CN103333083A - Compound and dichroic dye, and polarizing film - Google Patents

Compound and dichroic dye, and polarizing film Download PDF

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CN103333083A
CN103333083A CN201310064833XA CN201310064833A CN103333083A CN 103333083 A CN103333083 A CN 103333083A CN 201310064833X A CN201310064833X A CN 201310064833XA CN 201310064833 A CN201310064833 A CN 201310064833A CN 103333083 A CN103333083 A CN 103333083A
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polarizing film
liquid crystal
compound
formula
light polarizing
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CN103333083B (en
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大川春树
幡中伸行
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/14—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/30—Preparation of azo dyes from other azo compounds by esterification of —COOH or —SO3H groups
    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/22—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and nitrogen atoms as chain links, e.g. Schiff bases
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/24—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing nitrogen-to-nitrogen bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • C09K19/601—Azoic
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

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  • Engineering & Computer Science (AREA)
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  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
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  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

The subject of the invention provides a polarizing film novel compound with largest absorption and capable of forming high dichroism ratio in a wave length scope of 400-520 nm, and a polarizing film including the novel compound. The invention provides a compound, a composition including the compound and a liquid crystal compound and a polarizing film formed by the composition represented by the formula (1). In the formula (1), Y is a perssad represented by (Y1) or (Y2). R1 is a perssad represented by any one of formula (R1-1)- formula (R1-3). R2 is a perssad represented by any one of formula (R2-1)-formula (R2-6).

Description

Compound and dichroism pigment and light polarizing film
Technical field
The present invention relates to novel cpd and dichroism pigment and used light polarizing film of described dichroism pigment etc.
Background technology
The polarizer that is used for liquid crystal indicator using usually by with iodine staining the film that constitutes of polyvinyl alcohol.On the other hand, nearest liquid crystal indicator requires strong to its filming, and also this is corresponding, and the polarizer is also being pursued the more slim polarizer.As the light polarizing film that the slim polarizer has, the known light polarizing film that contains the dichroism pigment.
For example, in the patent documentation 1, be the light polarizing film that dye material forms though putting down in writing by the specific polyazo of evaporation, the special device that the formation of this light polarizing film need be as the evaporation coating device is so can not say so in industrial advantageous method.On the other hand, in the patent documentation 2, though putting down in writing the light polarizing film that is formed by the composition that contains polymerizable liquid crystal compound with height smectic type Sx phase and dichroism pigment, the light polarizing film that all is not documented in the dichroism pigment that wavelength 400 ~ 520nm has maximum absorption, the composition that contains described dichroism pigment, is formed by described composition.As the yellow that has maximum absorption at wavelength 400 ~ 520nm ~ orange dichroism pigment, putting down in writing the tetrazo with 1,4-naphthyl structure in the patent documentation 3 is pigment.
[prior art document]
[patent documentation]
No. the 3687130th, [patent documentation 1] Japanese Patent
No. the 4719156th, [patent documentation 2] Japanese Patent
No. the 1454637th, [patent documentation 3] Japanese Patent
Summary of the invention
The problem that invention will solve
Yet, the result of inventor's research has been clearly: when making the dichroism pigment (tetrazo is pigment) of patent documentation 3 records and highly the smectic liquid crystal compound making up, under the state between the molecular chain closely that is scattered in by described height smectic liquid crystal compound formation, can only make that dichroic ratio is low, the light polarizing film of polarizing properties difference.The object of the present invention is to provide at wavelength 400 ~ 520nm to have maximum absorption, can form the high light polarizing film of dichroic ratio compound, with described compound be effective constituent the dichroism pigment, contain the composition of described dichroism pigment and polymerizable liquid crystal compound and the light polarizing film that is formed by described composition.
The means of dealing with problems
The present invention includes following invention.
[1] a kind of compound is characterized in that, represents with formula (1).
Figure BDA00002871576900021
[in the formula (1),
Y is formula (Y1) or the represented group of formula (Y2).
Figure BDA00002871576900022
(in the formula, L be Sauerstoffatom or-NR-, R is the alkyl of hydrogen atom or carbonatoms 1 ~ 4.）
R 1Be formula (R 1-1), formula (R 1-2) or formula (R 1-3) represented group.
Figure BDA00002871576900023
(in the formula, ma is 0 ~ 10 integer, and when having 2 ma in same group, these 2 ma are identical or different mutually.* represent bonding position.）
R 2Be formula (R 2-1), formula (R 2-2), formula (R 2-3), formula (R 2-4), formula (R 2-5) or formula (R 2-6) represented group.
Figure BDA00002871576900024
(in the formula, mb is 0 ~ 10 integer.* represent bonding position.）]
[2] a kind of dichroism pigment is characterized in that, the compound of putting down in writing with [1] is effective constituent.
[3] a kind of composition is characterized in that, contains compound and the polymerizable liquid crystal compound of [1] record.
According to the composition of [3] record, it is characterized in that [4] described polymerizable liquid crystal compound is the compound that shows the smectic liquid crystal phase.
[5] according to the composition of [3] or [4] record, it is characterized in that, further contain solvent.
[6] composition of any record of basis [3] ~ [5] is characterized in that, further contains polymerization starter.
[7] a kind of light polarizing film is characterized in that, is formed by the composition of any record of [3] ~ [6].
According to the light polarizing film of [7] record, it is characterized in that [8] maximum absorption wavelength of light polarizing film (λ max1) moves to the wavelength that the maximum absorption wavelength (λ max2) than dichroism pigment is also grown.
According to the light polarizing film of [7] or [8] record, it is characterized in that [9] difference of the maximum absorption wavelength (λ max2) of the maximum absorption wavelength of light polarizing film (λ max1) and dichroism pigment is more than 20nm.
[10] light polarizing film of any record of basis [7] ~ [9] is characterized in that, obtains bragg peak in X-ray diffraction is measured.
[11] a kind of polarizer is characterized in that, has [7] ~ light polarizing film and the transparent substrate of any record of [10].
[12] a kind of manufacture method of the polarizer is characterized in that, has: the operation of the preparation laminate that the alignment films lamination forms on transparent substrate,
The composition of any record of described alignment films coating [3] ~ [6] of described laminate form coated film operation and
Make the operation of the described polymerizable liquid crystal compound polymerization that comprises in the described coated film.
[13] a kind of manufacture method of the polarizer is characterized in that, has: transparent substrate form operation that optical alignment film forms laminate,
The composition of any record of described optical alignment film coating [3] ~ [6] of described laminate form coated film operation and,
Make the operation of the described polymerizable liquid crystal compound polymerization that comprises in the described coated film.
[14] a kind of liquid crystal indicator is characterized in that, possesses [7] ~ light polarizing film of any record of [10].
[15] a kind of circularly polarizing plate is characterized in that, has [7] ~ light polarizing film and 1/4 wavelength plate of any record of [10], satisfies following (A1) and prerequisite (A2).
(A1) the slow axis angulation of the extinction axle of described light polarizing film and described 1/4 wavelength plate is about 45 °;
(A2) value that postpones with the front of described 1/4 wavelength plate of the light measurement of wavelength 550nm is the scope of 100 ~ 150nm.
[16] a kind of organic EL display possesses circularly polarizing plate and organic EL that [15] are put down in writing.
The invention effect
According to the present invention, can be provided at wavelength 400 ~ 520nm and have maximum absorption, can form the high light polarizing film of dichroic ratio compound, with described compound be effective constituent the dichroism pigment, contain the composition of described dichroism pigment and polymerizable liquid crystal compound and the light polarizing film that is formed by described composition.
Description of drawings
[Fig. 1] is the synoptic diagram of continuous manufacture method that comprises the polarizer (this polarizer) of light polarizing film of the present invention.
[Fig. 2] is the synoptic diagram of the relation between the carrying direction D1 of the expression differently-oriented directivity D2 of optical alignment film and film.
[Fig. 3] is the synoptic diagram of section constitution that the liquid crystal indicator of light polarizing film of the present invention has been used in expression.
[Fig. 4] is that expression is for the synoptic diagram of the sequence of this polarizer of the liquid crystal indicator of Fig. 3.
[Fig. 5] is that expression is for the synoptic diagram of the sequence of this polarizer of the liquid crystal indicator of Fig. 3.
[Fig. 6] is the synoptic diagram of section constitution that the EL display unit of light polarizing film of the present invention has been used in expression.
[Fig. 7] is the synoptic diagram of section constitution of the embodiment of expression this polarizer of comprising light polarizing film of the present invention.
[Fig. 8] is the synoptic diagram of an example of the continuous manufacture method of the expression circularly polarizing plate (this circularly polarizing plate) that comprises light polarizing film of the present invention.
[Fig. 9] is that expression is for the synoptic diagram of the sequence of this circularly polarizing plate of the EL display unit of Fig. 6.
[Figure 10] is the synoptic diagram of the section constitution of the expression EL display unit of using light polarizing film of the present invention.
[Figure 11] is the sketch chart that shows the formation of the projection-type liquid crystal display device that has used light polarizing film of the present invention.
Nomenclature
1 transparent substrate
2 optical alignment films
3 light polarizing film
100 polarizers
210 the 1st roller 210A roll up core
220 the 2nd roller 220A roll up core
230 the 3rd roller 230A roll up core
240 the 4th roller 240A roll up core
211A, 211B apparatus for coating
212A, 212B drying oven
213A polarized light UV irradiating unit
The 213B light irradiation device
300 help rolls
10 liquid crystal indicators
12a, the 12b polarizer
13a, 13b phase separation layer
14a, 14b substrate
15 colour filters
16 transparency electrodes
17 liquid crystal layers
18 interlayer dielectrics
19 modules backlight
20 stain matrixes
21 thin film transistors
22 pixel electrodes
23 pads
The 30EL display unit
31 circularly polarizing plates
32 phase retardation films
33 substrates
34 interlayer dielectrics
35 pixel electrodes
36 organic function layers
37 cathode electrodes
38 siccative
39 sealing covers
40 thin film transistors
41 ribs (Rib)
42 diaphragm seal films
The 44EL display unit
111 light sources
112 the 1st lens arras
The 112a lens
113 the 2nd lens arras
114 polarized light conversion elements
115 compound lenses
121,123,132 dichroic mirrors
122 speculums
140R, 140G, 140B liquid crystal panel
142,143 polarizers
150 cross colour splitting prisms (Crossdichroicprism)
170 projection lens
180 projection screens
Embodiment
The invention provides the represented compound of described formula (1) (below, according to circumstances be referred to as " compound (1) ".), with compound (1) be effective constituent the dichroism pigment (below, according to circumstances be referred to as " dichroism pigment (1) ".), contain described dichroism pigment and polymerizable liquid crystal compound composition (below, according to circumstances be referred to as " light polarizing film form use composition ".), by light polarizing film form the light polarizing film that forms with composition (below, according to circumstances be referred to as " this light polarizing film ".）。This light polarizing film not only can be used for liquid crystal indicator aptly, also make to make the circularly polarizing plate that is suitable for organic EL display (below, according to circumstances be referred to as " this circularly polarizing plate ".) become possibility.At first, compound (1) is described.
＜compound (1) 〉
Compound (1) is the represented material of described formula (1).
The preferred form of compound (1) waits to illustrate by each group of enumerating described formula (1).
The rotamerism at the nitrogen benzide position of preferred compound (1) is trans.
Y in the formula (1) is described formula (Y1) or the represented group of formula (Y2), is preferably the represented group of formula (Y1).In formula (Y1) and the formula (Y2), the straight line at two ends is represented bonding position, the bonding position in left side with have the phenylene bonding of azo-group, the bonding position on right side with have R 2The phenylene bonding.L be Sauerstoffatom or-NR-, R is the alkyl of hydrogen atom or carbonatoms 1 ~ 4.As described alkyl, can list methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-and the tertiary butyl etc.Wherein, preferred L be Sauerstoffatom or-NH-, more preferably Sauerstoffatom.
R 1Be described formula (R 1-1), formula (R 1-2) or formula (R 1-3) represented group is preferably formula (R 1-2) and formula (R 1-3) represented group.Formula (R 1-2) 2 ma in the represented group can be identical or different respectively, is preferably identical.Further preferred ma is 0 ~ 5 integer.
R 2Be described formula (R 2-1), formula (R 2-2), formula (R 2-3), formula (R 2-4), formula (R 2-5) or formula (R 2-6) represented group, more preferably formula (R 2-2), formula (R 2-5) or formula (R 2-6) represented group, more preferably formula (R 2-6) represented group.R 2Be formula (R 2-1), formula (R 2-2), formula (R 2-3), formula (R 2-5) or formula (R 2-6) during represented group, the mb that comprises in the preferred described group is 0 ~ 5 integer, more preferably 0 ~ 3 integer.
As preferred compound (1), can list the represented compound of following formula (1-1) ~ formula (1-8) etc.
Wherein, preferred formula (1-1), formula (1-2), formula (1-3), formula (1-5), formula (1-7) and the represented compound of formula (1-8) are preferably formula (1-1), formula (1-2), formula (1-3) and the represented compound of formula (1-7) especially.
Herein, the preparation method to compound (1) describes.Compound (1) can be prepared by following graphic shown reaction by the represented compound of for example formula (1X) [compound (1X)] and the represented compound [compound (1Y)] of formula (1Y).
Figure BDA00002871576900091
Described graphic in, R 1, R 2And Y and above-mentioned equivalent in meaning, Re 1And Re 2It is interreaction and become the group of the represented group of Y.As Re 1And Re 2Combination, can enumerate as combination of combination, carbon acyloxy alkyl and the amino (such amino can be replaced by R) of combination, carbon acyloxy alkyl and the hydroxyl of combination, phosphinylidyne halogen and the amino (such amino can be replaced by R) of combination, phosphinylidyne halogen and the hydroxyl of the combination of carboxyl and hydroxyl, carboxyl and amino (amino can be replaced by R) etc.In addition, though herein to having R 1Compound (1X) and have R 2Compound (1Y) describe, but also can make by suitable protecting group protection R 1The compound that forms and by suitable protecting group protection R 2The compound interreaction that forms afterwards, is made compound (1) by carrying out suitable deprotection reaction.
Reaction conditions when making the reaction of compound (1X) and compound (1Y) can suitably be selected the suitableeest known condition according to the compound (1X) that uses and the kind of compound (1Y).
For example, as Re 1Be carboxyl, Re 2For hydroxyl, Y be-C(=O)-reaction conditions during O-, can enumerate as: in solvent, in the presence of the esterification condensation agent, carry out the condition of condensation.As solvent, can list the solvent of dissolved compound (1X) and compound (1Y) simultaneously such as chloroform.As the esterification condensation agent, can list di-isopropyl carbodiimide (IPC) etc.Herein, further preferred and with the alkali of dimethyl aminopyridine (DMAP) etc.Temperature of reaction can be selected according to the kind of compound (1X) and compound (1Y), but can enumerate the scope as-15 ~ 70 ℃, is preferably 0 ~ 40 ℃ scope.Reaction times can be enumerated the scope as 15 minutes ~ 48 hours.
Can also suitably sample to the reaction mixture in the reaction process, by known analytical procedures such as liquid phase chromatography or vapor-phase chromatographies, the degree of the degree of the disappearance of affirmation compound (1X) and compound (1Y), the generation of compound (1), thus determine the reaction times.
By known method such as recrystallization, redeposition, extraction and various chromatographys or by these operations of combination, can extract compound (1) from reacted reaction mixture.
Compound (1) is as useful for the dichroism pigment of light polarizing film.As long as such dichroism pigment is in the degree that has maximum absorption in the scope of 400 ~ 520nm of significantly not damaging, just can contain compound (1) compound in addition, but the dichroism pigment that is preferably only constituted by compound (1).Dichroism pigment (1) more preferably its maximum absorption is 430 ~ 520nm, is preferably 440 ~ 510nm especially.And if dichroism pigment (1) is the material of the maximum absorption of the described scope of demonstration, then described dichroism pigment (1) just can contain multiple compound (1).
＜light polarizing film forms uses composition 〉
Then, light polarizing film formation of the present invention is described with composition.Light polarizing film forms and contains polymerizable liquid crystal compound with composition.
With respect to polymerizable liquid crystal compound 100 mass parts, preferred light polarizing film formation uses the content of the dichroism pigment (1) in the composition below 50 mass parts, the scope that more preferably 0.1 mass parts is above, 10 mass parts are following, the scope that more preferably 0.1 mass parts is above, 5 mass parts are following.If in described scope, then dichroism pigment (1) is abundant to the solvability of solvent, easily makes this light polarizing film that does not produce defective.In addition, if the content of dichroism pigment (1) is then in the formation of light polarizing film, chaotic preferred thereby the orientation of polymerizable liquid crystal compound is difficult in above-mentioned scope.
Light polarizing film formation of the present invention is described with dichroism pigment (1) constituent in addition in the composition.
＜polymerizable liquid crystal compound 〉
Form with composition polymerization under the state that makes the polymerizable liquid crystal compound orientation by the light polarizing film that will contain dichroism pigment (1) and polymerizable liquid crystal compound, form this light polarizing film.So-called polymerizable liquid crystal compound is the liquid crystalline cpd that intramolecularly has polymerizable group, and preferred especially described polymerizable group is free-radical polymerised group.Free-radical polymerised group refers to participate in the group of Raolical polymerizable.
It can be the compound that shows the nematic liquid crystal phase that light polarizing film of the present invention forms with the polymerizable liquid crystal compound that comprises in the composition, it also can be the compound that shows the smectic liquid crystal phase, can also be to show that nematic liquid crystal reaches smectic liquid crystal both compounds mutually mutually, but be preferably the polymerizability smectic liquid crystal compound that shows the smectic liquid crystal phase at least.Consider from obtaining more excellent this light polarizing film aspect of polarizing properties, the light polarizing film that preferably contains polymerizability smectic liquid crystal compound forms uses composition, further, because of dichroism pigment (1) though be in by polymerizability smectic liquid crystal compound formation, be scattered in the state between the molecular chain closely, also can make this high light polarizing film of dichroic ratio, so can further obtain the effect of described dichroism pigment (1).
As the shown smectic liquid crystal phase of polymerizability smectic liquid crystal compound, more preferably multidimensional smectic liquid crystal phase.Multidimensional smectic liquid crystal described herein refers to that mutually smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K reach smectic L phase mutually, and wherein, more preferably smectic B phase, smectic F reach smectic I phase mutually.If the shown smectic liquid crystal of polymerizable liquid crystal compound is these multidimensional smectic liquid crystal phases mutually, then can make this light polarizing film of ordered orientation Du Genggao.In addition, this light polarizing film of being made mutually by the high multidimensional smectic liquid crystal of ordered orientation degree like this can obtain deriving from hexagonal mutually or the bragg peak of the multidimensional structure that crystallization phases is such in X-ray diffraction is measured.Described bragg peak refers to derive from the peak of the face periodic structure of molecular orientation, forms by light polarizing film of the present invention and uses composition, and the cycle that can make is spaced apart This light polarizing film.
Light polarizing film forms whether show nematic liquid crystal or smectic liquid crystal with the polymerizable liquid crystal compound that comprises in the composition, for example can followingly confirm.Prepare suitable base material, after described base material coating light polarizing film forms with composition formation coated film, can not remove the solvent that contains in the coated film by heat treated or reduced pressure treatment under the condition of polymerization at polymerizable liquid crystal compound.Then, will be heated to the isotropic phase temperature in the coated film that base material forms, check the mesomorphic phase that shows by slowly cooling off by texture observation, X-ray diffraction mensuration or the differential scanning calorimetric measurement of using polarization microscope to carry out.In this checks, for example be preferably especially, show the nematic liquid crystal phase by cooling, further cool off and show the polymerizable liquid crystal compound of smectic liquid crystal phase.Nematic liquid crystal reach mutually smectic liquid crystal mutually in, for example, measure by the nephelometric turbidity unit that uses the surface observation that various microscopes carry out or use the mist degree instrument to carry out and can confirm that polymerizable liquid crystal compound and dichroism pigment (1) are not separated.
Below, list the concrete example as the preferred compound of polymerizable liquid crystal compound that uses in forming with composition in light polarizing film.
As preferred polymerizable liquid crystal compound, can enumerate suc as formula (2) represented compound (below, according to circumstances be referred to as " compound (2) ").
U 1-V 1-W 1-X 1-Y 1-X 2-Y 2-X 3-W 2-V 2-U 2 (2)
[in the formula (2),
X 1, X 2And X 3Independently of each other expression have or do not have substituent 1, the 4-phenylene or have or do not have substituent 1, the 4-cyclohexylidene.But, X 1, X 2And X 3Among at least 1 substituent 1 for having or not having, the 4-phenylene.Constitute have or do not have substituent 1, the 4-cyclohexylidene-CH 2-can by-O-,-S-or-NR-replaces.R is the alkyl or phenyl of carbonatoms 1～6.
Y 1And Y 2Expression-CH independently of each other 2CH 2-,-CH 2O-,-COO-,-OCOO-, singly-bound ,-N=N-,-CR a=CR b-,-C ≡ C-or-CR a=N-.R aAnd R bThe alkyl of representing hydrogen atom or carbonatoms 1～4 independently of each other.
U 1Expression hydrogen atom or polymerizable group.
U 2The expression polymerizable group.
W 1And W 2Represent independently of each other singly-bound ,-O-,-S-,-COO-or-OCOO-.
V 1And V 2Expression has or does not have the alkylidene group of substituent carbonatoms 1～20 independently of each other, constitute described alkylidene group-CH 2-can by-O-,-S-or-NH-replaces.]
In the compound (2), X 1, X 2And X 3Among, preferably at least 2 substituent 1 for having or not having, the 4-phenylene.
Preferably have or do not have substituent 1, the 4-phenylene does not replace.Preferably have or do not have substituent 1, the 4-cyclohexylene is for having or do not have substituent anti-form-1, and the 4-cyclohexylene more preferably has or do not have substituent anti-form-1, and the 4-cyclohexylene does not replace.
Substituent 1 as having or not having, 4-phenylene or have or do not have substituent 1, the substituting group that the 4-cyclohexylene has arbitrarily can list the alkyl of carbonatomss 1 ~ 4 such as methyl, ethyl and butyl; Cyano group; Halogen atom etc.
The Y of preferred compound (2) 1For-CH 2CH 2-,-COO-or singly-bound, preferred Y 2For-CH 2CH 2-or-CH 2O-.
U 2Be polymerizable group.U 1For hydrogen atom or polymerizable group, be preferably polymerizable group.Preferred U 1And U 2Be all polymerizable group, more preferably be all the optical polymerism group.Herein, the optical polymerism group refers to can participate in by the living radical that produced by the aftermentioned Photoepolymerizationinitiater initiater or acid etc. the group of polyreaction.Polymerizable liquid crystal compound with optical polymerism group is can be favourable aspect the polymerization under the cold condition more.
In the compound (2), U 1And U 2Polymerizable group can be mutually different, but be preferably the group of identical type.As polymerizable group, can list vinyl, vinyl oxygen base, 1-chlorovinyl, pseudoallyl, 4-ethenylphenyl, acryloxy, methacryloxy, epoxy ethyl, oxa-cyclobutyl etc.Wherein, be preferably acryloxy, methacryloxy, vinyl oxygen base, epoxy ethyl and oxa-cyclobutyl, more preferably acryloxy.
As V 1And V 2The alkylidene group of the carbonatoms 1 ~ 20 in the represented alkylidene group that has or do not have substituent carbonatoms 1 ~ 20, can list methylene radical, ethylidene, trimethylene, 1,3-butylidene, 1,4-butylidene, 1,5-pentylidene, hexamethylene, 1, the inferior heptyl, 1 of 7-, 8-is octylene, 1, the inferior decyl, 1 of 10-, the inferior tetradecyl of 14-and the inferior eicosyl of 1,20-etc.Preferred V 1And V 2Be the alkylidene group of carbonatoms 2 ~ 12, more preferably the alkylidene group of carbonatoms 6 ~ 12.
As the substituting group that the alkylidene group that has or do not have substituent carbonatoms 1 ~ 20 has arbitrarily, though can list cyano group and halogen atom etc., preferred described alkylidene group does not replace, and does not more preferably replace and the alkylidene group of straight chain shape.
W 1And W 2Be preferably independently of each other singly-bound or-O-.
As compound (2), can list the represented compound of formula (2-1) ~ formula (2-43) etc.When the concrete example of such compound (2) had 1,4-cyclohexylene, preferred such 1, the 4-cyclohexylene was trans body.
Figure BDA00002871576900141
Figure BDA00002871576900151
Figure BDA00002871576900161
Polymerizable liquid crystal compound can separately or be mixed for light polarizing film and form with in the composition more than 2 kinds.In addition, when mixing more than 2 kinds, preferably at least a kind is compound (2).Ratio of mixture during as 2 kinds of polymerizable liquid crystal compounds of mixing is generally 1:99 ~ 50:50, is preferably 5:95 ~ 50:50, more preferably 10:90 ~ 50:50.
Among the compound that illustrates for example (2), be preferably formula (2-5), formula (2-6), formula (2-7), formula (2-8), formula (2-9), formula (2-10), formula (2-11), formula (2-12), formula (2-13), formula (2-14), formula (2-15), formula (2-22), formula (2-24), formula (2-25), formula (2-26), formula (2-27), formula (2-28) and the represented compound of formula (2-29).By the interaction of these compounds and other polymerizable liquid crystal compounds, under the temperature condition that is lower than the crystallization phases transition temperature, namely under the state of the mesomorphic state that fully keeps the height smectic phase, polymerization easily.Particularly, these compounds are preferably under the temperature condition below 60 ℃ below 70 ℃, can carry out polymerization under the state of the mesomorphic state that fully keeps the height smectic phase.
Form the solid state component of using composition with respect to light polarizing film, it is 50 ~ 99.9 quality % that preferred light polarizing film forms proportional with containing of the polymerizable liquid crystal compound in the composition, more preferably 80 ~ 99.9 quality %.If containing of polymerizable liquid crystal compound is proportional in above-mentioned scope, thereby the tendency that then has the orientation of polymerizable liquid crystal compound to uprise is preferred.Herein, solid state component refers to, forms total amount with the composition behind the volatile components such as composition desolventizing from light polarizing film.
Polymerizable liquid crystal compound can be according to for example Lub et al.Recl.Trav.Chim.Pays-Bas, 115,321-328(1996) or the known method of putting down in writing in No. the 4719156th, the Japanese Patent etc. prepare.
＜solvent 〉
Preferred light polarizing film of the present invention forms and contains solvent with composition.As solvent, be preferably the solvent of solvent polymerization liquid crystalline cpd fully and dichroism pigment (1).In addition, be preferably the solvent that light polarizing film formation is inertia with the polyreaction of the polymerizable liquid crystal compound that comprises in the composition.
As solvent, can list alcoholic solvents such as methyl alcohol, ethanol, ethylene glycol, Virahol, propylene glycol, ethylene glycol monomethyl ether, butyl glycol ether and propylene glycol monomethyl ether; Ethyl acetate, butylacetate, ethylene glycol monomethyl ether acetate, gamma-butyrolactone or ester solvents such as propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, pimelinketone, 2-heptanone and methyl iso-butyl ketone (MIBK); Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbon solvents such as toluene and dimethylbenzene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran (THF) and glycol dimethyl ether; Chlorinated solvents such as chloroform and chlorobenzene; Deng.These solvents can use separately, also can multiplely be used in combination.
Form total amount with composition with respect to light polarizing film, preferred solvent to contain proportional be 50 ~ 98 quality %.In other words, preferred light polarizing film formation is 2 ~ 50 quality % with the solid state component in the composition.If solid state component is more than the 2 quality %, thereby then there is the tendency that easily makes this slim light polarizing film preferred.In addition, if described solid state component is below the 50 quality %, then because light polarizing film forms viscosity with composition, the roughly homogeneous that becomes of the thickness by light polarizing film becomes in described light polarizing film that to be difficult for producing inhomogeneous tendency preferred thereby have.In addition, the thickness that can consider light polarizing film is determined such solid state component.
＜polyreaction auxiliary agent 〉
Preferred light polarizing film of the present invention forms and contains polymerization starter with composition.Polymerization starter is the compound of polyreaction that can the initiated polymerization liquid crystalline cpd.As polymerization starter, under cold condition, can cause aspect the described polyreaction, be preferably Photoepolymerizationinitiater initiater.Particularly, can be used as Photoepolymerizationinitiater initiater by the effect generation living radical of light or the compound of acid.Among the Photoepolymerizationinitiater initiater, more preferably produce the material of living radical by the effect of light.
As polymerization starter, can enumerate as st-yrax compound, benzophenone cpd, alkyl phenyl ketone compound, acylphosphine oxide compound, triaizine compounds, salt compounded of iodine and sulfonium salt etc.
As the st-yrax compound, can enumerate as st-yrax, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether etc.
As benzophenone cpd, can enumerate as benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide, 3,3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone and 2,4,6-tri-methyl benzophenone etc.
As the alkyl phenones compound, can enumerate as diethoxy acetophenone, 2-methyl-2-morpholinyl-1-(4-methyl sulfenyl phenyl)-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1,2-phenylbenzene-2,2-dimethoxy-1-ethyl ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl]-oligopolymer of 1-acetone etc.
As the acylphosphine oxide compound, can list 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and two (2,4,6-trimethylbenzoyl) phenyl phosphine oxides etc.
As triaizine compounds, can enumerate two (trichloromethyl)-6-(4-p-methoxy-phenyls as: 2,4-)-1,3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl group naphthyls of 4-)-1,3,5-triazines, 2, two (the trichloromethyl)-6-(4-methoxyl-styrenes of 4-)-1,3,5-triazine, two (the trichloromethyl)-6-[2-(5-methyl of 2,4--2-furyl) vinyl]-1,3, the 5-triazine, two (the trichloromethyl)-6-[2-(2-furyls of 2,4-) vinyl]-1,3, the 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylins of 4--2-aminomethyl phenyl) vinyl]-1,3,5-triazines and 2, two (the trichloromethyl)-6-[2-(3 of 4-, the 4-Dimethoxyphenyl) vinyl]-1,3,5-triazines etc.
Polymerization starter can also use commercially available article.As commercially available polymerization starter, can list " gorgeous good solid (Irgacure) 907 ", " gorgeous good solid 184 ", " gorgeous good solid 651 ", " gorgeous good solid 819 ", " gorgeous good solid 250 ", " gorgeous good solid 369 " (vapour bar Japan (strain)); " Seikuol(セ イ Network オ one Le) BZ ", " Seikuol Z ", " Seikuol BEE " (Seiko chemistry (strain)); " kayacure(カ ヤ キ ユ ア one) BP100 " (Japanese chemical drug (strain)); " kayacure UV I-6992 " (the Dow Chemical Company's system); " Adeka Optomer(ア デ カ オ プ ト マ one) SP-152 ", " Adeka Optomer SP-170 " ((strain) Ai Dike); " TAZ-A ", " TAZ-PP " (Japanese Da Chang Waja society); And " TAZ-104 " (three and chemical society) etc.
When light polarizing film formation contains polymerization starter with composition, its content can form according to light polarizing film and do suitable adjustment with kind and the amount thereof of the polymerizable liquid crystal compound that contains in the composition, usually, content 100 mass parts with respect to polymerizable liquid crystal compound, the content of polymerization starter is 0.1 ~ 30 mass parts, be preferably 0.5 ~ 10 mass parts, more preferably 0.5 ~ 8 mass parts.If the content of polymerization starter is in described scope, then because of can under the situation of the orientation confusion that can not make polymerizable liquid crystal compound, making its polymerization so preferably.
When light polarizing film formation contained Photoepolymerizationinitiater initiater with composition, light polarizing film forms can contain photosensitizer with composition.As photosensitizer, can enumerate as xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone etc.); Anthracene and contain the anthracene compound such as anthracene (for example, dibutoxy anthracene etc.) of alkoxyl group; Thiodiphenylamine and rubrene etc.
When light polarizing film formation contained Photoepolymerizationinitiater initiater and photosensitizer with composition, the polyreaction that light polarizing film forms with the polymerizable liquid crystal compound that contains in the composition was further promoted.
The content of such photosensitizer can be according to also the Photoepolymerizationinitiater initiater of usefulness and kind and the amount thereof of polymerizable liquid crystal compound are done suitable adjustment, usually, content 100 mass parts with respect to polymerizable liquid crystal compound, it is 0.1 ~ 30 mass parts, be preferably 0.5 ~ 10 mass parts, more preferably 0.5 ~ 8 mass parts.
For the polyreaction that makes polymerizable liquid crystal compound is stably carried out, light polarizing film forms can contain stopper with composition.By stopper, can control the degree that the polyreaction of polymerizable liquid crystal compound is carried out.
As stopper, can enumerate as: Resorcinol, contain alkoxyl group Resorcinol, contain pyrocatechol (for example, butyl-catechol etc.), the pyrogallol, 2,2,6 of alkoxyl group, 6-tetramethyl--radical scavengers such as 1-piperidines oxygen base free radical; The thiophenol class; Beta-naphthylamine class and 2-Naphthol class etc.
When light polarizing film formation contains stopper with composition, its content can be done suitable adjustment according to the kind of the polymerizable liquid crystal compound that uses and the content of amount and photosensitizer thereof etc., usually, content 100 mass parts with respect to polymerizable liquid crystal compound, it is 0.1 ~ 30 mass parts, be preferably 0.5 ~ 10 mass parts, more preferably 0.5 ~ 8 mass parts.If the content of stopper is in above-mentioned scope, then because can under the situation of the orientation confusion of the polymerizable liquid crystal compound that light polarizing film is comprised in forming with composition, making its polymerization so preferably.
＜flow agent 〉
Preferred light polarizing film forms and contains flow agent with composition.Flow agent refers to have the material of regulating the function that light polarizing film forms flowability with composition, coated film that the formation of coating light polarizing film is made with composition is more smooth, can list tensio-active agent etc.As preferred flow agent, can list with the polyacrylic acid ester cpds and be the flow agent of principal constituent and be flow agent of principal constituent etc. with the compound of contain fluorine atoms.
As being the flow agent of principal constituent with the polyacrylic acid ester cpds, can list " BYK-350 ", " BYK-352 ", " BYK-353 ", " BYK-354 ", " BYK-355 ", " BYK-358N ", " BYK-361N ", " BYK-380 ", " BYK-381 " reaches " BYK-392 " [Bi Ke chemical company] etc.
Be the flow agent of principal constituent as the compound with contain fluorine atoms, can list " Megafac(メ ガ Off ア Star Network) R-08 ", Megafac " R-30 ", Megafac " R-90 ", Megafac " F-410 ", Megafac " F-411 ", Megafac " F-443 ", Megafac " F-445 ", Megafac " F-470 ", Megafac " F-471 ", Megafac " F-477 ", Megafac " F-479 ", Megafac " F-482 " and Megafac " F-483 " [big Japanese ink chemistry (strain)]; " Surflon(サ one Off ロ Application) S-381 ", Surflon " S-382 ", Surflon " S-383 ", Surflon " S-393 ", Surflon " SC-101 ", Surflon " SC-105 ", " KH-40 " reach " SA-100 " [AGC Seimi Chemical(AGC セ イ ミ ケ ミ カ Le) (strain)]; " E1830 ", " E5844 " [(strain) big aurin refinement institute]; " EFTOP(エ Off ト Star プ) EF301 ", EFTOP " EF303 ", EFTOP " EF351 " and EFTOP " EF352 " [the Mitsubishi Materials electronics changes into (strain)] etc.
When light polarizing film formation contained flow agent with composition, with respect to content 100 mass parts of polymerizable liquid crystal compound, its content was generally more than 0.3 mass parts, below 5 mass parts, is preferably more than 0.5 mass parts, below 3 mass parts.If the content of flow agent is in described scope, then because easily making polymerizable liquid crystal compound carry out horizontal alignment and tendency that the light polarizing film that makes becomes more level and smooth being arranged so preferably.If the content with respect to the flow agent of polymerizable liquid crystal compound surpasses described scope, then have in this light polarizing film that makes, easily to produce inhomogeneous tendency.And light polarizing film forms with composition can contain flow agent more than 2 kinds.
The formation method of＜this light polarizing film 〉
Then, describe formed the method that forms this light polarizing film with composition by light polarizing film.In such method, by being formed, light polarizing film is coated on the base material with composition, preferably be coated on the transparent substrate, form this light polarizing film.Below, transparent substrate is described.
＜transparent substrate 〉
Transparent substrate refers to have and can see through light, particularly can see through the base material of the transparency of the degree of visible light.The described transparency refers to, in the scope of wavelength 380 ~ 780nm to the transmittance of light in the characteristic more than 80%.Particularly, as transparent substrate, can list glass baseplate and plastic basis material etc.As the plastics that constitute plastic basis material, can enumerate as polyolefine such as polyethylene, polypropylene, norbornene-based polymer; Annular ethylene series resin; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylate; Polyacrylic ester; Cellulose ester such as triacetyl cellulose, diacetyl cellulose and cellulose ethanoate propionic ester; PEN; Polycarbonate; Polysulfones; Polyethersulfone; Polyetherketone; Plastics such as polyphenylene sulfide and polyphenylene oxide.Wherein, from can easily obtain from market, transparent excellent aspect considers, especially is preferably cellulose ester, annular ethylene series resin, polyethylene terephthalate or polymethacrylate.When using such transparent substrate to make this light polarizing film, aspect can under the situation of carrying, can not cause when taking care of described transparent substrate breakages such as destruction, easily operating, consider, also can stick support base material etc. at described transparent substrate.In addition, as described below, when making circularly polarizing plate by this light polarizing film, the situation of plastic basis material with phase differential of giving arranged.In the case, as long as wait to give phase differential by plastic basis material is carried out stretch processing.
When giving phase differential to plastic basis material, consider from its phase difference value aspect easy to control, preferably the plastic basis material that is constituted by cellulose ester or annular ethylene series resin.
Cellulose ester is that at least a portion of the hydroxyl that comprises in the Mierocrystalline cellulose is by the material of acid esterification.The cellulose ester film that is made of such cellulose ester can easily obtain from market.As commercially available triacetylcellulose film, for example have " fujitac(Off ジ タ Star Network) film " (Fujiphoto (strain)); " KC8UX2M ", " KC8UY " reach " KC4UY " (Konica Minolta precision optics (strain)) etc.Commercially available triacetylcellulose film like this can be directly or is given phase differential as required then as transparent substrate.In addition, surface treatments such as anti-dazzle processing, hard coat processing, anti-electrostatic processing or antireflection processing can be implemented, then as transparent substrate on the surface of ready transparent substrate.
Give plastic basis material with phase differential, as mentioned above, depend on the method for stretched plastic base material etc.The plastic basis material that is made of thermoplastic resin all can carry out stretch processing, but considers from phase differential easy to control aspect, more preferably the plastic basis material that is made of annular ethylene series resin.Annular ethylene series resin for example refers to by norbornylene or encircles the polymkeric substance of cyclic olefins such as norborneol alkene monomer or the material that multipolymer constitutes more that described annular ethylene series resin can contain the open loop position in the part.In addition, also can be the material that to contain after the annular ethylene series resin hydrogenation at open loop position.In addition, never can significantly damage transparent aspect or can not enlarge markedly the consideration of water absorbability aspect, described annular ethylene series resin for example can be the multipolymer of cyclic olefin, chain alkene or vinylated aromatics (vinylbenzene etc.) etc.In addition, described annular ethylene series resin can import at its intramolecularly polar group.
When annular ethylene series resin is the multipolymer of cyclic olefin, chain alkene or the aromatics with vinyl, as described chain alkene, be ethene or propylene etc., in addition, as vinylated aromatics, be vinylbenzene, alpha-methyl styrene and alkyl-substituted styrene etc.In such multipolymer, with respect to the entire infrastructure unit of annular ethylene series resin, derive from cyclic olefin structural unit to contain proportional be 50 moles below the %, for example, the scope of the degree of 15 ~ 50 moles of %.Annular ethylene series resin is during for the terpolymer that made by cyclic olefin, chain alkene and vinylated aromatics, for example, entire infrastructure unit with respect to described annular ethylene series resin, derive from chain alkene structural unit to contain proportional be the degree of 5 ~ 80 moles of %, derive from the vinylation aromatics structural unit to contain proportional be the degree of 5 ~ 80 moles of %.When making described annular ethylene series resin, the annular ethylene series resin of such terpolymer has can be so that the advantage that the consumption of the cyclic olefin of high price reduces relatively.
Annular ethylene series resin can easily be obtained from market.As commercially available annular ethylene series resin, can list " Topas " [Ticona society (solely)]; " Arton(ア one ト Application) " [Japanese synthetic rubber (strain)]; " ZEONOR(ゼ オ ノ ア) " reach " ZEONEX(ゼ オ ネ Star Network ス) " [Japanese auspicious father-in-law (strain)]; " apel(ア ペ Le) " [Mitsui Chemicals (strain) system] etc.Such annular ethylene series resin can be made film (annular ethylene series resin film) then for example by known film-forming method films processed such as solvent cast method or extrusion by meltings.In addition, also can use with the form of film commercially available the annular ethylene series resin film.As so commercially available annular ethylene series resin film can enumerate as: " エ ス シ one Na " reaches " SCA40 " [ponding chemical industry (strain)]; " ZEONOR film " [Optes(オ プ テ ス) (strain)]; " Arton film " [Japanese synthetic rubber (strain)] etc.
Then, describe with the method for phase differential giving plastic basis material.Plastic basis material can be given phase differential by known drawing process.For example, preparation is wound on roller (coiling body) on the roller with plastic basis material, continuously with the plastic basis material debatching, the plastic basis material of debatching is carried to process furnace from such coiling body.The design temperature of process furnace be near the glass transformation temperature of plastic basis material (℃) ~ [glass transformation temperature+100] (℃) scope, be preferably near the glass transformation temperature (℃) ~ [glass transformation temperature+50] (℃) scope.In described process furnace, when stretching towards the direct of travel of plastic basis material or towards the direction that intersects vertically with direct of travel, regulate carrying direction and tension force, towards arbitrarily angled inclination, carry out single shaft to or two axial thermal stretchs processing.The multiplying power that stretches is generally the scope of 1.1 ~ 6 times degree, is preferably the scope of 1.1 ~ 3.5 times degree.In addition, the method as stretching towards vergence direction so long as the method that makes axis of orientation tilt to desirable angle serially just is not particularly limited, can adopt known drawing process.Such drawing process can enumerate as: the Japanese Patent spy opens the method for putting down in writing in clear 50-83482 communique or the Japanese patent laid-open 2-113920 communique.
From the weight aspect of the degree that can carry out practicality ground operation and can guarantee that sufficient transparent aspect considers, the thin thickness of preferably transparent base material, but if too thin have then that intensity reduces, the tendency of processibility variation.The suitable thickness of glass baseplate is the degree of 100 ~ 3000 μ m for example, is preferably the degree of 100 ~ 1000 μ m.The suitable thickness of plastic basis material is the degree of 5 ~ 300 μ m for example, is preferably the degree of 20 ~ 200 μ m.When the circularly polarizing plate described later, the thickness of the transparent substrate during in particular as the circularly polarizing plate of mobile equipment purposes is preferably the degree of 20 ~ 100 μ m with this light polarizing film.And when giving phase differential by stretching to film, the thickness after the stretching is determined by the thickness before stretching and stretching ratio.
＜alignment films 〉
Preferably the base material in the manufacturing that is used for this light polarizing film forms alignment films.In the case, light polarizing film formation is coated on the alignment films with composition.Therefore, preferred described alignment films has and can not occur forming the solvent resistance that coating with composition etc. causes the degree of dissolving by light polarizing film.In addition, preferably in the heat treated that desolventizing and liquid crystal aligning are used, has thermotolerance.Such alignment films can use the orientation polymkeric substance to form.
As described orientation polymkeric substance, can enumerate as: intramolecularly have the polymeric amide of amido linkage or gelatin class, intramolecularly has the polyimide of imide bond and the polymkeric substance such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, poly-oxazole, polymine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylate(s) of hydrolysate thereof.Among these, preferably polyethylene alcohol.These orientation polymkeric substance that form alignment films can use separately or mixing use more than 2 kinds.
By be dissolved in the described orientation polymkeric substance of the orientation polymer composition (solution that contains the orientation polymkeric substance) in the solvent in base material coating conduct, can form alignment films at described base material.As described solvent, can enumerate water outlet; Alcoholic solvents such as methyl alcohol, ethanol, ethylene glycol, Virahol, propylene glycol, methylcyclohexane, ethylene glycol butyl ether and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butylacetate, ethylene glycol monomethyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, pimelinketone, Methyl amyl ketone and methyl iso-butyl ketone (MIBK); Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbon solvents such as toluene and dimethylbenzene, nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran (THF) and glycol dimethyl ether; Chlorine such as chloroform and chlorobenzene replaces hydrocarbon solvent etc.These organic solvents can use separately or multiple being used in combination.
In addition, as the orientation polymer composition that is used to form alignment films, can also directly use commercially available aligning film material.As commercially available aligning film material, can list Sunever(サ Application エ バ one) (registered trademark, daily output chemical industry (strain) system) or Optomer(オ プ ト マ one) (registered trademark, Japanese synthetic rubber (strain) system) etc.
As the method that forms alignment films at above-mentioned base material, can enumerate as at the base material above-mentioned orientation polymer composition of coating or commercially available aligning film material, then Tui Huo method etc.The thickness of the alignment films that so makes is generally the scope of 10nm ~ 10000nm, is preferably the scope of 10nm ~ 1000nm.
In order to give the orientation anchorage force to described alignment films, (rubbing manipulation) as required preferably rubs.By giving the orientation anchorage force polymerizable liquid crystal compound is orientated to desirable direction.
As the method for giving the orientation anchorage force by rubbing manipulation, can enumerate as the friction roller that prepared to have reeled friction cloth, rotating, to form the laminate that alignment films forms the coated film of usefulness at base material places on the Transport Desk (Stage), by it is carried towards the friction roller that is rotating, make described alignment films form the method that contacts with the friction roller that is rotating with coated film.
In addition, can also utilize so-called optical alignment film.Optical alignment film refers to, to contain polymkeric substance with photoreactive group or monomer and solvent composition (below, according to circumstances be referred to as " the light oriented layer forms and uses composition ") be coated on the base material, given the alignment films of orientation anchorage force by irradiation polarized light (being preferably polarized light UV).Photoreactive group refers to, produces the group of liquid crystal aligning energy by irradiates light (rayed).Particularly, its be by the orientation as molecule that irradiates light produces induce or isomerization reaction, dimerization reaction, photo-crosslinking or photolysis reactions, become liquid crystal aligning can the material of photoresponse of origin.Among the described photoreactive group, the smectic liquid crystal state aspect during from orientation excellence, the formation of maintenance light polarizing film is considered, preferably causes the material of dimerization reaction or photo-crosslinking.As the photoreactive group that can take place as above to react, be preferably and have unsaturated link(age), the group that particularly has two keys is preferably especially has at least one the group of selecting from the group that is made of the two keys (C=N key) of carbon-to-carbon double bond (C=C key), carbon-nitrogen, the two keys (N=N key) of nitrogen-nitrogen and the two keys (C=O key) of carbon-oxygen.
As the photoreactive group with C=C key, can enumerate as vinyl, polyene-based, stilbene radicals, stilbene azoles base, stibazole alkali (ス チ Le バ ゾ リ ウ system base), cinnamophenone base and cinnamoyl etc.As the photoreactive group with C=N key, can list and have aromatic series Schiff's base and the isostructural group of aromatic series hydrazone.As the photoreactive group with N=N key, can list azobenzene, azo naphthyl, heteroaromatic azo-group, tetrazo base and first Za base etc. or be the group of basic structure with the zinin.As the photoreactive group with C=O key, can list benzophenone base, tonka bean camphor base, anthraquinonyl and dimaleoyl imino etc.These groups can have substituting groups such as alkyl, alkoxyl group, aryl, allyloxy, cyano group, alkoxy carbonyl, hydroxyl, sulfonic group and halogenated alkyl.
Wherein, preferably can cause the photoreactive group of photodimerization reaction, because easily making the optical alignment film of the required polarizing light irradiation amount of light orientation less relatively and thermostability and ageing stability excellence, so preferred cinnamoyl and cinnamophenone base.If furtherly, as the polymkeric substance with photoreactive group, the distal portion that especially preferably has described polymer lateral chain becomes the material of the such cinnamoyl of styracin structure.
Form the solvent of using composition as the light oriented layer, preferred dissolution has the polymkeric substance of photoreactive group and the solvent of monomer, as described solvent, can enumerate the solvent that uses as in above-mentioned orientation polymer composition.
With respect to light oriented layer formation composition, have the polymkeric substance of photoreactive group or the concentration of monomer and can do suitable adjustment with the thickness of the optical alignment film of wanting to make according to the kind of the polymkeric substance with described photoreactive group or monomer, represent with solid component concentration, preferred its is at least 0.2 quality %, is preferably the scope of 0.3 ~ 10 quality % especially.In addition, in the scope of significantly not damaging the characteristic of optical alignment film, described oriented layer forms can contain macromolecular material, photosensitizers such as polyvinyl alcohol or polyimide with composition.
Use method for compositions as forming in the described orientation polymer composition of base material coating or light oriented layer, can adopt spin-coating method, extrusion process, intaglio plate coating method, die type coating method, bar type to be coated with the known method of print processes such as coating method such as (Bar coating) method and spreader method or flexographic printing method etc.And when implementing the manufacturing of this light polarizing film by the continuous manufacture method of aftermentioned volume to volume (roll to roll) form, described coating process adopts print processes such as intaglio plate coating method, die type coating method or flexographic printing method usually.
And, rub or during polarizing light irradiation, if shelter, then also can form the different a plurality of zones (pattern) of differently-oriented directivity.
The manufacture method of＜this light polarizing film 〉
At described base material or on the alignment films that base material forms, the coating light polarizing film forms and makes coated film with composition.As coating process, can enumerate as with as form the identical method of the method that illustrates for example with method for compositions in base material coating orientation polymer composition or light oriented layer.
Then, under the condition by the not polymerization of polymerizable liquid crystal compound that in described coated film, comprises solvent seasoning is removed, form dry overlay film.As drying means, can enumerate as natural seasoning, air seasoning method, heat drying and hypobaric drying method etc.
Then, as preferred mode, in case the mesomorphic state of the polymerizable liquid crystal compound that comprises in the described dry overlay film change into nematic liquid crystal mutually after, make described nematic liquid crystal change the smectic liquid crystal phase mutually into immediately.
Like this in order to form the smectic liquid crystal phase mutually via nematic liquid crystal, can adopt for example the polymerizable liquid crystal compound that comprises in the dry overlay film to be heated to more than the temperature that shows the nematic liquid crystal phase, then described polymerizable liquid crystal compound is cooled to the method till the temperature that shows the smectic liquid crystal phase.
Make the polymerizable liquid crystal compound in the described dry overlay film change the smectic liquid crystal phase into or make described polymerizable liquid crystal compound change the smectic liquid crystal phase time mutually into via nematic liquid crystal, by measuring the phase transition temperature of the polymerizable liquid crystal compound that uses, can obtain the condition (heating condition) of control mesomorphic state.The condition determination of this phase transition temperature is illustrated in the application's embodiment.
Then, the polymerization process to polymerizable liquid crystal compound describes.Herein, contain Photoepolymerizationinitiater initiater to making in light polarizing film forms with composition, make the mesomorphic state of the polymerizable liquid crystal compound in the dry overlay film change into smectic liquid crystal mutually after, under the state of the mesomorphic state that keeps this smectic liquid crystal phase, make described polymerizable liquid crystal compound carry out photopolymerisable method and be elaborated.In the photopolymerization, as the light to the irradiation of dry overlay film, can be undertaken by light or the active electrons bundle of suitably from the group that is constituted by visible light, UV-light and laser, selecting according to the kind of the Photoepolymerizationinitiater initiater that comprises in the described dry overlay film or the kind of polymerizable liquid crystal compound (the particularly kind of the polymerizable group that has of described polymerizable liquid crystal compound) and amount thereof.Among them, from the aspect consideration of carrying out the aspect and can use the device that is being widely used in the art to be used as relating to photopolymerisable device of polyreaction easy to control, preferred UV-light.Therefore, by UV-light, in order to carry out photopolymerization, preferably be chosen in light polarizing film in advance and form kind with the polymerizable liquid crystal compound that contains in the composition and Photoepolymerizationinitiater initiater.In addition, during polymerization, in UV-irradiation, by suitable refrigerating unit, by being cooled off also, dry overlay film can control polymerization temperature.By adopting such refrigerating unit, if can under low temperature more, implement the polymerization of polymerizable liquid crystal compound, even then use the relatively low material of thermotolerance in above-mentioned base material, the advantage that can form this light polarizing film is validly arranged also.And, during photopolymerization, by sheltering and development etc., also can make this light polarizing film that has formed pattern.
By carrying out photopolymerization as above, polymerizable liquid crystal compound forms this light polarizing film keeping nematic liquid crystal phase, smectic liquid crystal phase, being preferably polymerization under the state of the such height smectic liquid crystal phase that has illustrated for example.Polymerizable liquid crystal compound polymerization and this light polarizing film of making under the state of the mesomorphic state that keeps the smectic liquid crystal phase, be accompanied by the effect of dichroism pigment (1), with host-guest (Host-guest) type light polarizing film in the past, namely, the light polarizing film that makes keeping making under the state of nematic mesomorphic state polymerization such as polymerizable liquid crystal compound relatively has the high advantage of polarization property.Further, compare with the light polarizing film that only has been coated with lyotropic dichroism pigment, the advantage of excellent strength is arranged.
The thickness of preferred this light polarizing film that forms like this is in the scope more than the 0.5 μ m, below the 10 μ m, more preferably 1 μ m above, below the 5 μ m.Therefore, this light polarizing film forms with the thickness of coated film and can consider that the thickness of this light polarizing film of making determines.And the thickness of this light polarizing film is obtained by the mensuration of interfere type film thickness gauge, laser microscope or contact pin type film thickness gauge.
In addition, this light polarizing film of Xing Chenging is preferably this light polarizing film that can obtain bragg peak in X-ray diffraction is measured as mentioned above especially like this.As this light polarizing film of such obtained bragg peak, can enumerate as: show to derive from hexagonal mutually or this light polarizing film of the diffraction peak of crystallization phases.
The maximum absorption wavelength of this light polarizing film (λ max1) is present in 400 ~ 520nm.Preferred this maximum absorption wavelength (λ max1) is present in the scope of 430 ~ 520nm, more preferably is present in the scope of 440 ~ 510nm.In addition, preferably the maximum absorption wavelength of this light polarizing film (λ max1) moves to the wavelength of also growing than the maximum absorption wavelength (λ max2) of the dichroism pigment that uses in the manufacturing of this light polarizing film.The solution that preparation forms with suitable dissolution with solvents dichroism pigment, this maximum absorption wavelength (λ max2) obtains for mensuration under the state of this solution.The solvent of dissolving dichroism pigment may be selected to be and can fully dissolve solvent described dichroism pigment, do not have absorption in the light of the wavelength of 350 ~ 550nm.The appearance that such long wavelength side moves has shown: in this light polarizing film, when dichroism pigment (1) was scattered between the molecular chain that is formed by polymerizable liquid crystal compound, described dichroism pigment (1) was interacting consumingly with described molecular chain.And, long wavelength side move poor (the λ max1-λ max2) that refer to maximum absorption wavelength on the occasion of, but preferably should difference for more than the 20nm, more preferably more than the 30nm.
In addition, the dichroic ratio height of this light polarizing film, polarizing properties are very excellent.Particularly, usually, dichroic ratio is more than 15, to be preferably more than 25.
The continuous manufacture method of＜this light polarizing film 〉
More than, the summary of the manufacture method of this light polarizing film has been described, but when commercial this light polarizing film of manufacturing, has pursued the method for making this light polarizing film serially.Continuous manufacture method like this is the method by the volume to volume form, according to circumstances, is referred to as " this manufacture method ".And, in this manufacture method, be to be illustrated centered by the situation of transparent substrate by the base material.When base material was transparent substrate, the article that finally make became the polarizer with transparent substrate and this light polarizing film (below, according to circumstances be referred to as " this polarizer ").
This manufacture method for example has
Preparation with transparent substrate be wound on 1st roller of the 1st volume on the core operation,
From described the 1st roller continuously with the operation of described transparent substrate debatching,
On described transparent substrate, form continuously alignment films operation,
On described alignment films, be coated with continuously light polarizing film form operation with composition,
Form by the light polarizing film that under the condition of not polymerization of polymerizable liquid crystal compound, makes coating and to use composition dries, on described alignment films, form continuously dry overlay film operation,
Make the polymerizable liquid crystal compound that comprises in the described dry overlay film become the nematic liquid crystal phase, be preferably smectic liquid crystal mutually after, under the state that keeps described smectic liquid crystal phase, by making described polymerizable liquid crystal compound polymerization, make light polarizing film continuously, as the operation of the polarizer and
The polarizer that makes continuously is wound on the 2nd volume core, makes the operation of the 2nd roller.With reference to Fig. 1, particularly the situation that optical alignment film is used as alignment films to this manufacture method describing herein.
The 1st roller 210 that transparent substrate is wound on the 1st volume core 210A for example can easily obtain from market.As the transparent substrate that can obtain from market with the form of such roller, can list among the transparent substrate that has illustrated for example film that is constituted by cellulose ester, annular ethylene series resin, polyethylene terephthalate, polycarbonate or polymethacrylate etc.In addition, when the circularly polarizing plate, the transparent substrate of having given phase differential in advance also can easily obtain from market with this light polarizing film, can enumerate as the phase retardation film that is made of cellulose ester or annular ethylene series resin etc.
Then, from described the 1st roller 210 with the transparent substrate debatching.Be by the volume core 210A at described the 1st roller 210 suitable swivel arrangement to be set with the method for transparent substrate debatching, by described swivel arrangement 210 rotations of the 1st roller carried out by nationality.In addition, also can be in the direction from the 1st roller 210 carrying transparent substrates suitable help roll 300 to be set, the swivel arrangement by described help roll 300 is with the form of transparent substrate debatching.Further, can also be by in the 1st volume core 210A and help roll 300, swivel arrangement being set all, Yi Bian give the tension force of transparent substrate with appropriateness, Yi Bian with the form of transparent substrate debatching.
By apparatus for coating 211A the time, nationality is by described apparatus for coating 211A from the transparent substrate of described the 1st roller 210 debatchings, is coated with the lighting oriented layer in its surface and forms and use composition.Use composition in order to be coated with the formation of lighting oriented layer like this continuously, as mentioned above, by described apparatus for coating 211A, implement print processes such as intaglio plate coating method, die type coating method, flexographic printing method.
Transparent substrate through apparatus for coating 211A is carried to drying oven 212A, and nationality drying oven 212A heating thus forms the 1st dry overlay film continuously on transparent substrate.As drying oven 212A, can use for example hot air type drying oven etc.The design temperature of drying oven 212A can form according to the described smooth oriented layer by apparatus for coating 211A coating with the solvent types that comprises in the composition and wait to determine.In addition, can be that drying oven 212A is divided into a plurality of zones, the different form of design temperature difference in a plurality of zones of division can also be with a plurality of drying oven configured in series, the design temperature of each drying oven is the drying oven of different forms respectively.
Nationality by from process furnace 212A by and form the 1st dry overlay film continuously, then, shine polarized light UV by polarized light UV irradiating unit 213A on the surface of the 1st dry overlay film side or the surface of transparent substrate side, the described the 1st dry overlay film forms (light) alignment films.At this moment, the carrying direction D1 that can also make transparent substrate intersects with the differently-oriented directivity D2 angulation of the optical alignment film of formation.Fig. 2 is the synoptic diagram that is illustrated in the relation between the carrying direction D1 of the differently-oriented directivity D2 of the optical alignment film that polarized light UV irradiation back forms and transparent substrate.That is, Fig. 2 is representing: when observing the 1st laminate after polarized light UV irradiating unit 213A passes through surperficial from the differently-oriented directivity D2 of the carrying direction D1 of transparent substrate and optical alignment film, their angulations are shown as about 45 °.
Formed the transparent substrate (the 1st laminate) of optical alignment film so continuously by continuing by apparatus for coating 211B, after optical alignment film coating light polarizing film forms with composition, by drying oven 212B.Nationality is by passing through drying oven 212B, and light polarizing film forms with the polymerizable liquid crystal compound that comprises in the composition and forms the nematic liquid crystal phase, is preferably the smectic liquid crystal phase, forms the 2nd dry overlay film.
The solvent that contains in light polarizing film forms with composition is fully removed, the polymerizable liquid crystal compound in the 2nd dry overlay film remains the nematic liquid crystal phase, be preferably under the state of mesomorphic state of smectic liquid crystal phase, be carried to light irradiation device 213B through the transparent substrate of described drying oven 212B.By the rayed of carrying out with light irradiation device 213B, described polymerizable liquid crystal compound carries out photopolymerization under the state that keeps described mesomorphic state, form this light polarizing film on alignment films continuously, makes this polarizer.
This light polarizing film of Xing Chenging can be the form that comprises the laminate of transparent substrate and alignment films so continuously, is wound on the 2nd volume core 220A, makes the form of the 2nd roller 220.When this light polarizing film coiling that forms is made the 2nd roller, can use suitable pad together to reel.
So, by transparent substrate is passed through with the order of the 1st roller/apparatus for coating 211A/ drying oven 212A/ polarized light UV irradiating unit 213A/ apparatus for coating 211B/ drying oven 212B/ light irradiation device 213B, on the optical alignment film on the transparent substrate, form this light polarizing film continuously, make this polarizer.
In addition, in this manufacture method that shows among Fig. 1, though shown the continuous manufacture method from transparent substrate to this light polarizing film, but, for example, also can be by transparent substrate is passed through with the order of the 1st roller/apparatus for coating 211A/ drying oven 212A/ polarized light UV irradiating unit 213A, the 1st laminate that forms continuously is wound on the core, make the 1st laminate with the form of roller, from described roller with the 1st laminate debatching, the 1st laminate of debatching is passed through with the order of apparatus for coating 211B/ drying oven 212B/ light irradiation device 213B, make this polarizer.
By this polarizer that this manufacture method makes, it is the article that are shaped as film like and long chi shape.This this light polarizing film is used for the situation of liquid crystal indicator described later etc., can be cut into desired size according to the size of described liquid crystal indicator etc. and use then.
More than, though composition and manufacture method to this polarizer centered by the situation of the form of the laminate of transparent substrate/optical alignment film/this light polarizing film are illustrated, but as mentioned above, also can be by peel off this light polarizing film that optical alignment film and transparent substrate make individual layer from this polarizer.In addition, can also make layer beyond in this polarizer lamination transparent substrate/optical alignment film/this light polarizing film or the form of film.As these layer and film, as narrating, can make the form that further possesses phase retardation film, also can be the form that further possesses anti-reflection layer or brightness enhancement film.
In addition, by making transparent substrate originally as phase retardation film, also can be arranged to circularly polarizing plate or the elliptical polarization plate of the form of phase retardation film/optical alignment film/this light polarizing film.For example, 1/4 wavelength plate that uses uniaxial drawing is slightly at 45 with respect to the carrying direction of transparent substrate by the direction of illumination of setting polarized light UV during as phase retardation film, can make circularly polarizing plate by volume to volume.Preferably 1/4 wavelength plate that uses when so making circularly polarizing plate is 1/4 wavelength plate of the characteristic that phase difference value diminishes along with wavelength shortens in having the face of visible light.
In addition, use 1/2 wavelength plate as phase retardation film, making is the such straight line polarization plates roller that staggers with the angle initialization of the extinction axle of its slow axis and light polarizing film, by with the opposition side of the face that has formed described light polarizing film on further form 1/4 wavelength plate, also can be made into broadband circularly polarizing plate.
The purposes of＜this light polarizing film 〉
This light polarizing film can be used for various display unit.Display unit refers to have the device of display element, comprises luminous element or light-emitting device as luminous source.As display unit, can enumerate as: liquid crystal indicator, organic electroluminescent (EL) display unit, inorganic EL (EL) display unit, electron emission display (for example field emission display device (FED), Surface-conduction Electron-emitter Display device (SED)), Electronic Paper and (use the display unit, plasma display system, projection type image display apparatus (for example grating light valve (GLV) display unit, have the display unit of digital micro-mirror device (DMD)) of electric ink or electrophoresis element and piezoelectric ceramics display unit etc.Liquid crystal indicator comprises any one of transmission type liquid crystal display device, semitransparent liquid crystal display, reflection-type liquid-crystal display device, direct view liquid crystal display device and projection-type liquid crystal display device etc.These display unit can be the display unit that shows 2 dimension images, also can be the 3 d display devices that shows 3 d image.
This light polarizing film can be used for the display unit of organic electroluminescent (EL) display unit or inorganic EL (EL) display unit especially effectively.
Fig. 3 be the expression used this light polarizing film liquid crystal indicator (below, according to circumstances be referred to as " this liquid crystal indicator ".) synoptic diagram of 10 section constitution.Liquid crystal layer 17 is sandwiched among 2 substrate 14a and the substrate 14b.
Fig. 6 and Figure 10 be the expression used this light polarizing film the EL display unit (below, according to circumstances be referred to as " this EL display unit ".) the synoptic diagram of section constitution.
Figure 11 is the synoptic diagram of composition that the projection-type liquid crystal display device of this light polarizing film has been used in expression.
At first this liquid crystal indicator 10 that shows in Fig. 3 is described.
Disposing colour filter 15 in liquid crystal layer 17 sides of substrate 14a.Colour filter 15 clips liquid crystal layer 17, be configured in and pixel electrode 22 position in opposite directions, stain matrix 20 be configured in and pixel electrode between borderline phase to the position.Transparency electrode 16 is configured to cover colour filter 15 and stain matrix 20 fully in liquid crystal layer 17 sides.And, can have protection (overcoat) layer (not shown) between colour filter 15 and the transparency electrode 16.
Disposing thin film transistor 21 and pixel electrode 22 regularly on liquid crystal layer 17 sides of substrate 14b.Pixel electrode 22 clips liquid crystal layer 17 and is configured in and colour filter 15 position in opposite directions.Disposing the have connecting hole interlayer dielectric 18 of (not shown) between thin film transistor 21 and the pixel electrode 22.
As substrate 14a and substrate 14b, use glass substrate and plastic base.Such glass substrate and plastic base can adopt the base material with the identical material of base material that illustrates for example as the transparent substrate that is used for the manufacturing of this light polarizing film.In addition, the transparency carrier 1 of this light polarizing film can have substrate 14a and substrate 14b concurrently.When being manufactured on the colour filter 15 that forms on the substrate and thin film transistor 21, when needing the heat operation, preferred glass substrate or quartz base plate.
Thin film transistor can adopt only thin film transistor according to the material of substrate 14b.As thin film transistor 21, the low temperature polycrystalline silicon transistor that can list the high temperature polysilicon transistor that forms at quartz base plate, form at glass substrate, the unformed silicon transistor that forms at glass substrate or plastic base.In order to make the miniaturization more of this liquid crystal indicator, can form drive IC at substrate 14b.
Between transparency electrode 16 and pixel electrode 22, disposing liquid crystal layer 17.In order to keep the distance between substrate 14a and substrate 14b certain, in liquid crystal layer 17, disposing pad 23.And, illustrate the pad of column among Fig. 3, but described pad is not limited to column, as long as can make the distance between substrate 14a and substrate 14b keep certain, its shape is just arbitrarily.
Each member with the sequential lamination of substrate 14a, colour filter 15 and stain matrix 20, transparency electrode 16, liquid crystal layer 17, pixel electrode 22, interlayer dielectric 18 and thin film transistor 21 and substrate 14b.
Clip among the substrate 14a and substrate 14b of such liquid crystal layer 17, polarizer 12a and 12b in the arranged outside of substrate 14b, among them, at least 1 has been used this polarizer.
Further, preferred phase separation layer (for example, 1/4 wavelength plate or optical compensating film) 13a and 13b lamination.Among polarizer 12a and the 12b, by in this light polarizing film of polarizer 12b configuration, can give this liquid crystal indicator 10 with the function endowing that makes incident light change rectilinearly polarized light into.And, kind according to the liquid crystalline cpd that comprises in the structure of liquid crystal indicator and the liquid crystal layer 17, also can not dispose phase retardation film 13a and 13b, use transparency carrier as phase retardation film, when comprising the circularly polarizing plate of this light polarizing film, because described phase retardation film being made phase separation layer, so also can omit phase separation layer 13a and/or the 13b of Fig. 3.On the light emission side (outside) of the polarizer that comprises this light polarizing film, light polarizing film can be set further.
In addition, can dispose the antireflection film that prevents that external light reflection from using in the outside of the polarizer that comprises this light polarizing film (when on this light polarizing film, further light polarizing film being set, in its outside).
As mentioned above, in the polarizer 12a of this liquid crystal indicator 10 of Fig. 3 or 12b, can use this polarizer.By this polarizer is used among polarizer 12a and/or the 12b, the effect of the slimming that can realize this liquid crystal indicator 10 is arranged.
When being used in this polarizer among polarizer 12a or the 12b, its lamination is not particularly limited in proper order.Be explained with reference to the A of the dotted line of Fig. 3 and the partial enlarged drawing of B.
Fig. 4 is the amplification schematic cross-section of the A part of Fig. 3.When this polarizer 100 was used as polarizer 12a, (A1) of Fig. 4 shown from the set situation of phase separation layer 13a side with the arranged in order of this light polarizing film 3, optical alignment film 2 and transparent substrate 1.In addition, Fig. 4 (A2) shown from the set situation of phase separation layer 13a side with the arranged in order of transparent substrate 1, optical alignment film 2 and this light polarizing film 3.
Fig. 5 is the enlarged diagram of the B part of Fig. 3.When this polarizer 100 is used as polarizer 12b, in Fig. 5 (B1), with the arranged in order of transparent substrate 1, optical alignment film 2 and this light polarizing film 3 from phase retardation film 13b side.When this polarizer 100 is used as polarizer 12b, in Fig. 5 (B2), with the arranged in order of this light polarizing film 3, optical alignment film 2 and transparent substrate 1 from phase retardation film 13b side.
Disposing the module backlight 19 as luminous source in the outside of polarizer 12b.Module 19 backlight comprises light source, light guide, reflector, diffusion sheet and field angle adjustment sheet.As light source, can list electroluminescent, cold-cathode tube, hot-cathode lamp, photodiode (LED), LASER Light Source and mercury lamp etc.In addition, can select the kind of this light polarizing film according to the characteristic of such light source.
When this liquid crystal indicator 10 was transmission type liquid crystal display device, the white light that the light source from module 19 backlight sends was injected light guide, changed light path by reflector and spread in diffusion sheet.Diffusion light is adjusted into by the field angle adjustment sheet and injects polarizer 12b from module 19 backlight after having desirable directivity.
Among the incident light of non-polarized light, only the rectilinearly polarized light of a certain direction sees through the polarizer 12b of liquid crystal panel.This rectilinearly polarized light nationality is transformed to circularly polarized light or elliptically polarized light by phase separation layer 13b, sees through substrate 14b, pixel electrode 22 etc. successively and arrives liquid crystal layer 17.
According to pixel electrode 22 herein and and its transparency electrode 16 in opposite directions between have or not potential difference, the state of orientation of the liquid crystal molecule that comprises in the liquid crystal layer 17 changes, and can control from the brightness of the light of this liquid crystal indicator 10 emissions.Liquid crystal layer 17 is in when making the state of orientation that polarized light conversion sees through then, this polarized light sees through liquid crystal layer 17, transparency electrode 16, the light transmission colour filter 15 of a certain particular range of wavelengths arrives polarizer 12a, and liquid crystal indicator shows the color that is determined by colour filter the most brightly.
Conversely, liquid crystal layer 17 is in when making the state of orientation that polarized light directly sees through, and the light that sees through liquid crystal layer 17, transparency electrode 16 and colour filter 15 is polarized device 12a and absorbs.Thus, this pixel shows black.When the state of orientation of the centre of these 2 states, also become between described both centre from the brightness of the light of this liquid crystal indicator 10 emissions, this pixel shows middle shade.
When this liquid crystal indicator 10 is semitransparent liquid crystal display, the preferred article (circularly polarizing plate) that use this light polarizing film side at this polarizer that 1/4 wavelength plate lamination is formed.At this moment, pixel electrode 22 has the reflecting part that sees through portion and formed by catoptrical material that is formed by transparent material, sees through in the portion, similarly shows image with described transmission type liquid crystal display device.On the other hand, in the reflecting part, outer light is injected liquid crystal indicator, and by the effect of 1/4 wavelength plate that further possesses in this light polarizing film, the circularly polarized light that sees through this light polarizing film passes through from liquid crystal layer 17, is reflected and is used for showing by pixel electrode 22.
Then, this EL display unit 30 of having used this light polarizing film is described with reference to Fig. 6.In this EL display unit, when using this light polarizing film, preferably this light polarizing film is made circularly polarizing plate (below, according to circumstances be referred to as " this circularly polarizing plate ".) use then.There are 2 embodiments in this circularly polarizing plate.Therefore, before the formation of explanation this EL display unit 30 etc., 2 embodiments of this circularly polarizing plate are illustrated with reference to Fig. 7.
(A) of Fig. 7 is the sectional view that schematically shows the 1st embodiment of this circularly polarizing plate 110.This 1st embodiment further arranges phase separation layer (phase retardation film) 4 these circularly polarizing plates that form 110 on this light polarizing film 3 in this polarizer 100.(B) of Fig. 7 is the synoptic diagram of the 2nd embodiment of expression this circularly polarizing plate 110.This 2nd embodiment is for by using the transparent substrate 1(phase retardation film 4 given phase differential in advance) transparent substrate 1 that uses when making this polarizer, transparent substrate 1 is become itself have concurrently this circularly polarizing plate 110 as the article of the function of phase separation layer 4.
As this circularly polarizing plate that comprises this light polarizing film, because if the 2nd embodiment of above-mentioned circularly polarizing plate then constitutes easy so preferred, at this moment, preferably 1/4 wavelength plate is used as transparent substrate, further, use 1/4 wavelength plate as transparent substrate, preferred satisfied following (A1) and prerequisite (A2).
(A1) the slow axis angulation of the extinction axle of described light polarizing film and described 1/4 wavelength plate is about 45 °;
(A2) value that postpones of the front of described 1/4 wavelength plate of the light measurement by wavelength 550nm is the scope of 100 ~ 150nm.
Herein, in advance the manufacture method about this circularly polarizing plate 110 is described.The same with the 2nd embodiment of the circularly polarizing plate 110 that has illustrated, in this manufacture method of making this polarizer 100, by using the transparent substrate 1 of having given phase differential in advance as transparent substrate 1, that is, use phase retardation film to make.The 1st embodiment of this circularly polarizing plate 110 is so long as form phase separation layer 4 by applying phase retardation film on this light polarizing film 3 of being made by this manufacture method B and get final product.And, according to this manufacture method B, when making this polarizer 100 in the mode of the 2nd roller 220, can be with 100 debatchings of this polarizer from described the 2nd roller 220, be cut into specified dimension, the mode of applying phase retardation film on this polarizer 100 of cutting then, but by preparing that phase retardation film is wound on the 3rd roller on the core, also manufacturing serially is shaped as this circularly polarizing plate 110 of film like and long chi shape.
Method about the 1st embodiment of making this circularly polarizing plate 110 continuously describes with reference to Fig. 8.Such manufacture method by:
From described the 2nd roller 220 continuously with 100 debatchings of this polarizer, simultaneously the 3rd roller 230 of reeling from phase retardation film continuously with the operation of described phase retardation film debatching,
Will the light polarizing film that arrange at this polarizer 100 from 220 debatchings of described the 2nd roller and the operation of fitting to form this circularly polarizing plate 110 from the described phase retardation film of described the 3rd roller debatching continuously,
This circularly polarizing plate 110 that forms is wound on the 4th volume core 240A, and the operation that makes the 4th roller 240 constitutes.
More than, manufacture method to the 1st embodiment of this circularly polarizing plate 110 is illustrated, but when this light polarizing film 3 in the applying polarizer 100 and phase retardation film, can use suitable adhesive, Jie is by the bonding coat that is formed by described tackiness agent, this light polarizing film of fitting 3 and phase retardation film.
Then, this EL display unit that possesses this circularly polarizing plate 110 is described referring again to Fig. 6.
This EL display unit 30 be on the substrate 33 that has formed pixel electrode 35 lamination by the display unit as organic function layer 36 and the cathode electrode 37 of luminous source.With the opposition side of organic function layer 36 on, disposed circularly polarizing plate 31, sandwich substrate 33 uses this circularly polarizing plate 110 as such circularly polarizing plate 31.By applying positive voltage at pixel electrode 35, applying negative voltage, apply galvanic current between pixel electrode 35 and cathode electrode 37 at cathode electrode 37, organic function layer 36 is luminous.Organic function layer 36 as luminous source is made of electron transfer layer, luminescent layer and hole transmission layer etc.Pass through pixel electrode 35, interlayer dielectric 34, substrate 33, this circularly polarizing plate of circularly polarizing plate 31(110 from the light of organic function layer 36 emissions).Though the organic EL display with organic function layer 36 is described, the inorganic EL display unit with inorganic functional layer also can be suitable equally.
In order to make this EL display unit 30, at first, on substrate 33, form thin film transistor 40 with desirable shape.Interlayer dielectric 34 film forming are followed pixel electrode 35 by sputtering film-forming then, form pattern.Afterwards, with organic function layer 36 laminations.
Then, on the face opposite with the face of the thin film transistor 40 that substrate 33 is being set, this circularly polarizing plate of circularly polarizing plate 31(110 is set).
With this circularly polarizing plate 110 during as circularly polarizing plate 31, its lamination order describes with reference to the partial enlarged drawing of the C that the dotted line of Fig. 6 surrounds.With this circularly polarizing plate 110 during as circularly polarizing plate 31, the phase separation layer 4 in described circularly polarizing plate 110 is configured in substrate 33 sides.(C1) of Fig. 9 is the enlarged view that the 1st embodiment of this circularly polarizing plate 110 is used as circularly polarizing plate 31, and (C2) of Fig. 9 is the enlarged view that the 2nd embodiment of this circularly polarizing plate 110 is used as circularly polarizing plate 31.
Then, to this light polarizing film 31(circularly polarizing plate 110 of this EL display unit 30) in addition member describes.
As substrate 33, can list ceramic substrates such as sapphire glass substrate, quartz glass substrate, soda-lime glass substrate and aluminum oxide; Metal substrates such as copper; Plastic base etc.Though not shown, can form the heat conductivity film at substrate 33.As the heat conductivity film, can list diamond thin (DLC etc.) etc.When pixel electrode 35 is made reflection-type, to the reverse direction emission light of substrate 33.Therefore, not only can use transparent material, also can use non-permeable materials such as stainless steel.Substrate can form separately, a plurality of substrates is fitted by caking agent form laminated substrate.In addition, these substrates are not limited to tabular, can also be films.
As thin film transistor 40, can use as polycrystal silicon transistor etc.Thin film transistor 40 is arranged at the end of pixel electrode 35, and its size is the degree of 10 ~ 30 μ m.And the size of pixel electrode 35 is the degree of 20 μ m * 20 μ m ~ 300 μ m * 300 μ m.
The wire electrode of thin film transistor 40 is being set at substrate 33.The wired electric electrode resistance is low, have to be electrically connected with pixel electrode 35 and resistance value is suppressed lowlyer function, this distribution electrode uses any distribution electrode more than a kind or 2 kinds that contains Al, Al and transition metal (but removing Ti), Ti or titanium nitride (TiN) usually.
Between thin film transistor 40 and pixel electrode 35, be provided with interlayer dielectric 34.As long as interlayer dielectric 34 is to make SiO 2Deng inorganic based material such as silicon oxide, silicon nitride by sputter or vacuum evaporation and the article of film forming, by the SOG(spin-coating glass) interlayer dielectric with insulativity of filming etc. of the resin system materials such as silicon oxide layer, photo-resist, polyimide and acrylic resin that form, its just can be above-mentioned any one.
Form rib 41 at interlayer dielectric 34.Rib 41 is configured in the periphery (between neighbor) of pixel electrode 35.As the material of rib 41, can list acrylic resin and polyimide resin etc.The thickness of preferred rib 41 be 1.0 μ m above, below the 3.5 μ m, more preferably 1.5 μ m above, below the 2.5 μ m.
Then, to by describing as the pixel electrode 35 of transparency electrode, the EL element that constitutes as organic function layer 36 and the cathode electrode 37 of luminous source.Organic function layer 36 has at least 1 layer hole transmission layer and luminescent layer respectively, for example, has electronics successively and injects transport layer, luminescent layer, hole transmission layer and hole injection layer.
As pixel electrode 35, can enumerate as: the ITO(tin-doped indium oxide), IZO(mixes the zinc Indium sesquioxide), IGZO, ZnO, SnO 2And In 2O 3Deng, but preferred especially ITO and IZO.Certain above thickness that the thickness of pixel electrode 35 so long as have can fully carry out injecting in the hole gets final product, and is preferably the degree of 10 ~ 500nm.
Pixel electrode 35 can form by vapour deposition method (being preferably sputtering method).As sputter gas, be not particularly limited, can use rare gas element or their mixed gass such as Ar, He, Ne, Kr and Xe.
Constituent material as cathode electrode 37, can use as metallic elements such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn and Zr, but for the job stability that makes electrode improves, 2 kinds of compositions that preferred use is selected from the metallic element that illustrates for example or the alloy system of 3 kinds of compositions.As alloy system, preferably as AgMg(Ag:1 ~ 20at%), AlLi(Li:0.3 ~ 14at%), InMg(Mg:50 ~ 80at%) and AlCa(Ca:5 ~ 20at%) etc.
Cathode electrode 37 is by formation such as vapour deposition method and sputtering methods.The thickness of cathode electrode 37 is more than the 0.1nm, to be preferably 1 ~ 500nm.
Hole injection layer has to be made from the pixel electrode 35 injected holes easy function that becomes, and hole transmission layer has the function of transporting holes and hinders the function of electronics, is also referred to as electric charge injection layer and charge transport layer.
The thickness that the total thickness of the thickness of luminescent layer, hole injection layer and hole transmission layer and electronics inject transport layer is not particularly limited, though also according to the difference of formation method and difference, be preferably the degree of 5 ~ 100nm.Can use various organic compound in hole injection layer and the hole transmission layer.In the formation that hole injection/transport layer, luminescent layer and electronics inject transport layer, consider to use vacuum vapour deposition from forming homogeneous film aspect.
Can use the organic function layer of luminous (fluorescence) that utilizes singlet exciton as the organic function layer 36 of luminous source, utilize the organic function layer of luminous (phosphorescence) of triplet excitons, comprise the organic function layer of luminous (fluorescence) that utilizes singlet exciton and the organic function layer of the organic function layer of luminous (phosphorescence) that utilizes triplet excitons, the organic function layer that is formed by organism, the organic function layer of the functional layer that comprises the organic function layer that formed by organism and formed by inorganics, macromolecular material, low molecular material, comprise the organic function layer of macromolecular material and low molecular material etc.But, be not limited thereto, in this EL display unit 30, can use the organic function layer 36 of the known various materials of using as EL element.
Configuration siccative 38 in the space of cathode electrode 37 and sealing cover 39.This is because 36 pairs of humidity sensitives of organic function layer.Absorb moisture by siccative 38, prevent the deterioration of organic function layer 36.
Figure 10 is the sketch chart of section constitution of other forms of expression this EL display unit 30.This this EL display unit 30 has the sealed structure that has used diaphragm seal film 42, even all can obtain to launch light from the opposing face of array substrate.
As diaphragm seal film 42, the DLC(diamond-like carbon that preferably used on the film of chemical capacitor evaporation) DLC film.The DLC film has the characteristic of water vapour permeability extreme difference, the moisture-proof characteristic height.In addition, DLC film etc. can be on the surface of cathode electrode 37 directly evaporation form.In addition, can be multilayer with resin film and metallic film lamination, form diaphragm seal film 42.
As above, provide the novel display unit (this liquid crystal indicator and this EL display unit) that possesses this light polarizing film, this polarizer, this circularly polarizing plate and this light polarizing film.
At last, the projection-type liquid crystal display device that has used this light polarizing film is described.
Figure 11 is the sketch chart that shows the projection-type liquid crystal display device that has used this light polarizing film.
The polarizer 142 and/or the polarizer 143 as this projection-type liquid crystal display device use this light polarizing film.
From as the light source of luminous source (for example, high voltage mercury lamp) the light shafts nationality of 111 emissions by the 1st lens arra 112, the 2nd lens arra 113, polarized light conversion element 114, compound lens 115, carries out homogenization and the polarization light of the brightness on the reflection ray area of beam by at first.
Particularly, the light shafts nationality of launching from light source 111 forms rectangular the 1st lens arra 112 that forms by micro lens 112a and is split into many small light shafts.Possess the 2nd lens arra 113 and compound lens 115, it is all to make that divided light shafts shine respectively as 3 liquid crystal panel 140R, 140G, the 140B of lighting object, therefore, and each liquid crystal panel light incident side surface integral body roughly homogeneous of illumination that becomes.
Polarized light conversion element 114 is made of polarization beam splitter array, is configured between the 2nd lens arra 113 and the compound lens 115.The polarized light conversion element will be converted to the polarized light with specific polarization direction in advance from the random polarization of light source emission thus, reduce the optical loss in the aftermentioned light incident side polarizer, play a part to make the brightness of picture to improve.
The light that has as above carried out brightness homogenization and polarization light is separated into red channel, green channel, blue channel via speculum 122 nationalitys successively by being separated into the dichroic mirror 121,123,132 that the RGB3 primary colors uses, and injects liquid crystal panel 140R, 140G, 140B respectively.
Among liquid crystal panel 140R, 140G, the 140B, dispose the polarizer 142 at its light incident side, disposing the polarizer 143 respectively in emitting side.In this polarizer 142, the polarizer 143, can use this light polarizing film.
The extinction axle that the polarizer 142 that will dispose in each light path of RGB and the polarizer 143 are configured to separately intersects vertically.Each liquid crystal panel 140R, the 140G, the 140B that dispose in each light path have the function that the polarized light state of each pixel being controlled according to picture signal converts light quantity to.
The kind of the dichroism pigment by selecting to be suitable for corresponding passage, though this polarizer 100 in light paths such as blue channel, green channel and red channel also as the light polarizing film of excellent in te pins of durability and useful.
According to the view data of liquid crystal panel 140R, 140G, 140B, by making incident light each pixel is seen through the optical imagery made from different transmittances, synthetic by cross colour splitting prism 150, by projection lens 170 enlarging projection on projection screen 180.
As Electronic Paper, Electronic Paper, electronics and hole combination that the Electronic Paper that the Electronic Paper that the Electronic Paper that can list the Electronic Paper that shows by the molecule as optical anisotropy and dye molecule orientation, show by electrophoresis, particle motion, particle rotation, the such particle of phase change, the end by film move to show, the color development/phase change by molecule show, the photoabsorption by molecule show, the Electronic Paper that shows by luminous etc.More specifically, can list the microcapsule-type electrophoresis, move horizontally the type electrophoresis, vertical shifting type electrophoresis, spherically reverse that ball, magnetic reverse ball, cylinder reverses ball mode, charged toner, electronics powder fluid, magnetophoresis ejector half, magnetic strength hot type, moistening, the scattering of light (transparent/white opacity changes) of electricity, cholesteryl liquid crystal/optical conductive layer, cholesteryl liquid crystal, bistability nematic liquid crystal, lure electrical liquid crystal, 2 chromotropism pigment liquid crystal dispersion methods, movable film, color development colour killing, photochromic, electrochromism by leuco dye, galvanic deposit and the organic EL of elasticity etc. by force.Electronic Paper not only is used for individual's text and image, also can be used for advertisement demonstration (label) etc.By this light polarizing film, can make the thickness attenuation of Electronic Paper.
As 3 d display device, the for example method (the Japanese Patent spy opens the 2002-185983 communique) that different phase retardation films is alternately arranged as small polarization mode (マ イ Network ロ Port one Le mode) has been proposed, but if use this light polarizing film, then because forming pattern easily by printing, spray ink Printing, photoetching etc., the manufacturing process of display unit is shortened, and become and do not need phase retardation film.
[embodiment]
Below, further describe the present invention according to embodiment.As long as there is not explanation separately, it is quality % and mass parts that " % " in the example reaches " part ".
The preparation of embodiment 1[compound (1A) (following (1A) represented compound)]
Figure BDA00002871576900371
Compound (1A) synthesizes by following proposal.
Figure BDA00002871576900372
Compound [compound (1B)] 5.00g, 4-nipagin A 4.63g, dimethyl aminopyridine (DMAP) 0.23g and chloroform 25g that hybrid (1B) is represented under the lucifuge nitrogen atmosphere, stirred 10 minutes down at 5 ℃.In the mixed solution that makes, splashed into di-isopropyl carbodiimide (IPC) 2.58g in time-consuming 5 minutes, further stirred 4 hours.In the reaction solution that obtains, add methyl alcohol 75g, crystallization, filtration obtains crystallization.After further using the methanol wash crystallization of equivalent, by vacuum-drying, obtain compound (1A) 6.78g.Be benchmark with compound (1B), yield is 87%.
Compound (1A) 1H-NMR (CDCl 3): δ (ppm) 1.41 (t, 3H), 3.12 (s, 6H), 4.40 (m, 2H), 6.76 (m, 2H), 7.33 (m, 2H), 7.93 (dd, 4H), 8.15 (m, 2H), 8.30 (m, 2H).
Embodiment 2[compound (1D) (following (1D) represented compound)]
Figure BDA00002871576900381
Compound (1D) synthesizes according to following proposal.
Mixing cpd (1B) 5.00g, 4-butyl oxygen base phenol 4.63g, DMAP0.23g and chloroform 25g under the lucifuge nitrogen atmosphere, stirred 10 minutes down at 5 ℃.In the mixed solution that makes, splashed into IPC2.58g in time-consuming 5 minutes, further stirred 4 hours.In the reaction solution that obtains, add methyl alcohol 75g, crystallization, filtration obtains crystallization.Crystallization is dissolved in the 50g N,N-DIMETHYLACETAMIDE, by the diatomite filtration insolubles.Reclaim the filtrate water crystallization.The crystallization that makes further is dissolved in the 50g tetrahydrofuran (THF), after removing by filter insolubles, adds heptane, crystallization by vacuum-drying, obtains compound (1D) 4.66g.Be benchmark with compound (1B), yield is 60%.
Compound (1D) 1H-NMR (CDCl 3): δ (ppm) 0.99 (t, 3H), 1.45 (m, 2H), 1.78 (m, 2H), 3.12 (s, 6H), 3.98 (t, 2H), 6.77 (m, 2H), 6.93 (m, 2H), 7.15 (m, 2H), 7.92 (dd, 4H), 8.29 (dd, 2H).
Embodiment (manufacturings of this light polarizing film etc.) and reference example
[polymerizable liquid crystal compound]
Form with the polymerizable liquid crystal compound that comprises in the composition as light polarizing film, use the represented compound of following formula (2-6) [compound (2-6)], represented represented compound [compound (2-22)] and the represented compound [compound (2-25)] of following formula (2-25) of compound [compound (2-8)], following formula (2-22) of following formula (2-8).
And compound (2-6) is by Lub et al.Recl.Trav.Chim.Pays-Bas, and the method for 115,321-328 (1996) record is synthetic.In addition, according to this method, preparation compound (2-8).
Compound (2-22) and compound (2-25) are according to the method preparation of No. 4719156 record of Japanese Patent
Compound (2-6):
Figure BDA00002871576900391
[mensuration of phase transition temperature]
Confirmed the phase transition temperature of compound (2-6) by the phase transition temperature of obtaining the film that is constituted by compound (2-6).Its operation is as follows.
Form the film that is constituted by compound (2-6) at the glass substrate that has formed alignment films, by heating on one side, on one side the texture that carries out with polarization microscope (BX-51, Olympus society system) observe and confirm phase transition temperature.After will being warming up to 120 ° of C by the film that compound (2-6) constitutes, when cooling, change nematic phase mutually at 112 ° of C places, change smectic A phase mutually at 110 ° of C places, change smectic B phase mutually at 94 ° of C places.
Compound (2-8):
Figure BDA00002871576900392
[mensuration of phase transition temperature]
Measure the phase transition temperature of similarly confirming compound (2-8) with the phase transition temperature of compound (2-6).After compound (2-8) is warming up to 140 ° of C, when cooling, locate to change into mutually nematic phase at 131 ℃, change smectic A phase mutually at 80 ° of C places, locate to change into mutually smectic B phase at 68 ℃.
Compound (2-22):
Figure BDA00002871576900393
[mensuration of phase transition temperature]
Measure the phase transition temperature of similarly confirming compound (2-22) with the phase transition temperature of compound (2-6).After compound (2-22) is warming up to 140 ° of C, when cooling, locate to change into mutually nematic phase at 106 ℃, locate to change into mutually smectic A phase at 103 ℃, locate to change into mutually smectic B phase at 86 ℃.
Compound (2-25):
Figure BDA00002871576900394
[mensuration of phase transition temperature]
Measure the phase transition temperature of similarly determining compound (2-25) with the phase transition temperature of compound (2-6).After compound (2-25) is warming up to 140 ℃, when cooling, locate to change into mutually nematic phase at 119 ℃, locate to change into mutually smectic A phase at 100 ℃, locate to change into mutually smectic B phase at 77 ℃.
Embodiment 3
[light polarizing film forms and uses preparation of compositions]
Mix following compositions, by stirring 1 hour down at 80 ℃, make light polarizing film and form with composition (G).
Polymerizable liquid crystal compound; 75 parts of compounds (2-6)
25 parts of compounds (2-8)
The dichroism pigment; 2.5 parts of compounds (1A)
Polymerization starter;
2-dimethylamino-2-benzyl-1-(4-morpholinyl phenyl)-1-butanone (gorgeous good solid 369; Ciba society system) 6 part
Flow agent;
Polyacrylic acid ester cpds (BYK-361N; Bi Ke chemistry society system) 1.5 part
Solvent; 250 parts of toluene
[mensuration of phase transition temperature]
Identical with the situation of compound (2-6) and compound (2-8), obtain light polarizing film and form phase transition temperature with the polymerizable liquid crystal compound that comprises in the composition (G).After this polymerizable liquid crystal compound is warming up to 140 ℃, when cooling, locate to change into mutually nematic phase at 115 ℃, locate to change into mutually smectic A phase at 105 ℃, locate to change into mutually smectic B phase at 75 ℃.
[manufacturing of this light polarizing film and evaluation]
1. the formation of alignment films
Use glass substrate as transparent substrate.
On glass substrate, by the 2 quality % aqueous solution (orientation polymer composition) of spin-coating method pva coating (polyvinyl alcohol 1000 fully saponified types, Wako Pure Chemical Industries, Ltd.'s system), after the drying, form the film of thickness 100nm.Then, form alignment films by implementing friction treatment on the surface of the film that makes.Use semi-automatic friction gear (trade(brand)name: LQ-008 type, Joyo Engineering Co., Ltd.'s system), by cloth (trade(brand)name: YA-20-RW, Ji Chuan Chemical Co., Ltd system), under the condition of depth of indentation 0.15mm, revolution 500rpm, 16.7mm/s, carry out friction treatment.By such friction treatment, make the laminate 1 that has formed alignment films at glass substrate.
2. the formation of light polarizing film
On the alignment films of laminate 1, form with composition (G) by spin-coating method coating light polarizing film, be quickly cooled to room temperature at heat drying on the hot-plate of 120 ° of C after 1 minute, form dry overlay film in described alignment films.Then, use UV irradiating unit (SPOT CURE SP-7; Ushio Electric Inc's system), by dry overlay film is shone exposure 2000mJ/cm 2The ultraviolet ray of (365nm benchmark) makes the polymerizable liquid crystal compound polymerization that comprises in the described dry overlay film under the state of the mesomorphic state that keeps described polymerizable liquid crystal compound, form light polarizing film by described dry overlay film, makes laminate 2.
By the thickness of laser microscope (OLS3000 processed of Olympus Co., Ltd) mensuration light polarizing film at this moment, the result is 1.7 μ tm.
3.X ray diffraction determination
Using X-ray diffraction device X ' Pert PRO MPD (Spectris Co., Ltd. system) to carry out X-ray diffraction to this light polarizing film of the laminate 2 that makes measures.Use Cu as target, the X ray that sends under the condition of x-ray tube current 40mA, x-ray tube voltage 45kV is situated between (obtains the frictional direction of the alignment films under light polarizing film in advance by 1/2 ° of fixing divergent slit from frictional direction.) incident, under the scope of sweep limit 2 θ=4.0～40.0 °, with the step-scan of 2 θ=0.01671 °, measuring, the result obtains full width at half maximum (FWHM) (FWHM)=about 0.31 ° sharp-pointed diffraction peak (bragg peak) near 2 θ=20.1 °.In addition, also obtain same result from the incident of friction vertical direction.The order cycle of obtaining from the peak position (d) is for about
Figure BDA00002871576900411
Formed the structure of reflection height smectic phase as can be known.
4. the mensuration of dichroic ratio
In order to confirm the availability of this polarizer, following mensuration dichroic ratio.
Use is provided with the device of the folder (Folder) that has the polarizer at spectrophotometer (UV-3150 processed of Shimadzu Corporation), is determined at the axial absorbancy (A of printing opacity under the maximum absorption wavelength by reference beam method 1) and the axial absorbancy (A of extinction 2).Described folder is provided with in the reference side and light quantity is blocked 50% mesh.By the axial absorbancy (A of printing opacity that measures 1) and the axial absorbancy (A of extinction 2) value calculate than (A 2/ A 1), as dichroic ratio.Maximum absorption wavelength (λ max1) is 506nm, and the dichroic ratio under this wavelength is shown as 30 high value.We can say that dichroic ratio is more high, as light polarizing film and useful.In addition, the dichroism pigment that uses in this light polarizing film forms with composition is 450nm with the maximum absorption wavelength (λ max2) of the form mensuration of solution, clear and definite moves to long wavelength side.This has shown to the result that long wavelength side moves: in this light polarizing film, form in the polymerizable liquid crystal compound polymerization closely between the molecular chain, when compound (1A) was scattered in wherein, described compound (1A) was interacting consumingly with this molecular chain.
Embodiment 4
Except using compound (1B) replacement compound (1A), similarly to Example 3, make this light polarizing film.Similarly measure maximum absorption wavelength and dichroic ratio, maximum absorption wavelength (λ max1) is 494nm as a result, and dichroic ratio shows 30 high value.The maximum absorption wavelength (λ max2) of measuring the dichroism pigment solution is 446nm, clear and definite moves to long wavelength side.This result has shown: in this light polarizing film, form in the polymerizable liquid crystal compound polymerization closely between the molecular chain, when compound (1A) was scattered in wherein, described compound (1A) was interacting consumingly with this molecular chain.
Embodiment 5
Except using compound (2-22) replacement compound (2-6), use compound (2-25) replacement compound (2-8), make light polarizing film similarly to Example 3.Similarly measure maximum absorption wavelength and dichroic ratio, maximum absorption wavelength (λ max1) is 500nm as a result, and dichroic ratio is shown as 27 high value.The maximum absorption wavelength (λ max2) of measuring the dichroism pigment solution is 450nm, clear and definite moves to long wavelength side.
Embodiment 6
Except using compound (2-22) replacement compound (2-6), use compound (2-25) replacement compound (2-8), make light polarizing film similarly to Example 4.Similarly measure maximum absorption wavelength and dichroic ratio, maximum absorption wavelength (λ max1) is 492nm as a result, and dichroic ratio is shown as 28 high value.The maximum absorption wavelength (λ max2) of measuring the dichroism pigment solution is 446nm, clear and definite moves to long wavelength side.
Embodiment 7
Except use polymerizability nematic liquid crystal compound (the trade(brand)name LC242 processed of BASF society) 100 parts of replacements compound (2-6) and (2-8), make light polarizing film similarly to Example 3.Similarly measure maximum absorption wavelength and dichroic ratio, maximum absorption wavelength (λ max1) is that 464nm, dichroic ratio are 10 as a result.The maximum absorption wavelength (λ max2) of measuring the dichroism pigment solution is 450nm.
Embodiment 8
Except use polymerizability nematic liquid crystal compound (the trade(brand)name LC242 processed of BASF society) 100 parts of replacements compound (2-6) and (2-8), make light polarizing film similarly to Example 4.Similarly measure maximum absorption wavelength and dichroic ratio, maximum absorption wavelength is 462nm as a result, and dichroic ratio is 10.The maximum absorption wavelength (λ max2) of measuring the dichroism pigment solution is 446nm.
Comparative example 1
Except the compound of " the pigment numbering 5 " of using Japanese Patent 1454637 records replaces compound (1A), make light polarizing film similarly to Example 3.Similarly measure maximum absorption wavelength and dichroic ratio, maximum absorption wavelength (λ max1) is 398nm as a result, and dichroic ratio is 20.The maximum absorption wavelength (λ .max2) of measuring the dichroism pigment solution is 386nm.The maximum absorption wavelength of described dichroism pigment is below the 400nm, and is in addition, little to the long wavelength side amount of movement.
The compound of " pigment numbering 5 "
Comparative example 2
Except the compound of " the pigment numbering 1 " of using Japanese Patent 1454637 records replaces compound (1A), make light polarizing film similarly to Example 3.Similarly measure maximum absorption wavelength and dichroic ratio, maximum absorption wavelength is 446nm as a result, and dichroic ratio is 4.The maximum absorption wavelength (λ max2) of measuring the dichroism pigment solution and getting is 436nm.Dichroic ratio is low, and is little to the long wavelength side amount of movement.
The compound of " pigment numbering 1 "
Figure BDA00002871576900432
Utilizability on the industry
Novel cpd of the present invention is extremely useful with the dichroism pigment as the light polarizing film manufacturing, the value height on industry.

Claims (16)

1. a compound is characterized in that, with formula (1) expression,
Figure FDA00002871576800011
In the formula (1),
Y is formula (Y1) or the represented group of formula (Y2),
Figure FDA00002871576800012
In the formula, L be Sauerstoffatom or-NR-, R is the alkyl of hydrogen atom or carbonatoms 1 ~ 4,
R 1Be formula (R 1-1), formula (R 1-2) or formula (R 1-3) represented group,
Figure FDA00002871576800013
In the formula, ma is 0 ~ 10 integer, and when having 2 ma in same group, these 2 ma are identical or different mutually, and * represents bonding position,
R 2Be formula (R 2-1), formula (R 2-2), formula (R 2-3), formula (R 2-4), formula (R 2-5) or formula (R 2-6) represented group,
Figure FDA00002871576800014
In the formula, mb is 0 ~ 10 integer, and * represents bonding position.
2. a dichroism pigment is characterized in that, the compound of putting down in writing with claim 1 is effective constituent.
3. a composition is characterized in that, contains compound and the polymerizable liquid crystal compound of claim 1 record.
4. according to the composition of claim 3 record, it is characterized in that described polymerizable liquid crystal compound is the compound that shows the smectic liquid crystal phase.
5. according to the composition of claim 3 or 4 records, it is characterized in that, further contain solvent.
6. according to the composition of any record of claim 3 ~ 5, it is characterized in that, further contain polymerization starter.
7. a light polarizing film is characterized in that, its composition by any record of claim 3 ~ 6 forms.
8. according to the light polarizing film of claim 7 record, it is characterized in that the maximum absorption wavelength of light polarizing film (λ max1) moves to the wavelength that the maximum absorption wavelength (λ max2) than dichroism pigment is also grown.
9. according to the light polarizing film of claim 7 or claim 8 record, it is characterized in that the difference of the maximum absorption wavelength (λ max2) of the maximum absorption wavelength of light polarizing film (λ max1) and dichroism pigment is more than the 20nm.
10. according to the light polarizing film of any record of claim 7 ~ 9, it is characterized in that, in X-ray diffraction is measured, obtain bragg peak.
11. a polarizer is characterized in that, has light polarizing film and the transparent substrate of any record of claim 7 ~ 10.
12. the manufacture method of a polarizer is characterized in that, has: the operation of the preparation laminate that the lamination alignment films forms on transparent substrate,
The composition of any record of the described alignment films coating claim 3 ~ 6 of described laminate form coated film operation,
Make the operation of the described polymerizable liquid crystal compound polymerization that comprises in the described coated film.
13. the manufacture method of a polarizer is characterized in that, has: transparent substrate form operation that optical alignment film forms laminate,
The composition of any record of the described optical alignment film coating claim 3 ~ 6 of described laminate form coated film operation,
Make the operation of the described polymerizable liquid crystal compound polymerization that comprises in the described coated film.
14. a liquid crystal indicator is characterized in that, possesses the light polarizing film of any record of claim 7 ~ 10.
15. a circularly polarizing plate is characterized in that, has light polarizing film and 1/4 wavelength plate of any record of claim 7 ~ 10, satisfies following (A1) and prerequisite (A2),
(A1) the slow axis angulation of the extinction axle of described light polarizing film and described 1/4 wavelength plate is about 45 °;
(A2) value that postpones with the front of described 1/4 wavelength plate of the light measurement of wavelength 550nm is the scope of 100 ~ 150nm.
16. an organic EL display possesses circularly polarizing plate and organic EL that claim 15 is put down in writing.
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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KR102448436B1 (en) 2014-10-17 2022-09-27 스미또모 가가꾸 가부시끼가이샤 Compound and composition
CN107532009B (en) * 2015-04-20 2020-04-24 日本化药株式会社 Composition containing dichroic dye, dye film produced using the composition, and polarizing element having the dye film
WO2018186503A1 (en) * 2017-04-07 2018-10-11 富士フイルム株式会社 Anisotropic light absorbing film and laminated body
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EP4361705A1 (en) 2021-06-21 2024-05-01 FUJIFILM Corporation Image projection system

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080153A1 (en) * 1981-11-16 1983-06-01 Mitsubishi Kasei Corporation Pleochroic azo dyes, a liquid crystal composition containing the azo dyes and a display device using the liquid crystal composition
JPS58187456A (en) * 1982-04-27 1983-11-01 Nippon Kayaku Co Ltd Azo dye
US4588517A (en) * 1982-06-30 1986-05-13 Hitachi, Ltd. Liquid crystal composition
JPH11101964A (en) * 1997-08-01 1999-04-13 Sony Corp Polarization element and display device
CN1356585A (en) * 2000-11-24 2002-07-03 香港科技大学 Process for preparing optical orientation film
CN1623107A (en) * 2002-01-23 2005-06-01 日东电工株式会社 Optical film, laminated polarizing plate, liquid crystal display using the same, and self-light-emitting display using the same
JP2005189393A (en) * 2003-12-25 2005-07-14 Nitto Denko Corp Elliptical polarizing plate and image display device
CN1764702A (en) * 2003-03-26 2006-04-26 罗利克有限公司 Polymerizable dichroic azo dyes
CN101937112A (en) * 2009-06-26 2011-01-05 住友化学株式会社 Polarization plates and used the laminated optical component of this polarization plates
JP2011048311A (en) * 2009-08-28 2011-03-10 Fujifilm Corp Dichroic dye, light-absorbing anisotropic film, polarizer and method for producing the same, and display device
JP2011100059A (en) * 2009-11-09 2011-05-19 Nitto Denko Corp Liquid-crystalline coating solution and polarizing film
JP2011215336A (en) * 2010-03-31 2011-10-27 Fujifilm Corp Polarizing film, display device and method of manufacturing the same
WO2011136310A1 (en) * 2010-04-27 2011-11-03 住友化学株式会社 Composition

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4719156Y1 (en) 1968-01-24 1972-06-30
JPS5884858A (en) * 1981-11-16 1983-05-21 Mitsubishi Chem Ind Ltd Azo-based multicolor dyestuff and liquid crystal composition and display containing the same
JPH0613703B2 (en) * 1982-06-30 1994-02-23 三菱化成株式会社 Guest-host type liquid crystal composition
JP3734044B2 (en) * 1995-02-17 2006-01-11 大日本インキ化学工業株式会社 Polymerizable liquid crystal composition and method for producing optical anisotropic body
JP3687130B2 (en) 1995-04-07 2005-08-24 住友化学株式会社 Alignment dye film, production method thereof, polarizing element and liquid crystal display device
CN101208623B (en) * 2005-06-27 2011-08-31 住友化学株式会社 Dichroic guest-host polarizer
JP2011148746A (en) * 2010-01-22 2011-08-04 Asahi Glass Co Ltd Non-polymerizable liquid crystal compound, polymerizable liquid crystal compound, liquid crystal composition, optically anisotropic material, and optical element
JP2012003121A (en) * 2010-06-18 2012-01-05 Fujifilm Corp Stereoscopic image print and method for producing the same

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080153A1 (en) * 1981-11-16 1983-06-01 Mitsubishi Kasei Corporation Pleochroic azo dyes, a liquid crystal composition containing the azo dyes and a display device using the liquid crystal composition
JPS58187456A (en) * 1982-04-27 1983-11-01 Nippon Kayaku Co Ltd Azo dye
US4588517A (en) * 1982-06-30 1986-05-13 Hitachi, Ltd. Liquid crystal composition
JPH11101964A (en) * 1997-08-01 1999-04-13 Sony Corp Polarization element and display device
CN1356585A (en) * 2000-11-24 2002-07-03 香港科技大学 Process for preparing optical orientation film
CN1623107A (en) * 2002-01-23 2005-06-01 日东电工株式会社 Optical film, laminated polarizing plate, liquid crystal display using the same, and self-light-emitting display using the same
CN1764702A (en) * 2003-03-26 2006-04-26 罗利克有限公司 Polymerizable dichroic azo dyes
JP2005189393A (en) * 2003-12-25 2005-07-14 Nitto Denko Corp Elliptical polarizing plate and image display device
CN101937112A (en) * 2009-06-26 2011-01-05 住友化学株式会社 Polarization plates and used the laminated optical component of this polarization plates
JP2011048311A (en) * 2009-08-28 2011-03-10 Fujifilm Corp Dichroic dye, light-absorbing anisotropic film, polarizer and method for producing the same, and display device
JP2011100059A (en) * 2009-11-09 2011-05-19 Nitto Denko Corp Liquid-crystalline coating solution and polarizing film
JP2011215336A (en) * 2010-03-31 2011-10-27 Fujifilm Corp Polarizing film, display device and method of manufacturing the same
WO2011136310A1 (en) * 2010-04-27 2011-11-03 住友化学株式会社 Composition

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KATRITZKY, ALAN ROY等: "Convenient preparations of azo-dye labeled amino acids and amines", 《ORGANIC & BIOMOLECULAR CHEMISTRY》, vol. 6, no. 13, 31 December 2008 (2008-12-31) *
MATSUI, M.等: "Synthesis of fluorine-containing disazo dyes extended with ester linkages and their application to guest-host liquid crystal displays", 《LIQUID CRYSTALS》, vol. 23, no. 2, 31 December 1997 (1997-12-31), pages 222, XP 000701490, DOI: doi:10.1080/026782997208479 *
SANO, MASAHITO等: "Sugar-Dependent Spectral Responses of Azobenzene Glycopyranoside Monolayers", 《LANGMUIR》, vol. 17, no. 14, 31 December 2001 (2001-12-31), pages 4368 *

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* Cited by examiner, † Cited by third party
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