transition temperature measuring compound (1-6) determines the phase in version temperature of compound (1-7)
Degree.After compound (1-7) is warming up to 140 DEG C, during cooling, it is changed into nematic phase 133 DEG C of phases, is changed into 118 DEG C of phases
Smectic C, is changed into smectic B 78 DEG C of phases.
Embodiment 1
(preparations of this compositions etc.)
Mixing following compositions, stirs 1 hour at 80 DEG C, obtains this compositions (forming the compositions used by polarization film)
Polymerizable liquid crystal compound;Compound (1-6) 75 parts
Compound (1-7) 25 parts
Dichroism pigment;Compound (2-1-1) 2.5 parts
The D10 pigment that No. 3687130 publications of Japanese Patent No. are recorded
Polymerization initiator;
1-hydroxycyclohexylphenylketone
((ィ Le ガ キ ュ ァ 184: Ciba company limited (チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ society) system)
6 parts
Levelling agent: BYK 361N (BYK-Chemie society system) 1.5 parts
Polymerism non-liquid crystal compound;Polyfunctional acrylic ester (4-5) 5.0 parts
Solvent: Ketocyclopentane 250 parts
(mensuration of phase transition temperature)
In the same manner as compound (1-6) and compound (1-7), obtain this compositions that mode is prepared as described above
The phase transition temperature of the polymerizable liquid crystal compound contained by.It is warming up to 140 DEG C, during cooling, is changed into nematic 109 DEG C of phases
Phase, does not forms phase-separated state, is changed into smectic C 98 DEG C of phases, does not forms phase-separated state, the phase in version when 74 DEG C
For smectic B, do not form phase-separated state.
<manufacture of this polarization film and evaluation>
1. the formation of alignment films
Glass baseplate is used as transparent base.
On this glass baseplate, by spin-coating method pva coating (the fully saponified type of polyvinyl alcohol 1000, and light pure medicine work
Industry Co., Ltd. system) 2 mass % aqueous solutions (formed compositions) used by oriented layer, the dried film forming thickness 100nm.
Then, the surface to the film obtained is implemented friction treatment and is formed oriented layer, making polarization film.Friction treatment uses semi-automatic rubbing
Wipe device (trade name: LQ-008 type, Joyo Engineering Co., Ltd.'s system), by cloth (trade name: YA-20-RW, lucky river chemical industry strain
Formula commercial firm system), in pressure away from 0.15mm, rotating speed 500rpm, carry out under conditions of 16.7mm/s.Through such friction treatment,
Obtain being formed with the laminate 1 of alignment films on glass baseplate.
2. the formation of polarization film
In the alignment films of laminate 1, form the compositions used by above-mentioned polarization film, at 120 DEG C by spin-coating method coating
Hot plate on heat drying 1 minute, be rapidly cooled to room temperature, above-mentioned alignment films formed coated film.In such coated film
The mesomorphic state of contained polymerizable liquid crystal compound is smectic B.Then, with UV irradiation unit (SPOT CURE SP-7;ゥシ
ォ Electric Co., Ltd system), by light exposure 2000mJ/cm2To coated film irradiation ultraviolet radiation under (313nm benchmark), this painting
In cloth film, contained polymerizable liquid crystal compound is maintained under above-mentioned mesomorphic state polymerization, this coated film make polarization film.This
Time by laser microscope (society of Olympus Co., Ltd OLS3000) mensuration polarization film thickness, be 1.6 μm.
3.X ray diffraction determination
For the polarization film obtained, use X-ray diffraction device X ' Pert PRO MPD (ス ペ Network ト リ ス Co., Ltd.
System) carry out X-ray diffraction mensuration.Use Cu as target, produce under conditions of x-ray tube current 40mA, x-ray tube voltage 45kV
Raw X-ray is incident, with 2 in the range of sweep limits 2 θ=4.0 ~ 40.0 ° by differently-oriented directivity by fixing divergent slit 1/2 °
The step width of θ=0.01671 ° is scanned the result measured, and obtains half peak breadth (FWHM)=about near 2 θ=20.24 °
The sharp-pointed bragg peak of 0.1718 °.Meanwhile, entering by the direction parallel and vertical with differently-oriented directivity with polarization film surface
Penetrate and also obtain comparable results.It is about according to the lattice period (order cycle) (d) that peak position is obtainedIt can thus be appreciated that formed
The structure of reflection high order smectic phase.
4. the mensuration of dichroic ratio (DR)
It is determined by the following procedure dichroic ratio.
Use the folding being provided with the subsidiary polarizer on spectrophotometer (Shimadzu Corporation UV-3150)
The device of device, by dijection collimation method, measures maximum absorption wavelength at transmission axial absorbance (A1) and absorb direction of principal axis
Absorbance (A2).This folding device is provided with the mesh screen blocking 50% light quantity in reference side.With the axial extinction of the transmission measured
Degree (A1) and absorb axial absorbance (A2) value calculate than (A2/A1), as dichroic ratio.Dichroic ratio is the highest, then polarized light
The characteristic of film is the most excellent.Absorb axial absorbance (A2) maximum absorption wavelength and the measurement result of dichroic ratio of this wavelength
Displayed in Table 1.
5. the mensuration of turbidity value
For confirming this polariscopic transparency, with transmissometer (HZ-2;ス ガ testing machine (strain) makes) measure turbidity value.It is surveyed
Determine result displayed in Table 1.
Embodiment 2 ~ 8, reference example 1, comparative example 1 ~ 2 in addition to changing kind and the content of polymerism non-liquid crystal compound,
Other cost composition the most processed.Meanwhile, comparative example 3 making group under conditions of being added without polymerism non-liquid crystal compound
Compound, after being coated with and being moved quickly to after drying on the hot plate of 70 DEG C at 120 DEG C, makes polarization film under UV exposes.
The result measured respectively is displayed in Table 1.
In embodiment 9 ~ 15, dichroism pigment changes following structural formula (2-3-1) into, except polymerism non-liquid crystal compound
Outside kind changes with content, other makes polarization film similarly to Example 1.The result measured respectively is displayed in Table 1.
Table 1
There is not phase-separated state in embodiment 1 ~ 15, demonstrates the dichroism of good parallel-oriented property and height.Good
Good parallel-oriented property is because polymerizable liquid crystal compound display nematic liquid crystal phase, and the dichroism of height is because polymerism
Liquid-crystal compounds display smectic liquid crystal phase.
Industrial utilizability
This polarization film is suitable as display device (display).Accordingly, it is capable to manufacture the basis of such polarization film
Compositions industrially has height use value.
Claims (13)
1. a polarization film, is formed by the compositions formed used by polarization film, it is characterised in that described compositions contains poly-
Conjunction property liquid-crystal compounds, polymerism non-liquid crystal compound, dichroism pigment, polymerization initiator and solvent, and below meeting
(A) essential condition and (B) essential condition, described polymerizable liquid crystal compound is maintained at smectic phase,
(A) polymerizable liquid crystal compound and polymerism non-liquid crystal compound all contain polymerizable group;
(B) polymerizable liquid crystal compound contained in the coated film obtained by the compositions formed used by polarization film does not haves
Phase-separated state, and be as cooling and transferred to smectic liquid crystal phase mutually mutually by nematic liquid crystal.
Polarization film the most according to claim 1, it is characterised in that polymerizable liquid crystal compound is the change shown in formula (1)
Compound,
U1-V1-W1-X1-Y1-X2-Y2-X3-W2-V2-U2(1)
In formula, X1、X2And X3It is to represent independently of each other containing substituent group or the Isosorbide-5-Nitrae-phenylene without substituent group or contain
Substituent group or the hexamethylene-Isosorbide-5-Nitrae-diyl without substituent group, but, X1、X2And X3Among at least 1 be containing substituent group or
Isosorbide-5-Nitrae-phenylene without substituent group;Constitute-the CH of hexamethylene-Isosorbide-5-Nitrae-diyl2-replaced by-O-,-S-or-NR-or not by
Replace;R represents alkyl or the phenyl of carbon number 1~6;Y1And Y2Expression-CH independently of each other2CH2-、-CH2O-、-
COO-,-OCOO-, singly-bound ,-N=N-,-CRa=CRb-,-C ≡ C-or-CRa=N-;RaAnd RbRepresent hydrogen independently of each other
Atom or the alkyl of carbon number 1~4;U1Represent hydrogen atom or polymerism base;U2Represent polymerism base, W1And W2Phase
Represent singly-bound ,-O-,-S-,-COO-or-OCOO-independently mutually;V1And V2Represent independently of each other containing substituent group or not
The alkylidene of the carbon number 1~20 containing substituent group, constitutes-the CH of this alkylidene2-replaced by-O-,-S-or-NH-or not
It is replaced.
Polarization film the most according to claim 1 and 2, it is characterised in that polymerism non-liquid crystal compound is simple function third
Olefin(e) acid ester or polyfunctional acrylic ester.
Polarization film the most according to claim 1, it is characterised in that the polymerizable group that polymerizable liquid crystal compound contains
The polymerizable group contained with polymerism non-liquid crystal compound is independently of one another acryloxy (CH2=CHCOO-) or first
Base acryloxy (CH2=C (CH3)COO-)。
Polarization film the most according to claim 1, it is characterised in that the polymerizable group that polymerizable liquid crystal compound contains
The polymerizable group contained with polymerism non-liquid crystal compound is identical group.
Polarization film the most according to claim 1, it is characterised in that polymerizable liquid crystal compound intramolecular contains 1~2
Polymerizable group, polymerism non-liquid crystal compound molecule is contained within 2~6 polymerizable groups.
Polarization film the most according to claim 1, it is characterised in that the content of polymerism non-liquid crystal compound is relative to poly-
Conjunction property liquid-crystal compounds 100 mass parts, is more than 3 mass parts, below 10 mass parts.
8. the manufacture method of a polarization film, it is characterised in that containing following (I), (II) and (III) operation:
(I) compositions used by polarization film that formed described in any one of claim 1~7 is coated on base material or base material
In the alignment films of upper formation, remove solvent and form the operation of coated film;
(II) polymerizable liquid crystal compound contained in the coated film formed in (I) operation is made to become the work of smectic liquid crystal phase state
Sequence;
(III), in coated film that formed in (II) operation, that polymerizable liquid crystal compound is smectic liquid crystal phase state, polymerization is made
Property liquid-crystal compounds and polymerism non-liquid crystal compound copolymerization operation.
The manufacture method of polarization film the most according to claim 8, it is characterised in that base material implements orientation process
Transparent base.
The manufacture method of the polarization film the most according to Claim 8 or described in 9, it is characterised in that (II) operation comprises, and adds
Heat treatment is until polymerizable liquid crystal compound contained in the coated film of formation in (I) operation shows the operation of nematic liquid crystal phase
(I-1), cool down, directly with by middle for operation (I-1) coated film that this polymerizable liquid crystal compound is nematic liquid crystal phase state formed
Operation (I-2) to this polymerizable liquid crystal compound display smectic liquid crystal phase.
11. 1 kinds of polarization films, it is characterised in that by the manufacture method manufacture described in any one of claim 8~10.
12. polarization films according to claim 11, its X-ray diffraction shows bragg peak in measuring.
13. 1 kinds of display devices, it includes the polarization film described in claim 11 or 12.
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JP2020057020A (en) | 2020-04-09 |
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JP2018084845A (en) | 2018-05-31 |
TWI724121B (en) | 2021-04-11 |
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TWI585472B (en) | 2017-06-01 |
TW201331643A (en) | 2013-08-01 |
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KR102089807B1 (en) | 2020-03-16 |
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