CN103336325A - Polarizing film, circular polarizing plate and method of producing the same - Google Patents
Polarizing film, circular polarizing plate and method of producing the same Download PDFInfo
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- CN103336325A CN103336325A CN2013100648325A CN201310064832A CN103336325A CN 103336325 A CN103336325 A CN 103336325A CN 2013100648325 A CN2013100648325 A CN 2013100648325A CN 201310064832 A CN201310064832 A CN 201310064832A CN 103336325 A CN103336325 A CN 103336325A
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- polarizing film
- formula
- light polarizing
- light
- liquid crystal
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- 0 C*(*)*N(C)*(*)* Chemical compound C*(*)*N(C)*(*)* 0.000 description 4
- ZBGZVIGUXBTBGM-UHFFFAOYSA-N CCC(C)N(C)C(C)CC Chemical compound CCC(C)N(C)C(C)CC ZBGZVIGUXBTBGM-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/60—Pleochroic dyes
- C09K19/601—Azoic
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
Abstract
The subject of the invention is to provide a polarizing film which is easy to be thin and has excellent neutral hue, a polarizer with the polarizing film and methods of producing the same. The invention provides a polarizing film, a polarizer with the polarizing film and methods of producing the same, wherein the polarizing film includes a polymer formed by polymerized liquid crystal compounds,is dispersed in the polymer to test light absorption, possesses at least one maximum absorption dichroism pigment (1) in a wave length scope of 380-550 nm and at least two dichroism pigments (2) in a wave length scope of 550-700 nm. The dichroism pigment (2) preferentially includes dichroism pigment with absorption in a wave length scope of 550-600 nm and dichroism pigment with absorption in a wave length scope of 600-700 nm.
Description
Technical field
The present invention relates to light polarizing film, circularly polarizing plate and their manufacture method etc.
Background technology
Because the polarizer that is used to liquid crystal indicator has high transmission rate and degree of polarization concurrently, thus with dichroism pigment dyeings such as iodine, stretch processing the film (light polarizing film) that is constituted by polyvinyl alcohol (PVA) (iodine staining PVA) widely used.For example, putting down in writing the light polarizing film that is constituted by iodine staining PVA in the patent documentation 1.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese patent laid-open 7-142170 communique
Summary of the invention
The problem that invention will solve
Yet, easily be with yellow by the light polarizing film that iodine staining PVA constitutes, the problem of so-called muted color phasic property difference appears.In addition, the light polarizing film that is made of iodine staining PVA is difficult to filming, and the nearest display device aspect that is applied to pursue more slimming is limited.Therefore, the object of the present invention is to provide easy filming, the light polarizing film of muted color phasic property excellence, the polarizer that comprises described light polarizing film and manufacture method thereof etc.
The means of dealing with problems
The present invention includes following invention.
[1] a kind of light polarizing film, it contains the polymkeric substance that formed by polymerizable liquid crystal compound, is scattered in when measuring light absorption in the described polymkeric substance, has at least a kind of dichroism pigment (1) of absorption maximum and at least 2 kinds of dichroism pigments (2) that have absorption maximum in the scope of wavelength 550 ~ 700nm in the scope of wavelength 380 ~ 550nm.
[2] according to the light polarizing film of record in [1], wherein, when making described dichroism pigment (1) be scattered in the polymkeric substance that is formed by polymerizable liquid crystal compound the mensuration light absorption, has absorption maximum in the scope of wavelength 400 ~ 550nm.
[3] according to the light polarizing film of record in [1] or [2], wherein, be scattered in when measuring light absorption in the described polymkeric substance, when at least 2 kinds of dichroism pigments (2) that have an absorption maximum in the scope of wavelength 550 ~ 700nm are being scattered in and are measuring light absorption in the described polymkeric substance,
Contain scope at wavelength 550 ~ 600nm have absorption maximum dichroism pigment (2-1) and
The dichroism pigment (2-2) that has absorption maximum in the scope of wavelength 600 ~ 700nm.
[4] according to the light polarizing film of record among any of [1] ~ [3], polymerizable liquid crystal compound is the compound that shows the smectic crystal phase.
[5] light polarizing film of any record of basis [1] ~ [4], it obtains bragg peak in X-ray diffraction is measured.
[6] light polarizing film of any record of basis [1] ~ [5], wherein, L
*a
*b
*Chromaticity coordinates a in the colour system
*Value and b
*Value satisfies the relation of following formula (1F) and formula (2F).
-3≤colourity a
*≤ 3(1F)
-3≤colourity b
*≤ 3(2F)
[7] according to the light polarizing film of record among any of [1] ~ [6], wherein, dichroism pigment (1) and dichroism pigment (2) are azo-compound.
[8] according to the light polarizing film of record among any of [1] ~ [7], wherein, dichroism pigment (2) is made of the represented compound of formula (2).
[in the formula (2),
N is 1 or 2.
Ar
1And Ar
3Be any one represented group of formula (AR-1) ~ formula (AR-4) independently respectively.
Ar
2Be formula (AR2-1), formula (AR2-2) or the represented group of formula (AR2-3).
A
1And A
2Be any one represented group of formula (A-1) ~ formula (A-9) independently respectively, * represents bonding position.
(mc is 0 ~ 10 integer, and when having 2 mc in same group, these 2 mc can be identical or different mutually.）]
[9] according to the light polarizing film of record among any of [1] ~ [8], wherein, dichroism pigment (1) is made of the represented compound of formula (1).
[in the formula (1),
Y is formula (Y1) or the represented group of formula (Y2).
(in the formula, L be oxygen atom or-NR-, R is the alkyl of hydrogen atom or carbon number 1 ~ 4.）
R
1Be formula (R
1-1) ~ formula (R
1-3) group that any one is represented.
(in the formula, ma is 0 ~ 10 integer, and when having 2 ma in the same group, these 2 ma can be identical or different mutually.* represent bonding position.）
R
2Be formula (R
2-1) ~ formula (R
2-6) group that any one is represented.
(in the formula, mb is 0 ~ 10 integer.）]
[10] a kind of polarizer, it is to form in the light polarizing film that transparent base arranges any record of [1] ~ [9].
[11] manufacture method of the polarizer of basis [10] record, it has
Preparation transparent base possess the laminate of alignment films operation,
The operation of coating composition on the described alignment films of described laminate, described composition contains polymerizable liquid crystal compound, is scattered in when measuring light absorption in the polymkeric substance that is formed by described polymerizable liquid crystal compound, the 2 kinds of dichroism pigments (2) and the solvent that have a kind of dichroism pigment (1) of absorption maximum, have absorption maximum in the scope of wavelength 550 ~ 700nm in the scope of wavelength 380 ~ 550nm
Make the operation of the described polymerizable liquid crystal compound polymerization that comprises in the described composition.
[12] according to the manufacture method of record in [11], wherein, transparent base is plastic basis material, and described alignment films is optical alignment film.
[13] a kind of liquid crystal indicator, it possesses the light polarizing film of any record of [1] ~ [9].
[14] a kind of circularly polarizing plate, it has the light polarizing film of any record of [1] ~ [9] and λ/4 layer, satisfies following (A1) and necessary condition (A2).
(A1) the formed angle of slow axis of the extinction axle of described light polarizing film and described λ/4 layer is about 45 °;
(A2) value that postpones with the front of described λ/4 of the light measurement of wavelength 550nm layer is the scope of 100 ~ 150nm
[15] a kind of organic EL display, it possesses circularly polarizing plate and the organic EL of [14] record.
The invention effect
According to the present invention, can provide easy filming, muted color phasic property excellence light polarizing film, comprise the polarizer of described light polarizing film.
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 direction of orientation 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 device 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 device of Fig. 6.
[Figure 10] is the synoptic diagram of the section constitution of the expression EL display device of using light polarizing film of the present invention.
[Figure 11] is the skeleton diagram that shows the formation of the projection-type liquid crystal display device that has used light polarizing film of the present invention.
Symbol description
1 transparent base
2 optical alignment films
3 light polarizing film
4 phase separation layers
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 irradiation unit
The 213B light irradiation device
300 help rolls
10 liquid crystal indicators
11 sealers
12a, the 12b polarizer
13a, 13b phase separation layer
14a, 14b substrate
15 color filters
16 transparency electrodes
17 liquid crystal layers
18 interlayer dielectrics
19 modules backlight
20 stain matrixes
21 thin film transistor (TFT)s
22 pixel electrodes
23 pads
The 30EL display device
31 circularly polarizing plates
32 phase retardation films
33 substrates
34 interlayer dielectrics
35 pixel electrodes
36 organic function layers
37 cathode electrodes
38 drying agent
39 gland bonnets
40 thin film transistor (TFT)s
41 ribs (Rib)
42 diaphragm seal films
The 44EL display device
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 dichronic mirrors
122 catoptrons
140R, 140G, 140B liquid crystal panel
142,143 polarizers
150 cross colour splitting prisms (Cross dichroic prism)
170 projection lens
180 projection screens
Embodiment
Light polarizing film of the present invention (below, according to circumstances be referred to as " this light polarizing film ".) be characterised in that, contain the polymkeric substance that formed by polymerizable liquid crystal compound and specific dichroism pigment more than 3 kinds.Preferred this light polarizing film by contain polymerizable liquid crystal compound and described more than 3 kinds the dichroism pigment composition (below, according to circumstances be referred to as " light polarizing film forms and uses composition ".) form.At first, formation describes with composition to light polarizing film.
1. light polarizing film forms and uses composition
Light polarizing film of the present invention forms with composition as mentioned above, contains polymerizable liquid crystal compound and specific dichroism pigment more than 3 kinds, and preferably it further contains solvent.Form this light polarizing film that forms with composition by such light polarizing film and easily carry out filming.At first, formation describes respectively with each constituent that comprises in the composition to light polarizing film.
1-1. dichroism pigment
Light polarizing film forms and comprises with the dichroism pigment that comprises in the composition: the scope at wavelength 380 ~ 550nm when measuring light absorption in being scattered in the polymkeric substance that is formed by polymerizable liquid crystal compound has at least a kind of dichroism pigment (1) of absorption maximum and at least 2 kinds of dichroism pigments (2) that have absorption maximum in identical mensuration in the scope of wavelength 550 ~ 700nm.
1-1-1. dichroism pigment (1)
When dichroism pigment (1) is scattered in the polymkeric substance that is formed by polymerizable liquid crystal compound when measuring light absorption, has absorption maximum in the scope of wavelength 380 ~ 550nm.And, as long as this mensuration is following mensuration: preparation is replaced into the absorption maximum mensuration composition that desire is measured the dichroism pigment of absorption maximum with the dichroism pigment that the light polarizing film among the present invention forms with composition, by forming the identical method of the method for this light polarizing film with described later formation with composition by light polarizing film, form absorption maximum mensuration and use film, measure this absorption maximum and measure the light absorption of using film.The method of putting down in writing in the concrete grammar of measuring described absorption maximum and the embodiment of the present application is identical.
As dichroism pigment (1), can enumerate as azo-compound.Can preferably list the represented compound of described formula (1) (below, according to circumstances be referred to as " compound (1) ".）。
The rotamerism at the azobenzene 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 oxygen atom or-NR-, R is the alkyl of hydrogen atom or carbon number 1 ~ 4.As described alkyl, can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl and the tert-butyl group etc.Wherein, preferred L be oxygen atom or-NH-, more preferably oxygen atom.
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 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 ~ 10 integer, more preferably 0 ~ 5 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.
When obtaining the light absorption of dichroism pigment (1) by said determination, its scope at wavelength 380 ~ 550nm has absorption maximum, preferably the scope at wavelength 400 ~ 550nm has absorption maximum, more preferably the scope at wavelength 400 ~ 520nm has absorption maximum, further preferably have absorption maximum in the scope of wavelength 430 ~ 520nm, have absorption maximum particularly preferably in the scope of wavelength 440 ~ 510nm.If have absorption maximum in described scope, then also can use multiple compound (1) as dichroism pigment (1).
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).
Described graphic in, R
1, R
2And Y and above-mentioned equivalent in meaning, Re
1And Re
2It is interreaction and generate 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.
The reaction conditions in compound (1X) and compound (1Y) when reaction can be selected suitably according to the kind of the compound (1X) that uses and compound (1Y), the suitableeest known condition.
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 diisopropyl carbodiimides (IPC) etc.Herein, further preferred and with the alkali of dimethylamino naphthyridine (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 time can be enumerated the scope as 15 minutes ~ 48 hours.
Also can suitably sample to the reaction mixture in the course of reaction, by known analytical approachs such as liquid phase chromatography or vapor-phase chromatographies, the degree of the degree of the minimizing of affirmation compound (1X) and compound (1Y), the generation of compound (1), thus determine the reaction time.
By recrystallization, precipitate again, known method such as extraction and various chromatographys or by these operations of combination, can extract compound (1) from reacted reaction mixture.
1-1-2. dichroism pigment (2)
When implementing described mensuration, dichroism pigment (2) has absorption maximum in the scope of wavelength 550 ~ 700nm.The assay method of absorption maximum is identical with the situation of dichroism pigment (1).
In forming with composition, light polarizing film contains dichroism pigment (2) more than 2 kinds, wherein, the scope that more preferably contains at wavelength 550 ~ 600nm has the dichroism pigment (2-1) of absorption maximum and the dichroism pigment (2-2) that has absorption maximum in the scope of wavelength 600 ~ 700nm.Herein, further preferred dichroism pigment (2-1) has absorption maximum in the scope of wavelength 570 ~ 600nm, and further preferred dichroism pigment (2-2) has absorption maximum in the scope of wavelength 600 ~ 680nm.
As dichroism pigment (2), can enumerate as azo-compound.Preferred dichroism pigment (2) be the represented compound of described formula (2) (below, according to circumstances be referred to as " compound (2) ".）。
The rotamerism at the azobenzene position of preferred compound (2) is trans.
In the combination of each group of compound (2), by composition Ar
1, Ar
2And Ar
3, determine to can be used as the compound (2) that dichroism pigment (2-1) uses, so that described compound (2) has absorption maximum in the scope of wavelength 550 ~ 600nm in said determination.As concrete dichroism pigment (2-1), can list the shown compound (2) of combination of each group in the table 1.N in the table 1 in compound (2-1) expression (2) of the combination of each group of demonstration is 1 situation.And in the table 1, for example represented group of formula (AR-1) etc. is labeled as " (AR-1) " etc.
[table 1]
Then, in the combination of each group of compound (2), by combination Ar
1, Ar
2And Ar
3, determine can be used as the compound (2) of dichroism pigment (2-2), so that described compound (2) has absorption in the scope of wavelength 600 ~ 700nm in said determination.As concrete dichroism pigment (2-2), can list the shown compound (2) of the combination of each group in the table 2.N in the table 2 in compound (2-2) expression (2) of the combination of each group of demonstration is 1 situation.And the mark of the group in the table 2 is identical with the situation of table 1.
[table 2]
If specifically illustrate compound (2), then can list the compound represented respectively by formula (2-11) formula (2-39) etc. herein.
Among the concrete example of the compound that herein lists (2), as dichroism pigment (2-1), be equivalent to by formula (2-12), formula (2-13), formula (2-18), formula (2-20), formula (2-21), formula (2-22), formula (2-23), formula (2-24), formula (2-26), formula (2-27), formula (2-28), the compound that formula (2-29) and formula (2-30) are represented respectively, as dichroism pigment (2-2), be equivalent to by formula (2-31), formula (2-32), formula (2-33), formula (2-34), the compound that formula (2-35) and formula (2-36) are represented respectively.And the compound of being represented respectively by formula (2-11), formula (2-15) and formula (2-16) is not to show the pigment that absorbs in wavelength 550 ~ 700nm, but can also use with the pigment of formula (1) with replenishing.
Among the concrete example of compound (2), form with the dichroism pigment (2) that comprises in the composition, the more preferably material of being represented respectively by formula (2-15), formula (2-16), formula (2-18), formula (2-20), formula (2-21), formula (2-22), formula (2-23), formula (2-27), formula (2-29), formula (2-31), formula (2-32), formula (2-33), formula (2-34) and formula (2-35) as light polarizing film.Among these, if dichroism pigment (2) uses the combination of selecting from the concrete example of compound (2) more than 2 kinds to represent, though then different because of mixture ratio, and for example demonstration identical in the table 3.In this table 3, for example the represented compound (2) of formula (2-11) is expressed as " (2-11) ".
[table 3]
Light polarizing film formation is used with respect to the content of aftermentioned polymerizable liquid crystal compound 100 mass parts with the content of the dichroism pigment (1) in the composition and is represented, be preferably below 50 mass parts, more preferably 0.1 mass parts above, below 10 mass parts, more preferably 0.1 mass parts above, below 5 mass parts.
Light polarizing film formation is used with respect to the content of polymerizable liquid crystal compound 100 mass parts described later with the content of the dichroism pigment (2) in the composition and is represented, be preferably below 10 mass parts, more preferably 0.1 mass parts above, below 5 mass parts, more preferably 0.1 mass parts above, below 3 mass parts.
In addition, light polarizing film formation is used with respect to the content of aftermentioned polymerizable liquid crystal compound 100 mass parts with the total content of the dichroism pigment (1) in the composition and dichroism pigment (2) and is represented, be preferably below 30 mass parts, more preferably 0.1 mass parts above, below 20 mass parts, more preferably 1 mass parts above, below 15 mass parts.
If the content of each dichroism pigment is in described scope, then because forming, light polarizing film with the dichroism pigment in the composition solvent is shown sufficient dissolubility, so when making this light polarizing film with described light polarizing film formation with composition, can make this light polarizing film that does not produce defective.And, as mentioned above, light polarizing film forms with composition can contain more than a kind dichroism pigment (1) and dichroism pigment (2) more than 2 kinds, also can contain dichroism pigment (1) more than 2 kinds but described light polarizing film forms with composition, also can contain dichroism pigment (2) more than 3 kinds.When containing more than 2 kinds dichroism pigment (1), the content of dichroism pigment (1) is the total amount of the dichroism pigment (1) more than 2 kinds, when containing more than 3 kinds dichroism pigment (2), the content of dichroism pigment (2) is the total amount of the dichroism pigment (2) more than 3 kinds.
Dichroism pigment (2) can be opened clear 58-38756 communique, Jap.P. spy by for example Jap.P. spy and open clear 63-301850 communique, Jap.P. spy and open the known method of record in the clear 58-104984 communique etc. and make.
Then, formation describes with the constituent beyond the dichroism pigment in the composition to light polarizing film.
1-2. polymerizable liquid crystal compound
The liquid-crystal compounds of polymerizable liquid crystal compound for can carry out polymerization under the state of orientation, it has polymerizable group in molecule.The light polarizing film that contains polymerizable liquid crystal compound forms with composition by polymerization under the state that makes the polymerizable liquid crystal compound orientation, forms this light polarizing film.Special preferred polymeric group is free-radical polymerised group.Free-radical polymerised group refers to participate in the group of Raolical polymerizable.
Light polarizing film of the present invention form with the polymerizable liquid crystal compound that comprises in the composition can be demonstration nematic crystal phase (below, according to circumstances be referred to as " nematic crystal phase ".) compound, also can be show the smectic crystal phase (below, according to circumstances be referred to as " smectic crystal phase ".) compound, can also be to show that nematic crystal reaches smectic crystal both compounds mutually mutually, but be preferably the polymerism smectic crystal compound that shows the smectic crystal phase at least.The light polarizing film that contains polymerism smectic crystal compound forms with the interaction of composition by dichroism pigment (1) and dichroism pigment (2), and the muted color phasic property is very good, can make this more excellent light polarizing film of polarization property.
As the shown smectic crystal phase of polymerism smectic crystal compound, height smectic crystal phase more preferably.Height smectic 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 crystal of polymerizable liquid crystal compound is these height smectic 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 height smectic crystal of ordered orientation degree like this can obtain deriving from hexagonal mutually or the bragg peak of the equal multidimensional structure of crystallization 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 with the polymerizable liquid crystal compound that comprises in the composition whether show nematic crystal mutually or the smectic crystal phase, 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, the coated film that forms on the base material is heated to the isotropic phase temperature, examines Check by slowly cooling off the liquid crystal phase that shows by texture observation, X-ray diffraction mensuration or the differential scanning calorimetric determination of using polarization microscope to carry out.In this inspection Check, for example be preferably especially, show the nematic crystal phase by cooling, show the polymerizable liquid crystal compound of smectic crystal phase by further cooling.Nematic crystal reach mutually smectic 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 are not separated.
Below, list as being used for the concrete example that light polarizing film forms the preferred compound of polymerizable liquid crystal compound of using composition.
As preferred polymerizable liquid crystal compound, can enumerate suc as formula (4) represented compound (below, according to circumstances be referred to as " compound (4) ").
U
1-V
1-W
1-X
1-Y
1-X
2-Y
2-X
3-W
2-V
2-U
2?（4）
[in the formula (4),
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 carbon number 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 carbon number 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 of substituent carbon number 1 ~ 20 independently of each other, constitute described alkylidene-CH
2-can by-O-,-S-or-NH-replaces.]
In the compound (4), 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.
The Y of preferred compound (4)
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 photopolymerization group.The photopolymerization group refers to can participate in by the living radical that is produced by the aftermentioned photo-induced polymerization initiator or acid etc. the group of polyreaction.Polymerizable liquid crystal compound with photopolymerization group is can be favourable aspect the polymerization under the cryogenic conditions more.
In the compound (4), U
1And U
2Polymerizable group can be mutually different, but be preferably the group of identical type.As polymerizable group, can list vinyl, ethyleneoxy, 1-chlorovinyl, isopropenyl, 4-ethenylphenyl, acryloxy, methacryloxy, epoxy ethyl, oxa-cyclobutyl etc.Wherein, be preferably acryloxy, methacryloxy, ethyleneoxy, epoxy ethyl and oxa-cyclobutyl, more preferably acryloxy.
As V
1And V
2The alkylidene of the carbon number 1 ~ 20 in the represented alkylidene that has or do not have substituent carbon number 1 ~ 20, can list methylene, ethylidene, 1,3-propylidene, 1,3-butylidene, 1,4-butylidene, 1,5-pentylidene, 1,6-hexylidene, 1, the inferior heptyl, 1 of 7-, the inferior octyl group, 1 of 8-, the inferior decyl, 1 of 10-, the inferior myristyl of 14-and the inferior eicosyl of 1,20-etc.Preferred V
1And V
2Be the alkylidene of carbon number 2 ~ 12, more preferably the alkylidene of carbon number 6 ~ 12.
As the substituting group that the alkylidene that has or do not have substituent carbon number 1 ~ 20 has arbitrarily, though can list cyano group and halogen atom etc., preferred described alkylidene does not replace, and does not more preferably replace and the alkylidene of straight chain shape.
W
1And W
2Be preferably independently of each other singly-bound or-O-.
As compound (4), can list the represented compound of formula (4-1) ~ formula (4-43) etc.When the concrete example of such compound (4) had 1,4-cyclohexylene, preferred such 1, the 4-cyclohexylene was trans body.
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 (4).Mixing ratio 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 (4), be preferably formula (4-5), formula (4-6), formula (4-7), formula (4-8), formula (4-9), formula (4-10), formula (4-11), formula (4-12), formula (4-13), formula (4-14), formula (4-15), formula (4-22), formula (4-24), formula (4-25), formula (4-26), formula (4-27), formula (4-28) and the represented compound of formula (4-29).These compounds by with the interaction of other polymerizable liquid crystal compounds, under the temperature conditions that is lower than the crystallization phase 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 conditions 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 described 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 ingredients 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 Jap.P. etc. prepare.
1-3. solvent
Preferred light polarizing film forms and contains solvent with composition.As solvent, be preferably the solvent of solvent polymerization liquid-crystal compounds fully and dichroism pigment.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, isopropyl alcohol, propylene glycol, ethylene glycol monomethyl ether, butyl glycol ether and propylene glycol monomethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, gamma-butyrolacton or ester solvents such as propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; 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 and dimethoxy-ethane; Chlorinated solvents such as chloroform and chlorobenzene; Deng.These solvents can use separately, also can multiplely be used in combination.
Form the total amount of using composition with respect to described light polarizing film, the content of preferred solvent is 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 of this slim light polarizing film that easily makes one of purpose of the present invention 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.
1-4. other adjuvants
Light polarizing film among the present invention forms with composition and at random contains dichroism pigment, polymerizable liquid crystal compound and solvent adjuvant in addition.
1-4-1. polyreaction auxiliary agent
Preferred light polarizing film forms and contains polymerization initiator with composition.Described polymerization initiator is the compound of polyreaction that can the initiated polymerization liquid-crystal compounds.As polymerization initiator, but initiated polymerization is leavened dough under cryogenic conditions, is preferably photo-induced polymerization initiator.Particularly, can be used as photo-induced polymerization initiator by the effect generation living radical of light or the compound of acid.Among the described photo-induced polymerization initiator, more preferably produce the material of living radical by the effect of light.
As polymerization initiator, can enumerate as styrax compound, benzophenone cpd, alkyl phenyl ketonic compound, acylphosphine oxide compound, triaizine compounds, salt compounded of iodine and sulfonium salt etc.
As the styrax compound, can enumerate as styrax, 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 thio-phenyl)-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1,2-diphenyl-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]-oligomer 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-methoxyphenyls as: 2,4-)-1,3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl 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-methylfurans of 2,4--2-yl) vinyl]-1,3, the 5-triazine, two (the trichloromethyl)-6-[2-(furans of 2,4--2-yl) vinyl]-1,3, the 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylaminos 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 initiator can also use commercially available article.As commercially available polymerization initiator, 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 initiator 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, amount to 100 mass parts with respect to polymerizable liquid crystal compound, the content of polymerization initiator is 0.1 ~ 30 mass parts, be preferably 0.5 ~ 10 mass parts, more preferably 0.5 ~ 8 mass parts.If the content of polymerism initiating agent is in this scope, then because can not having to make its polymerization under the chaotic situation so preferred in the orientation of polymerizable liquid crystal compound.
1-4-2. photosensitizer
When light polarizing film formation contained photo-induced polymerization initiator 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 alkoxy; Phenothiazine and rubrene etc.
When light polarizing film formation contained photo-induced polymerization initiator 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 photo-induced polymerization initiator 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.
1-4-3. polymerization inhibitor
For the polyreaction that makes polymerizable liquid crystal compound is stably carried out, light polarizing film forms can contain polymerization inhibitor with composition.By polymerization inhibitor, can control the degree that the polyreaction of polymerizable liquid crystal compound is carried out.
As polymerization inhibitor, can enumerate as: p-dihydroxy-benzene, contain alkoxy p-dihydroxy-benzene, contain catechol (for example, butyl-catechol etc.), the pyrogallol, 2,2,6 of alkoxy, 6-tetramethyl-radical scavengers such as 1-piperidines oxygen base free radical; The benzenethiol class; Beta-naphthylamine class and betanaphthol class etc.
Light polarizing film forms when containing polymerization inhibitor in the 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, with respect to polymerizable liquid crystal compound 100 mass parts, 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 polymerization inhibitor is in above-mentioned scope, then do not have to make its polymerization so preferably under the situation of confusion because of the orientation of the polymerizable liquid crystal compound that can in light polarizing film forms with composition, contain.
1-4-4. levelling agent
Preferred light polarizing film forms and contains levelling agent with composition.Levelling 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 surfactant etc.As preferred levelling agent, can list with the polyacrylic acid ester compounds and be the levelling agent of major component and be the levelling agent etc. of major component with the compound of contain fluorine atoms.
As being the levelling agent of major component with the polyacrylic acid ester compounds, 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 (BYK Chemie)] etc.
Be the levelling agent of major component 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 research institute]; " EFTOP(エ Off ト Star プ) EF301 ", EFTOP " EF303 ", EFTOP " EF351 " and EFTOP " EF352 " [the Mitsubishi Materials electronics changes into (strain)] etc.
Light polarizing film is formed when containing levelling agent in the composition, with respect to content 100 mass parts of polymerizable liquid crystal compound, its content be generally 0.3 mass parts above, below 5 mass parts, be preferably more than 0.5 mass parts, below 3 mass parts.If the content of levelling 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 levelling agent of polymerizable liquid crystal compound surpasses described scope, then have in this light polarizing film that makes, easily to produce inhomogeneous tendency.And described light polarizing film forms with composition can contain levelling agent more than 2 kinds.
2. 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, and preferably be coated on the transparent base, thereby form this light polarizing film.
2-1. transparent base
Transparent base 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 base, can list glass baseplate and plastic basis material etc., be preferably plastic basis material.As the plastics that constitute plastic basis material, can enumerate as polyolefin such as tygon, polypropylene, norbornene-based polymer; Annular ethylene series resin; Polyvinyl alcohol (PVA); Polyethylene terephthalate; Polymethacrylate; Polyacrylate; Cellulose esters 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 esters, annular ethylene series resin, polyethylene terephthalate or polymethacrylate.When using such transparent base to make this light polarizing film, aspect can under the situation of carrying, can not cause when taking care of described transparent base breakages such as destruction, easily operating, consider, also can stick support base material etc. at described transparent base.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 esters or annular ethylene series resin.
Cellulose esters is that at least a portion of the hydroxyl that comprises in the cellulose is by the material of acid esterification.The cellulose ester film that is made of such cellulose esters 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 base.In addition, surface treatments such as anti-dazzle processing, hard coat processing, electrostatic prevention processing or antireflection processing can be implemented, then as transparent base on the surface of ready transparent base.
In order to 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 norborene 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 that the annular ethylene series resin that contains the open loop position is carried out material after the hydrogenation.In addition, never can significantly damage transparent aspect or can not enlarge markedly the consideration of hydroscopicity aspect, described annular ethylene series resin for example can be the multipolymer of cyclic olefin, chain alkene or vinylated aromatics (styrene etc.) etc.In addition, described annular ethylene series resin can import polar group in its molecule.
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 styrene, α-Jia Jibenyixi 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 vinylated 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 heating furnace from such coiling body.The design temperature of heating 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 heating 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 hot-stretch 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 Jap.P. 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 clear base material, but if too thin then have intensity to reduce the tendency of processability 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 base during in particular as the circularly polarizing plate of mobile device 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.
2-2. 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 the solvent resistance that the degree of the dissolving that coating with composition etc. causes can not occur being formed 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 form by the orientation polymkeric substance.
As described orientation polymkeric substance, can enumerate as: have the polyimide that has imide bond in the polyamide of amido link or gelatin class, the molecule and the polymkeric substance such as polyamic acid, polyvinyl alcohol (PVA), alkyl-modified polyvinyl alcohol (PVA), polyacrylamide, poly-oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylate of hydrolysate thereof in the molecule.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, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, gamma-butyrolacton, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; 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 and dimethoxy-ethane; Chlorine such as chloroform and chlorobenzene replaces hydrocarbon solvent; Deng.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 base material, can enumerate as orientation polymer composition or commercially available aligning film material as described in the base material coating, 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 with coated film 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 photoreaction 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).The photoreaction group refers to, produces the group of liquid crystal aligning energy by irradiates light (illumination is penetrated).Particularly, its be by irradiates light produce as the orientation of molecule induce or isomerization reaction, dimerization reaction, photo-crosslinking or photolysis reactions generation become liquid crystal aligning can the material of light reaction of origin.Among the described photoreaction group, keep the smectic crystal state aspect to consider from the orientation excellence, when light polarizing film forms, preferably cause the material of dimerization reaction or photo-crosslinking.As the photoreaction group that can take place as above to react, be preferably and have unsaturated link, 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 photoreaction group with C=C key, can enumerate as vinyl, polyene-based, stilbene radicals, stilbene azoles base, stibazole alkali, chalcone base and cinnamoyl etc.As the photoreaction group with C=N key, can list and have aromatic series schiff bases and the isostructural group of aromatic series hydrazone.As the photoreaction group with N=N key, can list azobenzene, azo naphthyl, heteroaromatic azo group, bisdiazo base and first Za base etc. or be the group of basic structure with the azoxybenzene.As the photoreaction group with C=O key, can list benzophenone base, cumarin base, anthraquinonyl and dimaleoyl imino etc.These groups can have substituting groups such as alkyl, alkoxy, aryl, allyloxy, cyano group, alkoxy carbonyl group, hydroxyl, sulfonic group and halogenated alkyl.
Wherein, preferably can cause the photoreaction group of photo-induced dimerization reaction, because easily making the optical alignment film of the required polarizing light irradiation amount of light orientation less relatively and thermal stability and ageing stability excellence, so preferred cinnamoyl and chalcone base.If furtherly, as the polymkeric substance with photoreaction group, the distal portion that especially preferably has described polymer lateral chain becomes the material of the such cinnamoyl of cinnamic acid structure.
Form the solvent of using composition as the light oriented layer, preferred dissolution has the polymkeric substance of photoreaction 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 photoreaction 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 photoreaction 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 (PVA) or polyimide with composition.
Use method for compositions as forming in base material coating orientation polymer composition or light oriented layer, can adopt spin-coating method, extrusion, intaglio plate rubbing method, die type rubbing method, bar type to be coated with the known method of print processes such as rubbing method such as (Bar coating) method and spreader method or flexographic printing method etc.And when the manufacturing of this light polarizing film was implemented by the continuous manufacture method of aftermentioned volume to volume (roll to roll) form, described coating process adopted print processes such as intaglio plate rubbing method, die type rubbing 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 direction of orientation.
2-3. the manufacture method of this light polarizing film
On the alignment films that described base material or base material form, the coating light polarizing film forms and makes coated film with composition.Form as the coating light polarizing film and use method for compositions, can enumerate as with as the identical method of the method that illustrates for example with method for compositions in base material coating orientation polymkeric substance or the formation of light reaction 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, aeration-drying method, heat drying and hypobaric drying method etc.
Then, as preferred mode, in case after the mesomorphic state of the polymerizable liquid crystal compound that comprises in the described dry overlay film changes nematic crystal into, make described nematic crystal change the smectic crystal phase mutually into immediately.
Like this in order to form the smectic crystal phase mutually via nematic 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 crystal phase, then described polymerizable liquid crystal compound is cooled to the method till the temperature that shows the smectic crystal phase.
Make the polymerizable liquid crystal compound in the described dry overlay film change the smectic crystal phase into, make described polymerizable liquid crystal compound change the smectic crystal phase time mutually into via nematic 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 such phase transition temperature is illustrated in the application's embodiment.
Then, the polymerization process to polymerizable liquid crystal compound describes.Herein, contain photo-induced polymerization initiator 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 crystal mutually after, under the state of the mesomorphic state that keeps this smectic crystal phase, the method that makes described polymerizable liquid crystal compound carry out photopolymerization is 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, ultraviolet light and laser, selecting according to the kind of the photo-induced polymerization initiator 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, carrying out the aspect and can use the device that is being widely used in the art to be used as to relate to the aspect of the device of photopolymerization to consider, preferred ultraviolet light from polyreaction easy to control.Therefore, by ultraviolet 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 photo-induced polymerization initiator.In addition, during polymerization, in UV-irradiation, by suitable cooling device, by being cooled off also, dry overlay film can control polymerization temperature.By adopting such cooling device, 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 is keeping nematic crystal phase, smectic crystal phase, is preferably polymerization under the state of the such height smectic crystal phase that has illustrated for example, forms this light polarizing film.Polymerizable liquid crystal compound polymerization and this light polarizing film of making under the state that keeps the smectic crystal phase, with host-guest (Host-guest) type light polarizing film in the past, namely, the light polarizing film that makes polymerization such as polymerizable liquid crystal compound and make under the state of the mesomorphic state that keeps the nematic crystal phase 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 phase.
Further, the muted color phasic property excellence of this light polarizing film of making like this.Herein, the light polarizing film of muted color phasic property excellence refers to L
*a
*b
*(Lab) the chromaticity coordinates a in the colour system
*Value and b
*Value satisfies the light polarizing film of the relation of following formula (1F) and formula (2F).And, these chromaticity coordinatess a
*Value and b
*Value is to obtain by the assay method that for example illustrates in the embodiment of the present application.
-3≤colourity a
*≤ 3(1F)
-3≤colourity b
*≤ 3(2F)
Also can be respectively with chromaticity coordinates a described herein
*Value and b
*Value is called " colourity a
*" reach " colourity b
*".This a
*And b
*All near 0(zero), then more can be judged as the light polarizing film that shows neutral form and aspect.Possess in the display device of such light polarizing film, can obtain not have painted good white to show.
In addition, in the form and aspect of light polarizing film, it is orthogonal crossing to make 2 light polarizing film be overlapped into the extinction axle, with the above-mentioned form and aspect of similarly obtaining this moment, calculates " orthogonal (intersecting vertically) a
*" reach " orthogonal b
*" time, further preferred such orthogonal a
*And orthogonal b
*Satisfy the relation of following formula (1F ') and formula (2F ') respectively.In possessing the display device of light polarizing film, these orthogonals a
*And orthogonal b
*Be to show whether the form and aspect of black display are neutral index.This orthogonal a
*And orthogonal b
*All near 0(zero), then more can obtain not have painted good black display.
-3≤orthogonal a
*≤ 3(1F ')
-3≤orthogonal b
*≤ 3(2F ')
3. 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 base by the base material.When base material was transparent base, the article that finally make became the polarizer with transparent base and this light polarizing film (below, according to circumstances be referred to as " this polarizer ").
This manufacture method for example has
Preparation with transparent base be wound on 1st roller of the 1st volume on the core operation,
The operation of continuously described transparent base being sent from described the 1st roller,
On described transparent base, form continuously alignment films operation,
On described oriented layer, 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 crystal phase, be preferably smectic crystal mutually after, under the state that keeps described smectic 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 is illustrated this manufacture method herein.
The 1st roller 210 that transparent base is wound on the 1st volume core 210A for example can easily obtain from market.As the transparent base that can obtain from market with the form of such roller, can list among the transparent base that has illustrated for example film that is constituted by cellulose esters, annular ethylene series resin, polyethylene terephthalate, polycarbonate or polymethacrylate etc.In addition, when the circularly polarizing plate, the transparent base 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 esters or annular ethylene series resin etc.
Then, from described the 1st roller 210 with the transparent base debatching.Be by the volume core 210A at described the 1st roller 210 suitable whirligig to be set with the method for transparent base debatching, by described whirligig 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 bases suitable help roll 300 to be set, the whirligig by described help roll 300 is with the form of transparent base debatching.Further, can also be by in the 1st volume core 210A and help roll 300, whirligig being set together, Yi Bian give the tension force of transparent base with appropriateness, Yi Bian with the form of transparent base debatching.
By apparatus for coating 211A the time, nationality is coated with the lighting oriented layer in its surface by described apparatus for coating 211A and forms and use composition from the transparent base of described the 1st roller 210 debatchings.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 rubbing method, die type rubbing method, flexographic printing method.
Transparent base 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 base.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, a plurality of zones of division can be the different forms of design temperature difference, also can be with a plurality of drying oven arranged in series, the design temperature of each drying oven is the drying oven of different forms respectively.
Nationality by from heating furnace 212A by and form the 1st dry overlay film continuously, then, shine polarized light UV by polarized light UV irradiation unit 213A on the surface of the 1st dry overlay film side or the surface of transparent base side, the described the 1st dry overlay film forms (light) alignment films.At this moment, the carrying direction D1 that can also make transparent base intersects with the direction of orientation D2 angulation of the optical alignment film of formation.Fig. 2 is the synoptic diagram of relation that is illustrated in the carrying direction D1 of the direction of orientation D2 of the optical alignment film that polarized light UV irradiation back forms and transparent base.That is, Fig. 2 is representing: when observing by the 1st laminate behind the polarized light UV irradiation unit 213A surperficial from the direction of orientation D2 of the carrying direction D1 of transparent base and optical alignment film, their angulations are shown as about 45 °.
Formed the transparent base (the 1st laminate) of optical alignment film so continuously, then, nationality is by passing through from apparatus for coating 211B, and after optical alignment film coating light polarizing film formed with composition, 212B passed through from drying oven.Nationality is by passing through from drying oven 212B, and light polarizing film forms with the polymerizable liquid crystal compound formation nematic crystal phase that comprises in the composition, is preferably the smectic crystal phase, forms the 2nd dry overlay film.
Transparent base from described drying oven 212B process, light polarizing film forms and is fully removed with the solvent that contains in the composition, polymerizable liquid crystal compound in keeping the 2nd dry overlay film is the nematic crystal phase, be preferably under the state of mesomorphic state of smectic crystal phase, be carried to light irradiation device 213B.Penetrate by the illumination 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 wound onto with the form of the laminate that comprises transparent base and alignment films on the 2nd volume core 220A so continuously, 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 base is passed through with the order of the 1st roller/apparatus for coating 211A/ drying oven 212A/ polarized light UV irradiation unit 213A/ apparatus for coating 211B/ drying oven 212B/ light irradiation device 213B, on the optical alignment film on the transparent base, 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 base to this light polarizing film, but, for example, also can be by transparent base is passed through with the order of the 1st roller/apparatus for coating 211A/ drying oven 212A/ polarized light UV irradiation 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 shape 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 required 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 base/optical alignment film/this light polarizing film are illustrated, also can be by peel off this light polarizing film that optical alignment film and transparent base make individual layer from this polarizer.In addition, can also in this polarizer, be arranged to the layer beyond transparent base/optical alignment film/this light polarizing film or the form of film lamination.As these layer and film, as narrating, this light polarizing film can further possess phase retardation film, can further possess anti-reflection layer or brightness enhancement film.
In addition, by making transparent base originally as phase retardation film, also can be arranged to circularly polarizing plate or the elliptic 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 tension is slightly at 45 with respect to the carrying direction of transparent base 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.
4. the purposes of this light polarizing film
This light polarizing film can be used for various display device.Display device refers to have the device of display element, comprises light-emitting component or light-emitting device as light emitting source.As display device, can enumerate as: liquid crystal indicator, organic electroluminescent (EL) display device, inorganic EL (EL) display device, electron emission display (for example field emission display device (FED), Surface-conduction Electron-emitter Display device (SED)), Electronic Paper and (use the display device, plasma display system, projection type image display apparatus (for example grating light valve (GLV) display device, have the display device of digital micro-mirror spare (DMD)) of e-inks or electrophoresis element and piezoelectric ceramics display device 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 device can be the display device 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 device of organic electroluminescent (EL) display device or inorganic EL (EL) display device especially effectively.
Fig. 3 be the expression liquid crystal indicator that uses this light polarizing film (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 device (below, according to circumstances be referred to as " this EL display device ".) the synoptic diagram of section constitution.
Figure 11 is the synoptic diagram of formation 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 color filter 15 in liquid crystal layer 17 sides of substrate 14a.Color 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 color filter 15 and stain matrix 20 fully in liquid crystal layer 17 sides.And, can have overlayer (not shown) between color filter 15 and the transparency electrode 16.
Disposing thin film transistor (TFT) 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 color filter 15 position in opposite directions.Disposing the have connecting hole interlayer dielectric 18 of (not shown) between thin film transistor (TFT) 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 base 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 color filter 15 that forms on the substrate and thin film transistor (TFT) 21, when needing the high temperature heating process, preferred glass substrate or quartz base plate.
Thin film transistor (TFT) can adopt only thin film transistor (TFT) according to the material of substrate 14b.As thin film transistor (TFT) 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, color filter 15 and stain matrix 20, transparency electrode 16, liquid crystal layer 17, pixel electrode 22, interlayer dielectric 18 and thin film transistor (TFT) 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, the function that makes incident light change rectilinearly polarized light into can be given to this liquid crystal indicator 10.And, kind according to the liquid-crystal compounds 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 emitting side (outside) of this polarizer 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 this polarizer (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 arranged on polarizer 12a and/or the 12b, the effect of the slimming that can realize this liquid crystal indicator 10 is arranged.
When this polarizer was used for polarizer 12a or 12b, its lamination was 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 base 1.In addition, Fig. 4 (A2) shown from the set situation of phase separation layer 13a side with the arranged in order of transparent base 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 base 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 base 1 from phase retardation film 13b side.
Disposing the module backlight 19 as light emitting source in the outside of polarizer 12b.Module 19 backlight comprises light source, light conductor, reflecting plate, diffusion sheet and field angle adjustment sheet.As light source, can list electroluminescence, cold-cathode tube, thermionic-cathode tube, light emitting diode (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 conductor, changed light path by reflecting plate 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 nonpolarized light, only the rectilinearly polarized light of a certain direction sees through the polarizer 12b of liquid crystal panel.This rectilinearly polarized light is transformed to circularly polarized light or elliptically polarized light by phase separation layer 13b, sees through substrate 14b, pixel electrode 22 etc. in turn 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 (PD), 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 color filter 15 of a certain particular range of wavelengths arrives polarizer 12a, and liquid crystal indicator shows the color that is determined by color 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 color filter 15 is polarized device 12a and absorbs.Thus, this pixel shows black.In 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, so this pixel shows Neutral colour.
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, by the effect of 1/4 wavelength plate that further possesses in this light polarizing film, sees through the circularly polarized light of this light polarizing film by liquid crystal layer 17, is reflected and is used for showing by pixel electrode 22.
Then, this EL display device 30 of having used this light polarizing film is described with reference to Fig. 6.In this EL display device, 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 composition of explanation this EL display device 30 etc., 2 embodiments of this circularly polarizing plate are illustrated with reference to Fig. 7.
(A) of Fig. 7 is the synoptic diagram of the 1st embodiment of expression 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 base 1(phase retardation film 4 given phase differential in advance) transparent base 1 that uses when making this polarizer, transparent base 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, if the 2nd embodiment because of above-mentioned circularly polarizing plate, then constitute easy so preferred, at this moment, preferably 1/4 wavelength plate is used as transparent base, further, use 1/4 wavelength plate as transparent base, preferred satisfied following (A1) and necessary condition (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 base 1 of having given phase differential in advance as transparent base 1, that is, use phase retardation film to make.The 1st embodiment of this circularly polarizing plate 110 can be to 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, 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 given size, the mode of applying phase retardation film on this polarizer 100 of cutting then, 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 shape 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 bonding agent, this light polarizing film of fitting 3 and phase retardation film.
Then, this EL display device that possesses this circularly polarizing plate 110 is described referring again to Fig. 6.
This EL display device 30 is on the substrate 33 that has formed pixel electrode 35, the display device that is formed by organic function layer 36 and cathode electrode 37 laminations as light emitting 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 DC current between pixel electrode 35 and cathode electrode 37 at cathode electrode 37, organic function layer 36 is luminous.Organic function layer 36 as light emitting 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 device with inorganic functional layer is suitable equally.
In order to make this EL display device 30, at first, on substrate 33, form thin film transistor (TFT) 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 (TFT) 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 drawing 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 drawing 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 device 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 aluminium 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 bonding agent form laminated substrate.In addition, these substrates are not limited to tabular, can also be films.
As thin film transistor (TFT) 40, can use as polycrystal silicon transistor etc.Thin film transistor (TFT) 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 (TFT) 40 is being set at substrate 33.Wire electrode resistance is low, has to be electrically connected with pixel electrode 35 and resistance value is suppressed lowlyer function, and this wire electrode uses any wire 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 (TFT) 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 monox, silicon nitride by sputter or vacuum evaporation and the article of film forming, by the SOG(spin-coating glass, spin-on-glass) interlayer dielectric with insulativity of filming etc. of resin system materials such as the silicon oxide layer of Xing Chenging, photoresist, polyimide and acryl resin, just can be above-mentioned any one.
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 light emitting 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 indium oxide), the IZO(indium zinc oxide), 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.
Composition 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, the preferred use from by 2 kinds of compositions selecting 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.
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 gross 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 compounds 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 light emitting 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 device 30, can use the organic function layer 36 of the known various materials of using as EL element.
Figure 10 is the skeleton diagram that the other forms of cross section of this EL of expression display device 30 is formed.This this EL display device 30 has the hermetically-sealed construction that has used diaphragm seal film 42, even all can obtain to launch light from the opposing face of array base palte.
As diaphragm seal film 42, the DLC(diamond-like-carbon that preferably used on the film of electrochemical capacitor evaporation) DLC film.The DLC film has the characteristic of moisture-penetrability 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 device (this liquid crystal indicator and this EL display device) that relates to novel light polarizing film of the present invention (this light polarizing film) and possess 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 skeleton diagram 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 light emitting source (for example, high-pressure sodium 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.To be converted to the polarized light with specific polarization direction in advance from the random polarization of light source emission thus, reduce the light loss consumption in the aftermentioned light incident side polarizer, and 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 catoptron 122 nationalitys successively by being separated into the dichronic 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 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, synthetic by cross colour splitting prism 150 by the optical imagery that each pixel sees through incident light to make with different transmittances, by projection lens 170 enlarging projection on projection screen 180.
As Electronic Paper, the Electronic Paper 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, Electronic Paper that the light absorption by molecule shows, the autoluminescence of sending by electronics and hole bonding show etc.More specifically, can list the microcapsule-type electrophoresis, move horizontally the type electrophoresis, vertical mobile model electrophoresis, spherically reverse that ball, magnetic reverse ball, cylinder reverses ball mode, charged toner, electronics powder fluid, magnetophoretic, magnetic strength heat, moistening, the light scattering (transparent/white opacity changes) of electricity, cholesteryl liquid crystal/optical conductive layer, cholesteryl liquid crystal, bistability nematic crystal, lure electrical liquid crystal, 2 chromotropism pigment liquid crystal dispersion methods, movable film, color development colour killing, photochromic, electrochromism by leuco dye, electro-deposition 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 Jap.P. spy opens the 2002-185983 communique) that different mutually phase retardation films is arranged as small polarization explicit representation has been proposed, but if use this light polarizing film, then because forming pattern easily by printing, inkjet printing, photoetching etc., the manufacturing process of display device 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 ".
In the present embodiment, use following dichroism pigment (1).
The preparation of compound (1-1) (following (1-1) represented compound)
Compound (1-1) synthesizes by following proposal.
Compound [compound (1B)] 5.00g, 4-nipagin A 4.63g, dimethylamino naphthyridine (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 liquor that makes, splashed into diisopropyl carbodiimides (IPC) 2.58g in time-consuming 5 minutes, further stirred 4 hours.In the reactant liquor that obtains, add methyl alcohol 75g, crystallization, filtration obtains crystallization.After further using the methanol wash crystallization of equivalent, by vacuum drying, obtain compound (1-1) 6.78g.Be benchmark with compound (1B), yield is 87%.
Compound (1-1)
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).
The preparation of compound (1-7) (following (1-7) represented compound)
Compound (1-7) synthesizes by following proposal.
Mixing cpd (1B) 5.00g, 4-butoxy phenol 4.63g, DMAP0.23g and chloroform 25g under the lucifuge nitrogen atmosphere, stirred 10 minutes under 5 ° of C.In the mixed liquor that makes, splashed into IPC2.58g in time-consuming 5 minutes, further stirred 4 hours.In the reactant liquor that obtains, add methyl alcohol 75g, crystallization, filtration obtains crystallization.Crystallization is dissolved in the 50g dimethyl acetamide, by the diatomite filtration insolubles.Reclaim the filtrate water crystallization.The crystallization that makes further is dissolved in the 50g tetrahydrofuran by after removing by filter insolubles, adds heptane, crystallization by vacuum drying, obtains compound (1-7) 4.66g.Be benchmark with compound (1B), yield is 60%.
Compound (1-7)
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).
In the present embodiment, use following polymerizable liquid crystal compound.
Compound (4-6) (the represented compound of following formula (4-6))
Compound (4-6) passes through Lub et al.Recl.Trav.Chim.Pays-Bas, and 115,321-328(1996) Ji Zai method is synthetic.
[mensuration of phase transition temperature]
Confirmed the phase transition temperature of compound (4-6) by the phase transition temperature of obtaining the film that is constituted by compound (4-6).Its operation is as follows.
Form the film that is constituted by compound (4-6) 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 ℃ by the film that compound (4-6) constitutes, when cooling, locate to change into mutually the nematic phase at 112 ℃, locate to change into mutually smectic A phase at 110 ℃, locate to change into mutually smectic B phase at 94 ℃.
Compound (4-8) (the represented compound of following formula (4-8))
Compound (4-8) synthesizes with reference to the synthetic method of above-claimed cpd (4-6).
[mensuration of phase transition temperature]
Measure the phase transition temperature of similarly confirming compound (4-8) with the phase transition temperature of compound (4-6).After compound (4-8) is warming up to 140 ℃, when cooling, locate to change into mutually the nematic phase at 131 ℃, locate to change into mutually smectic A phase at 80 ℃, locate to change into mutually smectic B phase at 68 ℃.
Compound (4-22) (the represented compound of following formula (4-22))
Compound (4-22) is synthetic with reference to the synthetic method of No. 4719156 record of Jap.P..
[mensuration of phase transition temperature]
Measure the phase transition temperature of similarly confirming compound (4-22) with the phase transition temperature of compound (4-6).After compound (4-22) is warming up to 140 ℃, when cooling, locate to change into mutually the 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 (4-25) (the represented compound of following formula (4-25))
Compound (4-25) is synthetic with reference to the synthetic method of No. 4719156 record of Jap.P..
[mensuration of phase transition temperature]
Measure the phase transition temperature of similarly determining compound (4-25) with the phase transition temperature of compound (4-6).After compound (4-25) is warming up to 140 ℃, when cooling, locate to change into mutually the nematic phase at 119 ℃, locate to change into mutually smectic A phase at 100 ℃, locate to change into mutually smectic B phase at 77 ℃.
[light polarizing film forms the preparation with composition (A)]
Mix following compositions, by stirring 1 hour down at 80 ℃, make light polarizing film and form with composition (A).And " compound (1-7) " of the dichroism pigment of Shi Yonging refers to the represented compound of described formula (1-7) herein, and the compound that uses as other dichroism pigments is also corresponding to the numbering of its formula.Below also identical.
2-dimethylamino-2-benzyl-1-(4-morpholinyl phenyl)-1-butanone (gorgeous good solid 369; Ciba society system) 6 part
Levelling agent;
Polyacrylic acid ester compounds (BYK-361N; Bi Ke chemistry society system) 1.2 part
Solvent; 250 parts of toluene
1.X ray diffraction determination
On glass substrate, the 2 quality % aqueous solution (oriented layer forms and uses composition) by spin-coating method pva coating (polyvinyl alcohol (PVA) 1000 fully saponified types, Wako Pure Chemical Industries, Ltd.'s system) after the drying, form the film of thickness 100nm.Then, form oriented layer by implementing friction treatment on the surface of the film that makes.Use semi-automatic rubbing device (trade name: LQ-008 type, Joyo Engineering Co., Ltd.'s system), by cloth (trade name: YA-20-RW, Ji Chuan Chemical Co., Ltd system), under the condition of depth of cup 0.15mm, revolution 500rpm, 16.7mm/s, carry out friction treatment.On the alignment films of so making, form with composition (A) by spin-coating method coating light polarizing film, be quickly cooled to room temperature at heat drying on 120 ℃ the heating plate after 1 minute, form dry overlay film in described oriented layer.Then, use UV irradiation unit (SPOT CURE SP-7; Ushio Electric Inc's system), by with exposure 2000mJ/cm
2(365nm benchmark) irradiation ultraviolet radiation on dry overlay film 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.The thickness of the light polarizing film of this moment is measured by laser microscope (OLS3000 processed of Olympus Co., Ltd), and the result is 1.7 μ m.This light polarizing film is used X-ray diffraction device X ' Pert PRO MPD(Spectris Co., Ltd. system) similarly carry out X-ray diffraction and measure, as a result, near 2 θ=20.2 °, obtain full width at half maximum (FWHM)=about 0.17 ° sharp-pointed diffraction peak (bragg peak).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
Confirmed to form the structure of reflection height smectic phase.
2. the making of the optical alignment film on transparent membrane
Use triacetylcellulose film (KC8UX2M, Konica Minolta (strain) system) as transparent base, make the represented light orientated polymer of following formula (3) be dissolved in 5% solution that toluene forms by the coating of bar type rubbing method, make dry overlay film 120 ℃ of following dryings.Make optical alignment film at this dry overlay film irradiation polarized light UV.Polarized light UV handles and uses UV irradiation unit (SPOT CUR SP-7; Ushio Electric Inc's system), under wavelength 365nm, measures, under the condition of intensity 100mJ, carry out.
3. the making of light polarizing film
Form with composition (A) by bar type rubbing method (#5 17mm/s) coating light polarizing film at the film that has attached the optical alignment film that as above makes, heat drying was cooled to room temperature after 1 minute in 120 ℃ drying oven.Then, use UV irradiation unit (SPOT CUR SP-7; Ushio Electric Inc's system), by shining exposure 2000mJ/cm to formed the layer that forms with composition by light polarizing film
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.The thickness of the light polarizing film of this moment is measured by laser microscope (OLS3000 processed of Olympus Co., Ltd), and the result is 1.6 μ m.The article that make like this are the polarizer that comprises light polarizing film and transparent base.
4. the mensuration of degree of polarization, transmittance, form and aspect
In order to confirm the serviceability of the polarizer, following mensuration apparent brightness is proofreaied and correct degree of polarization, apparent brightness is proofreaied and correct transmittance, colourity a
*Value, colourity b
*Value, orthogonal a
*And orthogonal b
*
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 transmittance (T of printing opacity in the scope of wavelength 380nm ~ 780nm by reference beam method
1) and the axial transmittance (T of extinction
2).Described folder is provided with in the reference side and light quantity is blocked 50% mesh.Use following formula (formula 1) and (formula 2), calculate monomer transmitance, the degree of polarization of each wavelength, further carry out apparent brightness according to the 2 degree visuals field (illuminant-C) of JIS Z8701 and proofread and correct, calculate apparent brightness and proofread and correct monomer transmitance (Ty) and apparent brightness correction degree of polarization (Py).In addition, use the isochrome function of illuminant-C, calculate L by the monomer transmitance of similarly measuring
*a
*b
*(CIE) the colourity a in the colour system
*And b
*Further, use the isochrome function of illuminant-C, calculate L by the orthogonal transmittance of similarly measuring
*a
*b
*(CIE) the orthogonal a in the colour system
*And orthogonal b
*Colourity a
*, colourity b
*, orthogonal a
*And orthogonal b
*Value more near 0, more can be judged as neutral form and aspect.These the results are shown in table 4.
Monomer transmitance (%)=(T1+T2)/2 ... (formula 1)
Degree of polarization (%)=(T1-T2)/(T1+T2) * 100 ... (formula 2)
1. the making of light polarizing film
The wide and coating speed (#715mm/s), make light polarizing film except the metal wire (ワ ノ ヤ one) of the rod that changes rod coater similarly to Example 1.By the thickness of laser microscope (OLS3000 processed of Olympus Co., Ltd) mensuration light polarizing film at this moment, the result is 1.8 μ m.
2. the mensuration of degree of polarization, transmittance, form and aspect
Measure the apparent brightness of the light polarizing film of making by method similarly to Example 1 and proofread and correct monomer transmitance (Ty) and apparent brightness correction degree of polarization (Py) and colourity a
*, colourity b
*, orthogonal a
*And orthogonal b
*, the results are shown in table 4.
Embodiment 3[light polarizing film forms the preparation with composition (B)]
Mix following compositions, by stirring 1 hour down at 80 ℃, make light polarizing film and form with composition (B).
2-dimethylamino-2-benzyl-1-(4-morpholinyl phenyl)-1-butanone (gorgeous good solid 369; Ciba society system) 6 part
Levelling agent;
Polyacrylic acid ester compounds (BYK-361N; Bi Ke chemistry society system) 1.2 part
Solvent; 250 parts of toluene
1. the making of light polarizing film
Be changed to light polarizing film formation with composition (B), further metal live width and the coating speed of the rod of rod coater become (#5 25mm/s) except light polarizing film being formed with composition (A), make light polarizing film similarly to Example 1.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 m.
2. the mensuration of degree of polarization, transmittance, form and aspect
Measure the apparent brightness of the light polarizing film of making by method similarly to Example 1 and proofread and correct monomer transmitance (Ty) and apparent brightness correction degree of polarization (Py) and colourity a
*, colourity b
*, orthogonal a
*And orthogonal b
*, the results are shown in table 4.
1. the making of light polarizing film
Except the metal live width and coating speed (#7 20mm/s) of the rod that changes rod coater, make light polarizing film similarly to Example 3.By the thickness of laser microscope (OLS3000 processed of Olympus Co., Ltd) mensuration light polarizing film at this moment, the result is 2.0 μ m.
2. the mensuration of degree of polarization, transmittance, form and aspect
Measure the apparent brightness of the light polarizing film of making by method similarly to Example 1 and proofread and correct monomer transmitance (Ty) and apparent brightness correction degree of polarization (Py) and colourity a
*, colourity b
*, orthogonal a
*And orthogonal b
*, the results are shown in table 4.
Embodiment 5
1. the making of black light polarizing film
Except changing into (#5 50mm/s), the pin of the rod of rod coater is wide and coating speed make light polarizing film similarly to Example 3.By the thickness of laser microscope (OLS3000 processed of Olympus Co., Ltd) mensuration light polarizing film at this moment, the result is 2.2 μ m.
2. the mensuration of degree of polarization, transmittance, form and aspect
Measure the apparent brightness of the light polarizing film of making by method similarly to Example 1 and proofread and correct monomer transmitance (Ty) and apparent brightness correction degree of polarization (Py) and colourity a
*, colourity b
*, orthogonal a
*And orthogonal b
*, the results are shown in table 4.
Embodiment 6[light polarizing film forms the preparation with composition (C)]
Mix following compositions, by stirring 1 hour down at 80 ℃, make light polarizing film and form with composition (C).
2-dimethylamino-2-benzyl-1-(4-morpholinyl phenyl)-1-butanone (gorgeous good solid 369; Ciba society system) 6 part
Levelling agent;
Polyacrylic acid ester compounds (BYK-361N; Bi Ke chemistry society system) 1.2 part
Solvent; 250 parts of toluene
1. the making of light polarizing film
Be changed to light polarizing film formation with composition (C), further metal live width and the coating speed of the rod of rod coater are changed into (#7 20mm/s) except light polarizing film being formed with composition (A), make light polarizing film similarly to Example 1.By the thickness of laser microscope (OLS3000 processed of Olympus Co., Ltd) mensuration light polarizing film at this moment, the result is 2.0 μ m.
2. the mensuration of degree of polarization, transmittance, form and aspect
Measure the apparent brightness of the light polarizing film of making by method similarly to Example 1 and proofread and correct monomer transmitance (Ty) and apparent brightness correction degree of polarization (Py) and colourity a
*, colourity b
*, orthogonal a
*And orthogonal b
*, the results are shown in table 4.
Embodiment 7
1. the making of black light polarizing film
Except the metal live width and coating speed (#5 50mm/s) of the rod that changes rod coater, make light polarizing film similarly to Example 6.By the thickness of laser microscope (OLS3000 processed of Olympus Co., Ltd) mensuration light polarizing film at this moment, the result is 2.2 μ m.
2. the mensuration of degree of polarization, transmittance, form and aspect
Measure the apparent brightness of the light polarizing film of making by method similarly to Example 1 and proofread and correct monomer transmitance (Ty) and apparent brightness correction degree of polarization (Py) and colourity a
*, colourity b
*, orthogonal a
*And orthogonal b
*, the results are shown in table 4.
Comparative example 1
1. the making of iodo-PVA polarization plates
With average degree of polymerization about 2,400, the polyvinyl alcohol film of the above thickness 75 μ m of 99.9 moles of % of saponification degree is with the dried forms uniaxial tension about 5 times, further, under the state that keeps tensile state, impregnated in 60 ℃ pure water after 1 minute, is 28 ℃ of 60 seconds of dipping down in 0.1/5/100 the aqueous solution at the mass ratio of iodine/potassium iodide/water.Afterwards, be 72 ℃ of 300 seconds of dipping down in the aqueous solution of 810.5/7.5/100 at the mass ratio of potassium iodide/boric acid/water.After washing for 5 seconds with 10 ℃ pure water then, 80 ℃ dry 3 minutes down, make the polarizer that on polyvinyl alcohol resin film iodine absorption has been orientated.
2. the mensuration of degree of polarization, transmittance, form and aspect
Measure the apparent brightness of the polarizer of making by method similarly to Example 1 and proofread and correct monomer transmitance (Ty) and apparent brightness correction degree of polarization (Py) and colourity a
*, colourity b
*, orthogonal a
*And orthogonal b
*, the results are shown in table 4.
[table 4]
| ? | |
|
|
|
Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example |
| Thickness (μ m) | 1.6 | 1.8 | 1.7 | 2.0 | 2.2 | 2.0 | 2.2 | 28 |
| Py（％） | 88.1 | 91.4 | 90.5 | 93.6 | 95.2 | 98.0 | 98.8 | 100 |
| Ty（％） | 47.0 | 45.5 | 46.1 | 44.7 | 44.0 | 43.0 | 41.8 | 42.3 |
| Colourity a * | -0.5 | -0.6 | -0.4 | -0.4 | -0.5 | -0.5 | -0.6 | -2.2 |
| Colourity b * | -1.5 | -0.9 | 1.4 | 1.8 | 2.1 | 2.5 | 2.9 | 3.8 |
| Orthogonal a * | 0.8 | 1.2 | 0.5 | 0.7 | 1.0 | 1.3 | 1.2 | 0.0 |
| Orthogonal b * | -5.4 | -5.8 | -2.8 | -3.3 | -2.2 | -0.8 | -0.4 | -0.2 |
As known from Table 4, the light polarizing film of embodiment 1 ~ 7 is all more slim than the iodo-PVA polarizer in the past.In addition, the light polarizing film of embodiment 1 ~ 7 all shows the muted color phasic property.
1. the making of the optical alignment film on the phase retardation film
Use phase retardation film (single axle drawn membrane WRF-S(modified polycarbonate is resin), phase difference value 137.5nm, thickness 50 μ m, Supreme Being people changes into (strain) system) as transparent base, replace triacetylcellulose film (KC8UX2M, Konica Minolta (strain) system), makes the represented light orientated polymer of described formula (3) be dissolved in 5% solution that cyclopentanone forms by the coating of bar type rubbing method, make dry overlay film 120 ℃ of following dryings.Make optical alignment film at this dry overlay film irradiation polarized light UV.Use UV irradiation unit (SPOT CURE SP-7; Ushio Electric Inc's system), under wavelength 365nm, measures, under the condition of intensity 100mJ, carry out polarized light UV and handle.In addition, at this moment, the direction of illumination of polarized light UV is implemented with respect to the slow axis of phase retardation film is at 45.
2. the making of circularly polarizing plate
Optical alignment film at the phase retardation film that has attached the optical alignment film of making forms with composition (C) by bar type rubbing method (#7 20mm/s) coating light polarizing film, and heat drying was cooled to room temperature after 1 minute in 120 ℃ drying oven.Then, use UV irradiation unit (SPOT CURE SP-7; Ushio Electric Inc's system), by shining exposure 2000mJ/cm to formed the layer that forms with composition by light polarizing film
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, make circularly polarizing plate by forming light polarizing film by described dry overlay film.By the thickness of laser microscope (OLS3000 processed of Olympus Co., Ltd) mensuration light polarizing film at this moment, the result is 2.0 μ m.
3. the affirmation of antireflection property
Jie is fitted phase retardation film side and the aluminium metal sheet of the circularly polarizing plate that makes by bonding agent, and the result disappears with the observed metallic luster of aluminium metal sheet monomer, obtains the black display of homogeneous.The circularly polarizing plate of being made by this light polarizing film like this has good preventing reflection characteristic as can be known.
Utilizability on the industry
This light polarizing film is extremely useful aspect manufacturing liquid crystal indicator, (organic) EL display device and projection-type liquid crystal display device.
Claims (15)
1. light polarizing film, it contains the polymkeric substance that formed by polymerizable liquid crystal compound, is scattered in when measuring light absorption in the described polymkeric substance, has at least a kind of dichroism pigment (1) of absorption maximum and at least 2 kinds of dichroism pigments (2) that have absorption maximum in the scope of wavelength 550 ~ 700nm in the scope of wavelength 380 ~ 550nm.
2. according to the light polarizing film of record in the claim 1, wherein, when making described dichroism pigment (1) be scattered in the polymkeric substance that is formed by polymerizable liquid crystal compound the mensuration light absorption, has absorption maximum in the scope of wavelength 400 ~ 550nm.
3. according to the light polarizing film of putting down in writing in claim 1 or the claim 2, wherein, be scattered in the described polymkeric substance when measuring light absorption, at least 2 kinds of dichroism pigments (2) that have absorption maximum in the scope of wavelength 550 ~ 700nm contain: be scattered in that the scope at wavelength 550 ~ 600nm has the dichroism pigment (2-1) of absorption maximum and the dichroism pigment (2-2) that has absorption maximum in the scope of wavelength 600 ~ 700nm when measuring light absorption in the described polymkeric substance.
4. according to the light polarizing film of any record of claim 1 ~ 3, wherein, polymerizable liquid crystal compound is the compound that shows the smectic crystal phase.
5. according to the light polarizing film of any record of claim 1 ~ 4, it obtains bragg peak in X-ray diffraction is measured.
6. according to the light polarizing film of any record of claim 1 ~ 5, wherein, L
*a
*b
*Chromaticity coordinates a in the colour system
*Value and b
*Value satisfies the relation of following formula (1F) and formula (2F).
-3≤colourity a
*≤ 3(1F)
-3≤colourity b
*≤ 3(2F)
7. according to the light polarizing film of any record of claim 1 ~ 6, wherein, dichroism pigment (1) and dichroism pigment (2) are azo-compounds.
8. according to the light polarizing film of any record of claim 1 ~ 7, wherein, dichroism pigment (2) is made of the represented compound of formula (2),
In the formula (2),
N is 1 or 2,
Ar
1And Ar
3Be any one represented group of formula (AR-1) ~ formula (AR-4) independently respectively,
Ar
2Be formula (AR2-1), formula (AR2-2) or the represented group of formula (AR2-3),
A
1And A
2Be any one represented group of formula (A-1) ~ formula (A-9) independently respectively, * represents bonding position,
Mc is 0 ~ 10 integer, and when having 2 mc in the same group, these 2 mc can be identical or different mutually.
9. according to the light polarizing film of any record of claim 1 ~ 8, wherein, dichroism pigment (1) is made of the represented compound of formula (1),
In the formula (1),
Y is formula (Y1) or the represented group of formula (Y2),
In the formula, L be oxygen atom or-NR-, R is the alkyl of hydrogen atom or carbon number 1 ~ 4,
R
1Be formula (R
1-1) ~ formula (R
1-3) group that any one is represented,
In the formula, ma is 0 ~ 10 integer, and when having 2 ma in the same group, these 2 ma can be identical or different mutually, and * represents bonding position,
R
2Be formula (R
2-1) ~ formula (R
2-6) group that any one is represented,
In the formula, mb is 0 ~ 10 integer.
10. polarizer, it is to form in the light polarizing film that transparent base arranges any record of claim 1 ~ 9.
11. the manufacture method of the polarizer of claim 10 record, it has
Preparation possesses the operation of the laminate of alignment films at transparent base;
The operation of coating composition on the described alignment films of described laminate, described composition contains polymerizable liquid crystal compound, be scattered in when measuring light absorption in the polymkeric substance that is formed by described polymerizable liquid crystal compound, the 2 kinds of dichroism pigments (2) and the solvent that have a kind of dichroism pigment (1) of absorption maximum, have absorption maximum in the scope of wavelength 550 ~ 700nm in the scope of wavelength 380 ~ 550nm;
Make the operation of the described polymerizable liquid crystal compound polymerization that comprises in the described composition.
12. according to the manufacture method of claim 11 record, wherein, transparent base is plastic basis material, and described alignment films is optical alignment film.
13. a liquid crystal indicator, it possesses the light polarizing film of any record of claim 1 ~ 9.
14. a circularly polarizing plate, it has the light polarizing film of any record of claim 1 ~ 9 and λ/4 layer, satisfies following (A1) and necessary condition (A2),
(A1) the slow axis angulation of the extinction axle of described light polarizing film and described λ/4 layer is about 45 °;
(A2) value that postpones with the front of described λ/4 of the light measurement of wavelength 550nm layer is the scope of 100 ~ 150nm.
15. an organic EL display, it possesses circularly polarizing plate and the organic EL of claim 14 record.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-041041 | 2012-02-28 | ||
| JP2012041041 | 2012-02-28 | ||
| JP2012046279 | 2012-03-02 | ||
| JP2012-046279 | 2012-03-02 |
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| Publication Number | Publication Date |
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| CN103336325A true CN103336325A (en) | 2013-10-02 |
| CN103336325B CN103336325B (en) | 2017-04-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201310064832.5A Active CN103336325B (en) | 2012-02-28 | 2013-02-28 | Polarizing film, circular polarizing plate and method of producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP6155697B2 (en) |
| KR (4) | KR102129135B1 (en) |
| CN (1) | CN103336325B (en) |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58187456A (en) * | 1982-04-27 | 1983-11-01 | Nippon Kayaku Co Ltd | Azo dye |
| JPH0461035B2 (en) * | 1982-06-30 | 1992-09-29 | Mitsubishi Kasei Kk | |
| JPH0517274B2 (en) * | 1981-11-16 | 1993-03-08 | Mitsubishi Kasei Kk | |
| CN1356585A (en) * | 2000-11-24 | 2002-07-03 | 香港科技大学 | Process for preparing optical orientation film |
| US20030035972A1 (en) * | 1998-01-13 | 2003-02-20 | 3M Innovative Properties Company | Color shifting film articles |
| WO2011024891A1 (en) * | 2009-08-28 | 2011-03-03 | 富士フイルム株式会社 | Dichroic dye composition, polarizing film, liquid crystal cells and display devices |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0613703B2 (en) * | 1982-06-30 | 1994-02-23 | 三菱化成株式会社 | Guest-host type liquid crystal composition |
| JP2761453B2 (en) | 1993-11-17 | 1998-06-04 | 出光興産株式会社 | Organic EL element and organic EL panel |
| JPH11101964A (en) * | 1997-08-01 | 1999-04-13 | Sony Corp | Polarization element and display device |
| EP2159611B1 (en) * | 2003-11-06 | 2018-01-03 | Sumitomo Chemical Company, Limited | Polymerizable liquid crystal and oriented polymer film |
| JP4404624B2 (en) * | 2003-12-25 | 2010-01-27 | 日東電工株式会社 | Elliptical polarizing plate and image display device |
| EP1593713A1 (en) * | 2004-05-04 | 2005-11-09 | Rolic AG | Polymerizable dichromophoric dichroic azo dyes |
| KR100789512B1 (en) * | 2005-06-01 | 2007-12-28 | 도시바 마쯔시따 디스플레이 테크놀로지 컴퍼니, 리미티드 | Liquid crystal display device |
| KR101348746B1 (en) | 2005-06-27 | 2014-02-13 | 스미또모 가가꾸 가부시끼가이샤 | Dichroic guest-host polarizer |
| US20090122237A1 (en) * | 2005-11-07 | 2009-05-14 | Fujifilm Corporation | Polymer film, method for producing polymer film, optical film and polarizing plate and liquid crystal display device using the same |
| KR101023182B1 (en) * | 2007-07-05 | 2011-03-18 | 주식회사 엘지화학 | Composition Comprising Curable Dichroic Dye for Forming Optical Component And An Optical Component Prepared Using the Same |
| JP4999633B2 (en) * | 2007-10-15 | 2012-08-15 | 日東電工株式会社 | Polarizing film and liquid crystal display device |
| US8927070B2 (en) * | 2008-09-30 | 2015-01-06 | Fujifilm Corporation | Dichroic dye composition, light absorption anisotropic film, and polarizing element |
| JP5557281B2 (en) * | 2009-06-26 | 2014-07-23 | 住友化学株式会社 | Polarizing plate and laminated optical member using the same |
| 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 |
| JP5300776B2 (en) * | 2010-03-31 | 2013-09-25 | 富士フイルム株式会社 | Polarizing film, display device, and manufacturing method thereof |
| JP5442518B2 (en) * | 2010-03-31 | 2014-03-12 | 富士フイルム株式会社 | Light-absorbing anisotropic film, polarizing film, method for producing the same, and display device using the same |
| US9057020B2 (en) * | 2010-06-14 | 2015-06-16 | Basf Se | Black dichroic dye |
| KR102073987B1 (en) * | 2012-02-28 | 2020-02-05 | 스미또모 가가꾸 가부시키가이샤 | Compound and dichroic dye, and polarizing film |
-
2013
- 2013-02-22 KR KR1020130019191A patent/KR102129135B1/en active IP Right Grant
- 2013-02-26 TW TW102106757A patent/TWI622814B/en active
- 2013-02-27 JP JP2013036738A patent/JP6155697B2/en active Active
- 2013-02-28 CN CN201310064832.5A patent/CN103336325B/en active Active
-
2020
- 2020-06-16 KR KR1020200072976A patent/KR102285105B1/en active IP Right Grant
-
2021
- 2021-07-22 KR KR1020210096595A patent/KR102450756B1/en active IP Right Grant
-
2022
- 2022-09-28 KR KR1020220123258A patent/KR20220133851A/en not_active Application Discontinuation
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0517274B2 (en) * | 1981-11-16 | 1993-03-08 | Mitsubishi Kasei Kk | |
| JPS58187456A (en) * | 1982-04-27 | 1983-11-01 | Nippon Kayaku Co Ltd | Azo dye |
| JPH0461035B2 (en) * | 1982-06-30 | 1992-09-29 | Mitsubishi Kasei Kk | |
| US20030035972A1 (en) * | 1998-01-13 | 2003-02-20 | 3M Innovative Properties Company | Color shifting film articles |
| CN1356585A (en) * | 2000-11-24 | 2002-07-03 | 香港科技大学 | Process for preparing optical orientation film |
| EP1209515B1 (en) * | 2000-11-24 | 2003-07-09 | The Hong Kong University of Science & Technology | Method of manufacturing a photo-alignment layer |
| WO2011024891A1 (en) * | 2009-08-28 | 2011-03-03 | 富士フイルム株式会社 | Dichroic dye composition, polarizing film, liquid crystal cells and display devices |
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| CN111566543A (en) * | 2017-11-08 | 2020-08-21 | 亚利桑那大学董事会 | Imaging method and apparatus using circularly polarized light |
| CN111656232A (en) * | 2018-02-01 | 2020-09-11 | 住友化学株式会社 | Composition for forming polarizing film |
| CN111971597A (en) * | 2018-04-13 | 2020-11-20 | 住友化学株式会社 | Polymerizable liquid crystal composition |
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| CN112703436A (en) * | 2018-09-21 | 2021-04-23 | 住友化学株式会社 | Polarizing film, polarizing plate comprising same and display device |
| CN112703436B (en) * | 2018-09-21 | 2023-10-17 | 住友化学株式会社 | Polarizing film, polarizing plate comprising same and display device |
| WO2022104538A1 (en) * | 2020-11-17 | 2022-05-27 | 京东方科技集团股份有限公司 | Optical film and manufacturing method therefor, and reflective liquid crystal display panel and display device |
| CN115023633A (en) * | 2020-11-17 | 2022-09-06 | 京东方科技集团股份有限公司 | Optical diaphragm, preparation method thereof, reflective liquid crystal display panel and display device |
| CN115023633B (en) * | 2020-11-17 | 2024-01-16 | 京东方科技集团股份有限公司 | Optical film, preparation method thereof, reflective liquid crystal display panel and display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6155697B2 (en) | 2017-07-05 |
| JP2013210624A (en) | 2013-10-10 |
| KR102285105B1 (en) | 2021-08-02 |
| KR20220133851A (en) | 2022-10-05 |
| CN103336325B (en) | 2017-04-12 |
| KR20200076658A (en) | 2020-06-29 |
| KR20210095109A (en) | 2021-07-30 |
| TWI622814B (en) | 2018-05-01 |
| TW201344255A (en) | 2013-11-01 |
| KR102129135B1 (en) | 2020-07-01 |
| KR20130098914A (en) | 2013-09-05 |
| KR102450756B1 (en) | 2022-10-04 |
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