CN103336325B - Polarizing film, circular polarizing plate and method of producing the same - Google Patents

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

Light polarizing film, circularly polarizing plate and their manufacture method

Technical field

The present invention relates to light polarizing film, circularly polarizing plate and their manufacture method etc..

Background technology

Because the polarizer for being used for liquid crystal indicator has high transmission rate and degree of polarization concurrently, therefore with the dichroism pigment such as iodine Dyeing, stretch processing by polyvinyl alcohol（Iodine staining PVA）The film of composition（Light polarizing film）It is widely used.For example, patent Described in document 1 light polarizing film being made up of iodine staining PVA.

[prior art literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 7-142170 publication

The content of the invention

Problems to be solved by the invention

However, the light polarizing film being made up of iodine staining PVA easily takes yellow, the problem for so-called muted color phasic property difference occur. Additionally, the light polarizing film being made up of iodine staining PVA is difficult to filming, it is applied to and pursues the nearest display device being more thinned Aspect is limited.Therefore, it is an object of the invention to provide easily the excellent light polarizing film of filming, muted color phasic property, comprising described Polarizer and its manufacture method of light polarizing film etc..

The means of solve problem

The present invention includes following invention.

[1] a kind of light polarizing film, its contain formed by polymerizable liquid crystal compound polymer, be scattered in the polymer When determining light absorbs, there is at least a kind dichroism pigment of absorption maximum in the scope of 380 ~ 550nm of wavelength（1）With in ripple The scope of long 550 ~ 700nm has at least 2 kinds dichroism pigments of absorption maximum（2）.

[2] light polarizing film according to described in [1], wherein, make the dichroism pigment（1）It is scattered in by polymerizable liquid crystal When determining light absorbs in the polymer that compound is formed, there is absorption maximum in the scope of 400 ~ 550nm of wavelength.

[3] according to the light polarizing film described in [1] or [2], wherein, when being scattered in measure light absorbs in the polymer, The scope of 550 ~ 700nm of wavelength has at least 2 kinds dichroism pigments of absorption maximum（2）Survey in the polymer is scattered in When determining light absorbs,

There is the dichroism pigment of absorption maximum containing the scope in 550 ~ 600nm of wavelength（2-1）With

There is the dichroism pigment of absorption maximum in the scope of 600 ~ 700nm of wavelength（2-2）.

[4] light polarizing film according to described in any one of [1] ~ [3], polymerizable liquid crystal compound is to show smectic type liquid The compound of crystalline phase.

[5] light polarizing film recorded according to any one of [1] ~ [4], it obtains bragg peak in X-ray diffraction measure.

[6] light polarizing film recorded according to any one of [1] ~ [5], wherein, L^*a^*b^*Chromaticity coordinates a in colour system^*Value And b^*Value meets following formula（1F）And formula（2F）Relation.

- 3≤colourity a^*≤3（1F）

- 3≤colourity b^*≤3（2F）

[7] light polarizing film according to described in any one of [1] ~ [6], wherein, dichroism pigment（1）And dichroism Pigment（2）For azo-compound.

[8] light polarizing film according to described in any one of [1] ~ [7], wherein, dichroism pigment（2）By formula（2）Institute The compound of expression is constituted.

[formula（2）In,

N is 1 or 2.

Ar¹And Ar³It is separately formula（AR-1）~ formula（AR-4）Any one represented by group.

Ar²For formula（AR2-1）, formula（AR2-2）Or formula（AR2-3）Represented group.

A₁And A₂It is separately formula（A-1）~ formula（A-9）Any one represented by group, * represents bonding position.

（Mc is 0 ~ 10 integer, and when there is 2 mc in same group, 2 mc can be mutually identical or different.）]

[9] light polarizing film according to described in any one of [1] ~ [8], wherein, dichroism pigment（1）By formula（1）Institute The compound of expression is constituted.

[formula（1）In,

Y is formula（Y1）Or formula（Y2）Represented group.

（In formula, L is that oxygen atom or-NR-, R are hydrogen atom or the alkyl of carbon number 1 ~ 4.）

R¹For formula（R¹-1）~ formula（R¹-3）Any one represented by group.

（In formula, ma for 0 ~ 10 integer, when there is 2 ma in same group, 2 ma can be mutually identical or not Together.* bonding position is represented.）

R²For formula（R²-1）~ formula（R²-6）Any one represented by group.

（In formula, mb is 0 ~ 10 integer.）]

[10] a kind of polarizer, it is that the light polarizing film of any one record for arranging [1] ~ [9] over the transparent substrate is formed 's.

[11] manufacture method of the polarizer recorded according to [10], it has

The operation of the prepared laminate for possessing alignment films over the transparent substrate,

The operation of coating composition in the alignment films of the laminate, the composition contains polymerizable liquid crystal Compound, be scattered in the polymer formed by the polymerizable liquid crystal compound determine light absorbs when, 380 ~ 550nm's of wavelength Scope has a kind of dichroism pigment of absorption maximum（1）, in the scope of 550 ~ 700nm of wavelength there is 2 kind two of absorption maximum Chromotropism pigment（2）And solvent,

The operation for making the polymerizable liquid crystal compound included in the composition be polymerized.

[12] according to the manufacture method described in [11], wherein, transparent base is plastic basis material, also, the alignment films For optical alignment film.

[13] a kind of liquid crystal indicator, the light polarizing film that its any one for possessing [1] ~ [9] is recorded.

[14] a kind of circularly polarizing plate, it has the light polarizing film of any one record of [1] ~ [9] and λ/4 layer, meets following 's（A1）And（A2）Necessary condition.

（A1）The angle that the extinction axle of the light polarizing film is formed with the slow axis of λ/4 layer is about 45 °；

（A2）Value with the front retardation of λ/4 layer of the light measurement of wavelength 550nm is the scope of 100 ~ 150nm

[15] a kind of organic EL display, it possesses the circularly polarizing plate and organic EL element of [14] record.

Invention effect

According to the present invention, it is possible to provide easy filming, muted color phasic property excellent light polarizing film, being polarized comprising the light polarizing film Device.

Description of the drawings

[Fig. 1] is the polarizer of the light polarizing film comprising the present invention（This polarizer）Continuous manufacture method schematic diagram.

[Fig. 2] is the schematic diagram of the relation between the carrying direction D1 of the differently- oriented directivity D2 and film for representing optical alignment film.

[Fig. 3] is the schematic diagram of the section constitution of the liquid crystal indicator for representing the light polarizing film for having used the present invention.

[Fig. 4] is the schematic diagram of the sequence of this polarizer for representing the liquid crystal indicator for Fig. 3.

[Fig. 5] is the schematic diagram of the sequence of this polarizer for representing the liquid crystal indicator for Fig. 3.

[Fig. 6] is the schematic diagram of the section constitution of the EL display devices for representing the light polarizing film for having used the present invention.

[Fig. 7] is the schematic diagram of the section constitution of the embodiment of this polarizer for representing the light polarizing film comprising the present invention.

[Fig. 8] is the circularly polarizing plate for representing the light polarizing film comprising the present invention（This circularly polarizing plate）Continuous manufacture method The schematic diagram of one example.

[Fig. 9] is the schematic diagram of the sequence of this circularly polarizing plate for representing the EL display devices for Fig. 6.

[Figure 10] is the schematic diagram of the section constitution of the EL display devices for representing the light polarizing film using the present invention.

[Figure 11] is the skeleton diagram of the composition of the projection-type liquid crystal display device for showing the light polarizing film for having used the present invention.

Symbol description

1 transparent base

2 optical alignment films

3 light polarizing films

4 phase separation layers

100 polarizers

210 the 1st roller 210A core

220 the 2nd roller 220A core

230 the 3rd roller 230A core

240 the 4th roller 240A core

211A, 211B apparatus for coating

212A, 212B drying oven

213A polarised light UV irradiation units

213B light irradiation devices

300 help rolls

10 liquid crystal indicators

11 sealers

12a, 12b polarizer

13a, 13b phase separation layer

14a, 14b substrate

15 colour filters

16 transparency electrodes

17 liquid crystal layers

18 interlayer dielectrics

19 backlight modules

20 stain matrixes

21 thin film transistor (TFT)s

22 pixel electrodes

23 pads

30EL display devices

31 circularly polarizing plates

32 phase retardation films

33 substrates

34 interlayer dielectrics

35 pixel electrodes

36 organic function layers

37 cathode electrodes

38 drier

39 closures

40 thin film transistor (TFT)s

41 ribs（Rib）

42 diaphragm seal films

44EL display devices

111 light sources

112 the 1st lens arras

112a lens

113 the 2nd lens arras

114 polarization light conversion elements

115 compound lenses

121st, 123,132 dichronic mirror

122 speculums

140R, 140G, 140B liquid crystal panel

142nd, 143 polarizer

150 cross colour splitting prisms（Cross dichroic prism）

170 projection lens

180 projection screens

Specific embodiment

The light polarizing film of the present invention（Hereinafter, according to circumstances it is referred to as " this light polarizing film ".）It is characterised by, containing by polymerism Polymer and specific more than 3 kinds dichroism pigments that liquid-crystal compounds is formed.It is preferred that this light polarizing film is by containing polymerism liquid The composition of crystallization compound and more than the 3 kinds dichroism pigments（Hereinafter, according to circumstances it is referred to as " light polarizing film formation group Compound ".）Formed.First, light polarizing film formation is illustrated with composition.

1. light polarizing film formation composition

The present invention light polarizing film formation composition as described above, containing polymerizable liquid crystal compound and it is specific 3 kinds with Upper dichroism pigment, preferred its further contains solvent.This light polarizing film formed with composition is formed by such light polarizing film Easily carry out filming.First, each constituent to including in light polarizing film formation composition is illustrated respectively.

1-1. dichroism pigments

The dichroism pigment included in light polarizing film formation composition is included：It is being scattered in by polymerizable liquid crystal compound Scope when light absorbs are determined in the polymer of formation in 380 ~ 550nm of wavelength has at least a kind dichroism of absorption maximum Pigment（1）With at least 2 kinds dichroism pigments that the scope that 550 ~ 700nm of wavelength is fixed in identical survey has absorption maximum （2）.

1-1-1. dichroism pigments（1）

When dichroism pigment（1）When being scattered in measure light absorbs in the polymer formed by polymerizable liquid crystal compound, There is absorption maximum in the scope of 380 ~ 550nm of wavelength.And, as long as the measure is determined as follows：Prepare in the present invention Light polarizing film formation composition dichroism pigment be replaced into absorption maximum to be determined dichroism pigment maximum suction Measure composition is received, by the way that the method identical method that this light polarizing film is formed with composition is formed by light polarizing film with described later, Absorption maximum measure film is formed, the light absorbs of this absorption maximum measure film are determined.Determine the concrete side of the absorption maximum Method is identical with the method described in the embodiment of the present application.

As dichroism pigment（1）, can enumerate such as azo-compound.Preferably include the formula（1）It is represented Compound（Hereinafter, according to circumstances it is referred to as " compound（1）”.）.

Preferred compound（1）Azobenzene position geometrical isomerism for trans.

Formula（1）In Y be the formula（Y1）Or formula（Y2）Represented group, preferably formula（Y1）Represented group. Formula（Y1）And formula（Y2）In, the straight line at two ends represents bonding position, the bonding position in left side and the phenylene key with azo group Close, the bonding position on right side with have R²Phenylene bonding.L is oxygen atom or-NR-, R are hydrogen atom or carbon number 1 ~ 4 Alkyl.As the alkyl, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl group etc. can be included. Wherein, preferred L is oxygen atom or-NH-, more preferably oxygen atom.

R¹For the formula（R¹-1）, formula（R¹-2）Or formula（R¹-3）Represented group, preferably formula（R¹-2）And formula（R¹- 3）Represented group.Formula（R¹-2）2 ma in represented group can be identical or different respectively, preferably identical.Enter The preferred ma of one step is 0 ~ 5 integer.

R²For formula（R²-1）, formula（R²-2）, formula（R²-3）, formula（R²-4）, formula（R²-5）Or formula（R²-6）Represented group, More preferably formula（R²-2）, formula（R²-5）Or formula（R²-6）Represented group, more preferably formula（R²-6）Represented base Group.R²For formula（R²-1）, formula（R²-2）, formula（R²-3）, formula（R²-5）Or formula（R²-6）During represented group, the preferred group In the mb that includes for 0 ~ 10 integer, more preferably 0 ~ 5 integer.

As preferred compound（1）, following formula can be included（1-1）~ formula（1-8）Represented compound etc..

Wherein, preferred formula（1-1）, formula（1-2）, formula（1-3）, formula（1-5）, formula（1-7）And formula（1-8）Represented chemical combination Thing, particularly preferably formula（1-1）, formula（1-2）, formula（1-3）And formula（1-7）Represented compound.

Dichroism pigment is obtained by said determination（1）Light absorbs when, it has in the scope of 380 ~ 550nm of wavelength Absorption maximum, the preferably scope in 400 ~ 550nm of wavelength have absorption maximum, and the more preferably scope in 400 ~ 520nm of wavelength has Have absorption maximum, the further preferably scope in 430 ~ 520nm of wavelength has absorption maximum, particularly preferably wavelength 440 ~ The scope of 510nm has absorption maximum.If there is absorption maximum in the scope, as dichroism pigment（1）Can also Using multiple compounds（1）.

Herein, to compound（1）Preparation method illustrate.Compound（1）Can be by such as formula（1X）Represented Compound [compound（1X）] and formula（1Y）Represented compound [compound（1Y）] by the reaction shown by following schemas To prepare.

In the schema, R¹、R²And Y is equivalent in meaning with above-mentioned, Re¹And Re²It is interreaction and generates the base represented by Y The group of group.As Re¹And Re²Combination, can enumerate as：The combination of carboxyl and hydroxyl, carboxyl and amino（Such amino can To be replaced by R）Combination, the combination of phosphinylidyne halogen and hydroxyl, phosphinylidyne halogen and amino（Such amino can be replaced by R）'s Combination, the combination of carbon acyloxyallcyl and hydroxyl, carbon acyloxyallcyl and amino（Such amino can be replaced by R）Combination Deng.In addition, although herein to R¹Compound（1X）And with R²Compound（1Y）Illustrate, but can also make R is protected by appropriate protection group¹Compound and R is protected by appropriate protection group²Compound it is mutually contrary Should, afterwards, by carrying out appropriate deprotection reaction compound is manufactured（1）.

Make compound（1X）And compound（1Y）Reaction condition during reaction can be according to the compound for using（1X）And change Compound（1Y）Species selecting appropriate, most suitable known condition.

For example, as Re¹For carboxyl, Re²It is-C for hydroxyl, Y（=O）Reaction condition during-O-, can enumerate as：In solvent In, the condition being condensed in the presence of esterification condensation agent.Used as solvent, can include chloroform etc. can be while dissolved compound （1X）And compound（1Y）Solvent.As esterification condensation agent, Diisopropylcarbodiimide can be included（IPC）Deng.Herein, Further preferably and use dimethylamino naphthyridine（DMAP）Deng alkali.Reaction temperature can be according to compound（1X）And compound（1Y） Species selecting, but the scope such as -15 ~ 70 DEG C can be enumerated, preferably 0 ~ 40 DEG C of scope.Reaction time can enumerate such as 15 points The scope of clock ~ 48 hour.

Reactant mixture in course of reaction can also suitably be sampled, by liquid chromatography or gas chromatography Deng known analysis method, compound is confirmed（1X）And compound（1Y）Reduction degree, compound（1）Generation journey Degree, so that it is determined that the reaction time.

By method known to recrystallization, reprecipitation, extraction and various chromatographys etc. or by combining these operations, can be with Compound is extracted from reacted reactant mixture（1）.

1-1-2. dichroism pigments（2）

When implementing the measure, dichroism pigment（2）There is absorption maximum in the scope of 550 ~ 700nm of wavelength.It is maximum The assay method of absorption and dichroism pigment（1）Situation it is identical.

Contain two or more dichroism pigment in light polarizing film formation composition（2）, wherein, further preferably in ripple The scope of long 550 ~ 600nm has the dichroism pigment of absorption maximum（2-1）Have most with the scope in 600 ~ 700nm of wavelength The big dichroism pigment for absorbing（2-2）.Herein, further preferred dichroism pigment（2-1）In the model of 570 ~ 600nm of wavelength Enclose with absorption maximum, further preferred dichroism pigment（2-2）There is absorption maximum in the scope of 600 ~ 680nm of wavelength.

As dichroism pigment（2）, can enumerate such as azo-compound.It is preferred that dichroism pigment（2）For the formula（2） Represented compound（Hereinafter, according to circumstances it is referred to as " compound（2）”.）.

Preferred compound（2）Azobenzene position geometrical isomerism for trans.

In compound（2）Each group combination in, by composition Ar¹、Ar²And Ar³, it is determined that can be used as dichroism Pigment（2-1）The compound for using（2）, so that the compound（2）Scope in 550 ~ 600nm of wavelength in said determination has There is absorption maximum.As specific dichroism pigment（2-1）, the change shown by the combination of each group in table 1 can be included Compound（2）.The compound of the combination of each group is shown in table 1（2-1）Expression（2）In n be 1 situation.And, in table 1, Such as formula（AR-1）Represented group etc. be labeled as "（AR-1）" etc..

[table 1]

Then, in compound（2）Each group combination in, by combine Ar¹、Ar²And Ar³, it is determined that can be used as dichroic Property pigment（2-2）Compound（2）, so that the compound（2）Scope in 600 ~ 700nm of wavelength in said determination has Absorb.As specific dichroism pigment（2-2）, the compound shown by the combination of each group in table 2 can be included（2）. The compound of the combination of each group is shown in table 2（2-2）Expression（2）In n be 1 situation.And, the group in table 2 Mark is identical with the situation of table 1.

[table 2]

Herein, if specifically illustrating compound（2）, then can include by formula（2-11）Formula（2-39）The compound for representing respectively Deng.

The compound for including herein（2）Concrete example among, as dichroism pigment（2-1）, 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）, formula（2-29）And formula（2-30）The compound for representing respectively, as dichroism pigment（2-2）, phase When in by formula（2-31）, formula（2-32）, formula（2-33）, formula（2-34）, formula（2-35）And formula（2-36）The compound for representing respectively. And, by formula（2-11）, formula（2-15）And formula（2-16）The compound for representing respectively is not to show in 550 ~ 700nm of wavelength The pigment of absorption, but can addedly with formula（1）Pigment be used in combination.

Compound（2）Concrete example among, as the dichroism pigment included in light polarizing film formation composition（2）, More preferably 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）The material for representing respectively. Among these, if dichroism pigment（2）With from compound（2）Concrete example in the combination of more than two kinds selected represent, though then It is so different because blending ratio is different but identical with what is shown in such as table 3.In the table 3, such as formula（2-11）Represented Compound（2）Be expressed as "（2-11）”.

[table 3]

Dichroism pigment in light polarizing film formation composition（1）Content with relative to aftermentioned polymerizable liquid crystal chemical combination The content of the mass parts of thing 100 is represented, below preferably 50 mass parts, more than more preferably 0.1 mass parts, below 10 mass parts, More than more preferably 0.1 mass parts, below 5 mass parts.

Dichroism pigment in light polarizing film formation composition（2）Content with relative to polymerizable liquid crystal described later The content of the mass parts of compound 100 is represented, below preferably 10 mass parts, more than more preferably 0.1 mass parts, below 5 mass parts, More than more preferably 0.1 mass parts, below 3 mass parts.

Additionally, the dichroism pigment in light polarizing film formation composition（1）And dichroism pigment（2）Total content use Represent relative to the content of the mass parts of aftermentioned polymerizable liquid crystal compound 100, below preferably 30 mass parts, more preferably 0.1 More than mass parts, below 20 mass parts, more than more preferably 1 mass parts, below 15 mass parts.

If the content of each dichroism pigment is in the scope, because of the dichroism in light polarizing film formation composition Pigment shows sufficient dissolubility to solvent, therefore when manufacturing this light polarizing film with the light polarizing film formation composition, can be obtained not There is this light polarizing film for producing defect.And, as described above, light polarizing film formation composition can contain more than a kind dichroism Pigment（1）With two or more dichroism pigment（2）, but the light polarizing film formation composition can also containing two or more two to Color pigment（1）, it is also possible to containing more than 3 kinds dichroism pigments（2）.Containing two or more dichroism pigment（1）When, two Chromotropism pigment（1）Content be dichroism pigment of more than two kinds（1）Total amount, containing more than 3 kinds dichroism pigments （2）When, dichroism pigment（2）Content be more than 3 kinds of dichroism pigment（2）Total amount.

Dichroism pigment（2）Can be for example, by Japanese Patent Laid-Open No. Sho 58-38756 publication, Japanese Patent Laid-Open Known method described in clear 63-301850 publications, Japanese Patent Laid-Open No. Sho 58-104984 publication etc. is manufacturing.

Then, the constituent beyond dichroism pigment in light polarizing film formation composition is illustrated.

1-2. polymerizable liquid crystal compound

Polymerizable liquid crystal compound is the liquid-crystal compounds that may be polymerized in the state of orientation, and it has in intramolecular Polymerizable group.Light polarizing film formation composition containing polymerizable liquid crystal compound is orientated by making polymerizable liquid crystal compound In the state of be polymerized, form this light polarizing film.Particularly preferably polymerizable group is free-radical polymerised group.Free-radical polymerised base Group refers to the group for participating in Raolical polymerizable.

The polymerizable liquid crystal compound included in the light polarizing film formation composition of the present invention can show nematic liquid Crystalline phase（Hereinafter, according to circumstances it is referred to as " Nematic liquid crystalline phase ".）Compound, or show smectic crystal phase（With Under, according to circumstances it is referred to as " smectic crystal phase ".）Compound, can also be display Nematic liquid crystalline phase and smectic type liquid The compound of both crystalline phases, but preferably at least show the polymerism smectic crystal compound of smectic crystal phase.Containing poly- The light polarizing film formation of conjunction property smectic crystal compound passes through dichroism pigment with composition（1）And dichroism pigment（2） Interaction, muted color phasic property is extremely good, and this more excellent light polarizing film of polarization property can be obtained.

As the smectic crystal phase shown by polymerism smectic crystal compound, more preferably height smectic crystal Phase.Height smectic crystal described herein mutually refers to smectic B, smectic D phases, smectic E phases, smectic F phases, smectic G phases, smectic H phases, smectic I phases, smectic J phases, smectic K phases and smectic L phases, wherein, more preferably smectic B, smectic F phases and smectic I phases.

If the smectic crystal shown by polymerizable liquid crystal compound is mutually these height smectic crystal phases, can manufacture This light polarizing film of ordered orientation Du Genggao.Additionally, the sheet for mutually being made by the high height smectic crystal of ordered orientation degree like this Light polarizing film can obtain from hexagonal phase or crystallize the bragg peak of equal multidimensional structure in X-ray diffraction measure.The cloth Glug peak refers to the peak of the face periodic structure from molecularly oriented, by the light polarizing film formation composition of the present invention, can make Obtaining period distances isThis light polarizing film.

Whether the polymerizable liquid crystal compound included in light polarizing film formation composition shows Nematic liquid crystalline phase or smectic Type liquid crystalline phase, for example, can be carried out as follows confirmation.Prepare appropriate base material, light polarizing film formation combination is coated with the substrate Thing is formed after coated film, is removed by heating or reduced pressure treatment under conditions of polymerizable liquid crystal compound will not be polymerized The solvent contained in coated film.Then, the coated film formed on base material is heated to into isotropic phase temperature, by using polarization The observation of texture that light microscope is carried out, X-ray diffraction measure or Differential Scanning Calorimetry determined and shown by slowly cooling down examining Check The liquid crystalline phase for revealing.In inspection Check, particularly preferably for example, Nematic liquid crystalline phase is shown by cooling, by further Cool down and the polymerizable liquid crystal compound of display smectic crystal phase.In Nematic liquid crystalline phase and smectic crystal phase, for example, The surface observation carried out by using various microscopes or the nephelometric turbidity unit carried out using mist degree instrument are determined and can confirm that polymerism liquid Crystallization compound and dichroism pigment are not separated.

Hereinafter, include as the preferred compound of polymerizable liquid crystal compound for light polarizing film formation composition Concrete example.

As preferred polymerizable liquid crystal compound, can enumerate such as formula（4）Represented compound（Hereinafter, according to circumstances Referred to as " compound（4）”）.

U¹-V¹-W¹-X¹-Y¹-X²-Y²-X³-W²-V²-U²（4）

[formula（4）In,

X¹、X²And X³Represent independently of each other with or without the 1,4- phenylenes of substituent or with or without taking The 1,4- cyclohexylidenes of Dai Ji.But, X¹、X²And X³Among at least one be 1,4- phenylenes with or without substituent. Constitute-the CH of the 1,4- cyclohexylidenes with or without substituent₂- can be replaced by-O- ,-S- or-NR-.R is carbon atom The alkyl or phenyl of number 1 ~ 6.

Y¹And Y²Expression-CH independently of each other₂CH₂-、-CH₂O- ,-COO- ,-OCOO-, singly-bound ,-N=N- ,-CR^a=CR^b-、- C ≡ C- or-CR^a=N-。R^aAnd R^bThe alkyl of hydrogen atom or carbon number 1 ~ 4 is represented independently of each other.

U¹Represent hydrogen atom or polymerizable group.

U²Represent polymerizable group.

W¹And W²Singly-bound ,-O- ,-S- ,-COO- or-OCOO- are represented independently of each other.

V¹And V²The alkylidene of the carbon number 1 ~ 20 with or without substituent is represented independently of each other, is constituted described - the CH of alkylidene₂- can be replaced by-O- ,-S- or-NH-.]

Compound（4）In, X¹、X²And X³Among, preferably at least 2 is Isosorbide-5-Nitrae-phenylene with or without substituent.

It is preferred that unsubstituted with or without the 1,4- phenylenes of substituent.It is preferred that with or without the 1,4- of substituent Cyclohexylene is the anti-form-1 with or without substituent, 4- cyclohexylenes, more preferably with or without the anti-of substituent Formula -1,4- cyclohexylenes are unsubstituted.

As the 1,4- phenylenes with or without substituent or the 1,4- cyclohexylenes with or without substituent The substituent arbitrarily having, can include the alkyl of the carbon numbers such as methyl, ethyl and butyl 1 ~ 4；Cyano group；Halogen atom etc..

Preferred compound（4）Y¹For-CH₂CH₂- ,-COO- or singly-bound, preferred Y²For-CH₂CH₂- or-CH₂O-。

U²For polymerizable group.U¹For hydrogen atom or polymerizable group, preferably polymerizable group.It is preferred that U¹And U²It is all Polymerizable group, is more preferably all photo polymerization group.Photo polymerization group is referred to by being caused by aftermentioned photo polymerization The living radical of agent generation or acid etc. may participate in the group of polymerisation.Polymerizable liquid crystal with photo polymerization group Compound is favourable at the aspect that can be polymerized under more cryogenic conditions.

Compound（4）In, U¹And U²Polymerizable group can be with mutually different, but the preferably group of identical type.As Polymerizable group, can include vinyl, ethyleneoxy, 1- chlorovinyls, isopropenyl, 4- ethenylphenyls, acryloyl-oxy Base, methacryloxy, epoxy ethyl, oxetanylmethoxy etc..Wherein, preferably acryloxy, methacryloxy, Ethyleneoxy, epoxy ethyl and oxetanylmethoxy, more preferably acryloxy.

As V¹And V²Carbon number in the represented alkylidene with or without the carbon number 1 ~ 20 of substituent 1 ~ 20 alkylidene, can include methylene, ethylidene, 1,3- propylidene, 1,3- butylidenes, Isosorbide-5-Nitrae-butylidene, 1,5- Asias penta Base, 1,6- hexylidenes, 1,7- heptamethylenes, 1,8- octamethylenes, 1,10- decylenes, 1,14- Asia myristyls and 1,20- sub- 20 Alkyl etc..It is preferred that V¹And V²For the alkylidene of carbon number 2 ~ 12, the more preferably alkylidene of carbon number 6 ~ 12.

As the substituent that the alkylidene of the carbon number 1 ~ 20 with or without substituent arbitrarily has, although can arrange Cyano group and halogen atom etc. are enumerated, but the preferably alkylidene is unsubstituted, more preferably unsubstituted and straight-chain alkylidene.

W¹And W²Singly-bound or-O- are preferably independently of each other.

As compound（4）, formula can be included（4-1）~ formula（4-43）Represented compound etc..Such compound （4）Concrete example when there is Isosorbide-5-Nitrae-cyclohexylene, preferably such Isosorbide-5-Nitrae-cyclohexylene is trans body.

Polymerizable liquid crystal compound can individually or two or more is mixed in light polarizing film formation composition.Additionally, mixed When closing two or more, preferably at least a kind is compound（4）.As mixing 2 kinds of polymerizable liquid crystal compounds when mixing ratio, generally For 1:99~50:50, preferably 5:95~50:50, more preferably 10:90~50:50.

Exemplified compound（4）Among, 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 formula（4-29）Represented compound.These compounds by with its The interaction of his polymerizable liquid crystal compound, under the temperature conditionss less than crystallization phase transition temperature, i.e., is fully keeping high In the state of the mesomorphic state of degree smectic phase, can easily be polymerized.Specifically, these compounds are below 70 DEG C, and preferably 60 Under temperature conditionss below DEG C, may be polymerized in the state of the mesomorphic state for fully keeping height smectic phase.

Relative to the solid state component of light polarizing film formation composition, the polymerism liquid in preferred light polarizing film formation composition The content ratio of crystallization compound be 50 ~ 99.9 mass %, more preferably 80 ~ 99.9 mass %.If polymerizable liquid crystal compound contains It is proportional in the scope, then the orientation for having the tendency of polymerizable liquid crystal compound is uprised so as to preferred.Herein, solid-state into Divide and refer to, the total amount of the composition after the volatile ingredients such as solvent is removed with composition from light polarizing film formation.

Polymerizable liquid crystal compound can according to such as Lub et al.Recl.Trav.Chim.Pays-Bas, 115, 321-328（1996）Or the known method described in Japanese Patent No. 4719156 etc. is preparing.

1-3. solvent

It is preferred that light polarizing film formation composition contains solvent.As solvent, polymerizable liquid crystal can be preferably completely dissolved The solvent of compound and dichroism pigment.Furthermore it is preferred that being the polymerizable liquid crystal to including in light polarizing film formation composition The inert solvent of the polymerisation of compound.

As solvent, methyl alcohol, ethanol, ethylene glycol, isopropanol, propane diols, EGME, butyl glycol ether can be included And the alcoholic solvent such as propylene glycol monomethyl ether；Ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, gamma-butyrolacton or propane diols first The ester solvent such as ether acetic acid ester and ethyl lactate；Acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-HEPTANONE and methyl iso-butyl ketone (MIBK) Deng ketone solvent；The aliphatic hydrocarbon solvents such as pentane, hexane and heptane；The aromatic hydrocarbon solvents such as toluene and dimethylbenzene；The nitriles such as acetonitrile are molten Agent；The ether solvents such as tetrahydrofuran and dimethoxy-ethane；The chlorinated solvents such as chloroform and chlorobenzene；Deng.These solvents can individually make With, it is also possible to multiple combination is used.

Relative to the total amount of the light polarizing film formation composition, the content of preferred solvent is 50 ~ 98 mass %.In other words, It is preferred that the solid state component in light polarizing film formation composition is 2 ~ 50 mass %.If solid state component is more than 2 mass %, there is easily system The tendency of this slim light polarizing film of an object of the present invention is obtained so as to preferred.If additionally, the solid state component is 50 mass % Hereinafter, then become substantially homogeneous by the thickness of light polarizing film because of the viscosity of light polarizing film formation composition, have described inclined Become to be not likely to produce uneven tendency in light film so as to preferred.Furthermore, it is possible to consider that the thickness of light polarizing film is such to determine Solid state component.

1-4. other additives

Light polarizing film formation in present invention composition arbitrarily containing dichroism pigment, polymerizable liquid crystal compound and Additive beyond solvent.

1-4-1. polymerisation auxiliary agents

It is preferred that light polarizing film formation composition contains polymerization initiator.The polymerization initiator can be to cause polymerism liquid The compound of the polymerisation of crystallization compound.As polymerization initiator, under cryogenic can initiated polymerization fermentation, preferably For photo-induced polymerization initiator.Specifically, the compound for producing living radical or acid by the effect of light can be used as photo polymerization Initiator.Among the photo-induced polymerization initiator, more preferably the material of living radical is produced by the effect of light.

As polymerization initiator, can enumerate as：Rest in peace aroma compounds, benzophenone cpd, alkyl phenyl assimilation compound, Acylphosphine oxide compound, triaizine compounds, salt compounded of iodine and sulfonium salt etc..

As aroma compounds of resting in peace, 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 hexichol first Ketone, 4- -4 '-methyldiphenyl sulfides of benzoyl, 3,3 ', 4,4 '-four（T-butyl peroxy carbonyl）Benzophenone and 2,4, 6- tri-methyl benzophenones etc..

As 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- morpholino phenyls）- 1- butanone, 2- hydroxy-2-methyl -1- Phenyl -1- acetone, 1,2- diphenyl -2,2- dimethoxy -1- ethyl ketones, 2- hydroxy-2-methyl -1- [4-（2- hydroxyl-oxethyls） Phenyl] -1- acetone, 1- hydroxycyclohexylphenylketones and 2- hydroxy-2-methyl -1- [4-（1- methyl ethylenes）Phenyl] -1- third Oligomer of ketone etc..

As acylphosphine oxide compound, TMDPO and double can be included（2, 4,6- trimethylbenzoyls）Phenyl phosphine oxide etc..

As triaizine compounds, can enumerate as：2,4- is double（Trichloromethyl）-6-（4- methoxyphenyls）- 1,3,5- triazines, 2,4- is double（Trichloromethyl）-6-（4- methoxyl group naphthyls）- 1,3,5- triazines, 2,4- are double（Trichloromethyl）-6-（4- methoxybenzene second Thiazolinyl）- 1,3,5- triazines, 2,4- are double（Trichloromethyl）-6-[2-（5- methylfuran -2- bases）Vinyl] -1,3,5- triazines, 2, 4- is double（Trichloromethyl）-6-[2-（Furans -2- bases）Vinyl] -1,3,5- triazines, 2,4- be double（Trichloromethyl）-6-[2-（4- bis- Ethylamino -2- aminomethyl phenyls）Vinyl] -1,3,5- triazines and 2,4- be double（Trichloromethyl）-6-[2-（3,4- dimethoxy benzenes Base）Vinyl] -1,3,5- triazines etc..

Polymerization initiator can also use commercially available article.As commercially available polymerization initiator, can include " 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 Ba Ben（Strain））；“Seikuol（The Le of セ イ Network オ mono-）BZ”、“Seikuol Z”、“Seikuol BEE”（Seiko chemistry （Strain））；“kayacure（カ ヤ キ ユ ア mono-）BP100”（Japanese chemical drug（Strain））；“kayacure UV I-6992”（Tao Shi is public Department's system）；“Adeka Optomer（ア デ カ オ プ ト マ mono-）SP-152 ", " Adeka Optomer SP-170 "（（Strain）Ai Di Section）；“TAZ-A”、“TAZ-PP”（Japanese big Chang Hua Jia She）；And " TAZ-104 "（Three and chemical society）Deng.

When light polarizing film formation composition contains polymerization initiator, its content can be according in light polarizing film formation composition The species and its amount of the polymerizable liquid crystal compound for containing makes the appropriate adjustments, and generally, amounts to relative to polymerizable liquid crystal compound 100 mass parts, the content of polymerization initiator is 0.1 ~ 30 mass parts, preferably 0.5 ~ 10 mass parts, more preferably 0.5 ~ 8 mass Part.If the content of polymerizing initiator is within this range, because the feelings without confusion can be orientated in polymerizable liquid crystal compound Make under condition its polymerization so it is preferred that.

1-4-2. photosensitizer

When light polarizing film formation composition contains photo-induced polymerization initiator, light polarizing film formation composition can contain photosensitive Agent.As photosensitizer, can enumerate as：The xanthone compound such as xanthone and thioxanthone（For example, 2,4- diethyl Thioxanthone, 2- isopropyl thioxanthones etc.）；Anthracene and the anthracene containing alkoxyl（For example, dibutoxy anthracene etc.）Deng anthracene compound；Fen Thiazine and rubrene etc..

When light polarizing film formation composition contains photo-induced polymerization initiator and photosensitizer, in light polarizing film formation composition The polymerisation of the polymerizable liquid crystal compound for containing further is promoted.The content of such photosensitizer can be according to being used in combination Photo-induced polymerization initiator and polymerizable liquid crystal compound species and its amount make the appropriate adjustments, generally, relative to polymerism liquid The mass parts of content 100 of crystallization compound, it is 0.1 ~ 30 mass parts, preferably 0.5 ~ 10 mass parts, more preferably 0.5 ~ 8 mass Part.

1-4-3. polymerization inhibitor

In order that the polymerisation of polymerizable liquid crystal compound is stably carried out, light polarizing film formation composition can contain Polymerization inhibitor.By polymerization inhibitor, the degree that the polymerisation of polymerizable liquid crystal compound is carried out is can control.

As polymerization inhibitor, can enumerate as：Hydroquinones, the hydroquinones containing alkoxyl, the catechol containing alkoxyl（Example Such as, butyl-catechol etc.）, pyrogallol, the radical scavenger such as 2,2,6,6- tetramethyl -1- piperidines epoxide free radicals；Benzene Thiophenols；Beta-naphthylamine class and betanaphthol class etc..

When containing polymerization inhibitor in light polarizing film formation composition, its content can be according to the polymerizable liquid crystal compound for using Species and its content etc. of amount and photosensitizer make the appropriate adjustments, generally, relative to the mass of polymerizable liquid crystal compound 100 Part, it is 0.1 ~ 30 mass parts, preferably 0.5 ~ 10 mass parts, more preferably 0.5 ~ 8 mass parts.

If the content of polymerization inhibitor is within the above range, because of the polymerism liquid that can contain in light polarizing film formation composition The orientation of crystallization compound without confusion in the case of make its polymerization so it is preferred that.

1-4-4. levelling agent

It is preferred that light polarizing film formation composition contains levelling agent.Levelling agent is referred to regulation light polarizing film formation composition Mobility, make the material of coating light polarizing film formation composition and the more flat function of obtained coated film, can include Surfactant etc..As preferred levelling agent, can include based on polyacrylic acid ester compounds the levelling agent of composition and with Compound containing fluorine atom is levelling agent of principal component etc..

As the levelling agent of the composition based on polyacrylic acid ester compounds, can include " BYK-350 ", " BYK-352 ", " BYK-353 ", " BYK-354 ", " BYK-355 ", " BYK-358N ", " BYK-361N ", " BYK-380 ", " BYK-381 " and " BYK-392 " [Bi Ke chemical companies（BYK Chemie）] etc..

As the levelling agent with the compound containing fluorine atom as principal component, " Megafac can be included（メガフアツク） 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（The Off ロ Application of サ mono-） S-381”、Surflon“S-382”、Surflon“S-383”、Surflon“S-393”、Surflon“SC-101”、Surflon " SC-105 ", " KH-40 " and " SA-100 " [AGC Seimi Chemical（AGCセイミケミカル）（Strain）]；“E1830”、 “E5844”[（Strain）Great Jin fine chemistries research institute]；“EFTOP（エフトツプ）EF301”、EFTOP“EF303”、EFTOP [Mitsubishi Materials electronics is melted into for " EF351 " and EFTOP " EF352 "（Strain）] etc..

When making to contain levelling agent in light polarizing film formation composition, relative to the matter of content 100 of polymerizable liquid crystal compound Amount part, its content is usually more than 0.3 mass parts, below 5 mass parts, more than preferably 0.5 mass parts, below 3 mass parts.If The content of levelling agent in the scope, then because easily making polymerizable liquid crystal compound carry out horizontal alignment and have obtained polarisation Film become smoother tendency so it is preferred that.If exceeding the model relative to the content of the levelling agent of polymerizable liquid crystal compound Enclose, then have the tendency of to be also easy to produce in obtained this light polarizing film uneven.And, the light polarizing film formation composition can contain There is levelling agent of more than two kinds.

2. the forming method of this light polarizing film

Then, illustrate to forming the method for forming this light polarizing film with composition by light polarizing film.In such method, By the way that light polarizing film formation composition is coated on base material, it is preferably coated onto on transparent base, so as to form this light polarizing film.

2-1. transparent base

Transparent base is referred to the transparent base material that can pass through light, the degree of particularly permeable visible ray.It is described The transparency refers to, in the characteristic of the scope to the light transmittance of light more than 80% of 380 ~ 780nm of wavelength.Specifically, as transparent Base material, can include glass baseplate and plastic basis material etc., preferably plastic basis material.As the plastics for constituting plastic basis material, can arrange Lift such as：The polyolefin such as polyethylene, polypropylene, norbornene-based polymer；Annular ethylene series resin；Polyvinyl alcohol；Gather to benzene two Formic acid glycol ester；Polymethacrylates；Polyacrylate；Triacetyl cellulose, diacetyl cellulose and cellulose acetate The cellulose esters such as ester propionic ester；PEN；Merlon；Polysulfones；Polyether sulfone；Polyether-ketone；Polyphenylene sulfide and The plastics such as polyphenylene oxide.Wherein, from can easily obtain from market, the transparency it is excellent from the aspect of, especially preferably cellulose Ester, annular ethylene series resin, polyethylene terephthalate or polymethacrylates.Manufactured using such transparent base During this light polarizing film, from can carry, keeping the transparent base when will not cause destruction etc. breakage in the case of easily carry out From the aspect of operation, supporting base material etc. can be also sticked on the transparent base.Additionally, it is as described below, by this light polarizing film system When making circularly polarizing plate, there is imparting plastic basis material with the situation of phase difference.In the case of this, as long as by drawing plastic basis material Stretch process etc. to give phase difference.

When giving phase difference to plastic basis material, from from the aspect of its phase difference value easy to control, preferably by cellulose esters or The plastic basis material that annular ethylene series resin is constituted.

Cellulose esters is the material of at least a portion by acid esterification of the hydroxyl included in cellulose.By such fiber The cellulose ester film that plain ester is constituted can easily be obtained from market.As commercially available triacetylcellulose film, have for example “fujitac（フジタツク）Film "（Fujiphoto（Strain））；" KC8UX2M ", " KC8UY " and " KC4UY "（Konica U.S. energy Up to precision optics（Strain））Deng.Such commercially available triacetylcellulose film can be right directly or according to imparting phase difference is needed It is used as transparent base afterwards.Additionally, can implement on the surface of ready transparent base anti-dazzle process, hard coat process, Antistatic process or antireflection process etc. are surface-treated, and are then used as transparent base.

In order to give plastic basis material with phase difference, as described above, depending on the method for stretched plastic base material etc..By thermoplastic Property the plastic basis material that constitutes of resin can all carry out stretch processing, but from from the aspect of phase difference easy to control, more preferably by ring The plastic basis material that shape olefin-based resin is constituted.Annular ethylene series resin is referred to for example by ENB or polycyclic ENB system list The material that the polymer of the cyclic olefins such as body or copolymer are constituted, the annular ethylene series resin can locally contain open loop portion Position.In addition it is also possible to be the material after hydrogenating to the annular ethylene series resin containing open loop position.Additionally, never showing Write infringement transparency aspect or will not significantly increase from the aspect of hygroscopicity, the annular ethylene series resin for example can be ring-type Alkene, chain olefin or vinylated aromatic compound（Styrene etc.）Deng copolymer.Additionally, the cycloolefin tree Fat can import polar group in its intramolecular.

Annular ethylene series resin is the copolymer of cyclic olefin, chain olefin or the aromatic compound with vinyl When, be ethene or propylene etc. as the chain olefin, additionally, as vinylated aromatic compound, be styrene, α- Methyl styrene and alkyl-substituted styrene etc..In such copolymer, relative to the entire infrastructure of annular ethylene series resin Unit, is 50 moles of below %, for example, the degree of 15 ~ 50 moles of % from the content ratio of the construction unit of cyclic olefin Scope.Annular ethylene series resin is the ternary polymerization by obtained in cyclic olefin, chain olefin and vinylated aromatic compound During thing, for example, relative to the entire infrastructure unit of the annular ethylene series resin, the construction unit from chain olefin contains Proportional is the degree of 5 ~ 80 moles of %, is 5 ~ 80 from the content ratio of the construction unit of vinylated aromatic compound The degree of mole %.When manufacturing the annular ethylene series resin, the annular ethylene series resin of such terpolymer has permissible Make the relative advantage for reducing of consumption of the cyclic olefin of high price.

Annular ethylene series resin can easily be obtained from market.As commercially available annular ethylene series resin, can include " Topas " [Ticona society（Solely）]；“Arton（The ト Application of ア mono-）" [Japan Synthetic Rubber（Strain）]；“ZEONOR（ゼオノア）" and “ZEONEX（ゼオネツクス）" [Japanese auspicious father-in-law（Strain）]；“apel（アペル）" [Mitsui Chemicals（Strain）System] etc..It is such Then annular ethylene series resin for example by film-forming method masking known to solvent cast method or extrusion by melting etc. can be made Film（Annular ethylene series resin film）.Additionally, it is also possible to use commercially available in the form of a film annular ethylene series resin Film.As such commercially available annular ethylene series resin film can enumerate as：" Na of エ ス シ mono- " and " SCA40 " [ponding Learn industry（Strain）]；" ZEONOR films " [Optes（オプテス）（Strain）]；" Arton films " [Japan Synthetic Rubber（Strain）] Deng.

Then, illustrate in the method for phase difference to giving plastic basis material.Plastic basis material can be by known drawing Stretching method gives phase difference.For example, the roller by plastic basis material on roller is prepared（Coiling body）, connect from such coiling body The plastic basis material of debatching is carried to heating furnace by plastic basis material debatching by continuous ground.The design temperature of heating furnace is plastic basis material Near glass transformation temperature（℃）~ [glass transformation temperature+100]（℃）Scope, preferably near glass transformation temperature（℃）~ [glass transformation temperature+50]（℃）Scope.In the heating furnace, towards the direct of travel or court and direct of travel of plastic basis material When the direction for intersecting vertically is stretched, adjust and carry direction and tension force, towards arbitrarily angled inclination, carry out uniaxially or two is axial Hot-stretch is processed.The multiplying power of stretching is usually the scope of 1.1 ~ 6 times of degree, the scope of preferably 1.1 ~ 3.5 times of degree.This Outward, as the method stretched towards incline direction, as long as can continuously make axis of orientation tilt to the method for desired angle just It is not particularly limited, known drawing process can be adopted.Such drawing process can enumerate as：Japanese Patent Laid-Open No. Sho 50- Method described in No. 83482 publications or Japanese Patent Laid-Open 2-113920 publication.

In terms of the weight of the degree for operating with can carrying out practicality and can ensure that from the aspect of the sufficiently transparency, preferably The thickness of thin of transparent base, but have intensity decreases if too thin, the tendency that processability is deteriorated.The appropriate thickness of glass baseplate is Such as 100 ~ 3000 μm of degree, preferably 100 ~ 1000 μm of degree.The appropriate thickness of plastic basis material is such as 5 ~ 300 μm Degree, preferably 20 ~ 200 μm of degree.When this light polarizing film is used as into circularly polarizing plate described later, particularly as mobile device The thickness of the transparent base during circularly polarizing plate of purposes is preferably 20 ~ 100 μm of degree.And, film is given by stretching During phase difference, the thickness after stretching is determined by the thickness and stretching ratio before stretching.

2-2. alignment films

It is preferred that forming alignment films on the base material for the manufacture of this light polarizing film.In the case of this, by light polarizing film formation group Compound is coated in alignment films.It is therefore preferable that it is not in be formed with the coating of composition by light polarizing film that the alignment films have Etc. the solvent resistance of the degree of the dissolving for causing.Furthermore it is preferred that having in the heating of solvent and liquid crystal aligning is removed Heat resistance.Such alignment films can be formed by orientation polymer.

As the orientation polymer, can enumerate as：Intramolecular has the polyamide of amido link or gelatin class, intramolecular The polyamic acid of the polyimides with imide bond and its hydrolysate, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polypropylene Acid amides, poly- oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylate etc. are polymerized Thing.Among these, preferred polyvinyl alcohol.These orientation polymer of formation alignment films can be used alone or two or more is mixed Conjunction is used.

By the coating on base material as the orientation polymer composition being dissolved in solvent（Containing orientation polymer Solution）The orientation polymer, can on the substrate form alignment films.As the solvent, water outlet can be enumerated； The alcoholic solvents such as methyl alcohol, ethanol, ethylene glycol, isopropanol, propane diols, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether；Second The esters such as acetoacetic ester, butyl acetate, ethylene glycol monomethyl ether acetate, gamma-butyrolacton, propylene glycol methyl ether acetate and ethyl lactate are molten Agent；The ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl iso-butyl ketone (MIBK)；Pentane, hexane and The aliphatic hydrocarbon solvents such as heptane；The nitrile solvents such as the aromatic hydrocarbon solvents such as toluene and dimethylbenzene, acetonitrile；Tetrahydrofuran and dimethoxy The ether solvents such as ethane；The chlorine such as chloroform and chlorobenzene replaces hydrocarbon solvent；Deng.These organic solvents can be used alone or multiple combination makes With.

Additionally, as being used to form the orientation polymer composition of alignment films, can also directly use commercially available orientation Membrane material.As commercially available aligning film material, Sunever can be included（サ Application エ バ mono-）（Registration mark, Nissan Chemical Industries （Strain）System）Or Optomer（オ プ ト マ mono-）（Registration mark, Japan Synthetic Rubber（Strain）System）Deng.

Method as alignment films are formed on base material, can enumerate the orientation combination of polymers as described in the coating on base material Thing or commercially available aligning film material, the method then annealed etc..The thickness of so obtained alignment films be usually 10nm ~ The scope of the scope of 10000nm, preferably 10nm ~ 1000nm.

In order to the alignment films are given with orientation anchorage force, preferably rubbed as needed（Rubbing manipulation）.By giving Orientation anchorage force can be such that polymerizable liquid crystal compound is orientated to desired direction.

As by rubbing manipulation give orientation anchorage force method, can enumerate as：Preparation has wound friction cloth, has been rotating Friction roller, by the laminate that alignment films formation coated film is defined on base material Transport Desk is placed in（Stage）On, by by its Carry towards the friction roller being rotating, the method for making the alignment films formation coated film contact with the friction roller being rotating.

Further, it is also possible to using so-called optical alignment film.Optical alignment film is referred to, will contained with photoreaction group The composition of polymer or monomer and solvent（Hereinafter, according to circumstances it is referred to as " light redirecting layer formation composition "）It is coated on base On material, by irradiating polarised light（Preferably polarised light UV）And impart the alignment films of orientation anchorage force.Photoreaction group Refer to, by irradiation light（Light irradiation）Produce the group of liquid crystal aligning energy.Specifically, it is produced as molecule by irradiation light Orientation induction or such generation of isomerization reaction, dimerization, photo-crosslinking or photolysis reactionses become liquid crystal and take To the material of the light reaction of the origin of energy.Among the photoreaction group, keep when orientation is excellent, light polarizing film is formed The material of the consideration of smectic crystal state aspect, preferred initiation dimerization or photo-crosslinking.It is as above anti-as occurring The photoreaction group answered, it is however preferred to have unsaturated bond, the particularly group with double bond, particularly preferably with from by Carbon-to-carbon double bond（C=C keys）, carbon-to-nitrogen double bond（C=N keys）, nitrogen-nitrogen double bond（N=N keys）And carbon-oxygen double bond（C=O keys）The group of composition The group of at least one selected in group.

As the photoreaction group with C=C keys, can enumerate as：Vinyl, polyene-based, stilbene radicals, stilbene oxazolyl, benzene second Thiazolinyl pyridine alkali, chalcone base and cinnamoyl etc..As the photoreaction group with C=N keys, can include and have Aromatic series schiff bases and the isostructural group of aromatic series hydrazone.As the photoreaction group with N=N keys, azo can be included Phenyl, azo naphthyl, heteroaromatic azo group, bisazo base and formazan base etc. or the base with azoxybenzene as basic structure Group.As the photoreaction group with C=O keys, benzophenone base, cumarin base, anthraquinonyl and maleimide can be included Amido etc..These groups can have alkyl, alkoxyl, aryl, allyloxy, cyano group, alkoxy carbonyl group, hydroxyl, sulfonic group and The substituents such as halogenated alkyl.

Wherein, the photoreaction group that can preferably cause photo-induced dimerizationization to react, it is inclined needed for because of easy prepared light orientation The optical alignment film that light irradiation amount of shaking is relatively fewer and heat endurance and ageing stability are excellent, therefore it is preferred that cinnamoyl and Cha Er Ketone group.If furtherly, as the polymer with photoreaction group, particularly preferably with the end of the polymer lateral chain End position becomes the material of cinnamoyl as cinnamic acid structure.

As the solvent of light redirecting layer formation composition, preferred polymer of the dissolving with photoreaction group and list The solvent of body, as the solvent, can enumerate such as the solvent used in above-mentioned orientation polymer composition.

Can be with relative to the concentration of light redirecting layer formation composition, the polymer with photoreaction group or monomer Do suitable according to the species of the polymer with the photoreaction group or monomer and the thickness of the optical alignment film for wanting to manufacture Work as adjustment, represented with solid component concentration, preferably it is at least 0.2 mass %, the particularly preferably scope of 0.3 ~ 10 mass %.This Outward, in the scope of the characteristic for significantly not damaging optical alignment film, the oriented layer formation composition can containing polyvinyl alcohol or Polyimides Polymer material, photosensitizer.

Method as orientation polymer composition or light redirecting layer formation composition is coated with base material, can adopt With spin-coating method, extrusion, gravure coating process, die type rubbing method, bar type coating（Bar coating）Method and spreader method etc. are applied The known method of the print process such as cloth method or flexographic printing process etc..And, this light polarizing film is manufactured by aftermentioned volume to volume（roll to roll）When the continuous manufacture method of form is to implement, the coating process is generally applied using gravure coating process, die type The print process such as cloth method or flexographic printing process.

And, rubbed or during polarizing light irradiation, if being sheltered, can also form the different multiple areas of differently- oriented directivity Domain（Pattern）.

The manufacture method of 2-3. this light polarizing film

In the alignment films formed on the base material or base material, coating light polarizing film formation is obtained coated film with composition.Make Method to be coated with light polarizing film formation composition, can enumerate such as with as being coated with orientation polymer or light reaction on base material Layer formation composition method and exemplified method identical method.

Then, the polymerizable liquid crystal compound by including in the coated film makes solvent seasoning under conditions of not being polymerized Remove, formation is dried overlay film.As drying means, can enumerate as：Natural seasoning, aeration-drying method, heat drying and decompression Seasoning etc..

Then, as preferred mode, once the liquid crystal shape for being dried the polymerizable liquid crystal compound included in overlay film State is changed into after nematic crystal, makes the Nematic liquid crystalline phase be changed into smectic crystal phase immediately.

Like this in order to form smectic crystal phase via Nematic liquid crystalline phase, can be wrapped using being for example dried in overlay film The polymerizable liquid crystal compound for containing is heated to more than the temperature of display Nematic liquid crystalline phase, then by the polymerizable liquid crystal chemical combination Thing is cooled to the method till showing the temperature of smectic crystal phase.

The polymerizable liquid crystal compound being dried in overlay film is set to be changed into smectic crystal phase, make the polymerizable liquid crystal When compound is changed into smectic crystal phase via Nematic liquid crystalline phase, by the phase for determining the polymerizable liquid crystal compound for using Transition temperature, can obtain the condition of control mesomorphic state（Heating condition）.The condition determination of such phase transition temperature is in this Shen It is explained in embodiment please.

Then, the polymerization process of polymerizable liquid crystal compound is illustrated.Herein, to making to be combined in light polarizing film formation Contain photo-induced polymerization initiator in thing, the mesomorphic state for making the polymerizable liquid crystal compound being dried in overlay film is changed into smectic type liquid After crystalline phase, in the state of the mesomorphic state for keeping this smectic crystal phase, carry out the polymerizable liquid crystal compound photic The method of polymerization is described in detail.

In photo polymerization, as the light to being dried overlay film irradiation, can be by being dried the light included in overlay film according to described Cause the species of polymerization initiator or the species of polymerizable liquid crystal compound（What particularly described polymerizable liquid crystal compound had The species of polymerizable group）And its light suitably selected from the group being made up of visible ray, ultraviolet light and laser of amount or work Property electron beam is carrying out.Among them, in terms of the carrying out of polymerisation easy to control and it is usable in this area extensively being made With device be used as from the aspect of the device for being related to photo polymerization, preferred ultraviolet light.Therefore, by ultraviolet light, in order to Photo polymerization is carried out, the polymerizable liquid crystal compound that contains in light polarizing film formation composition and photic poly- is preferably pre-selected Close the species of initiator.Additionally, during polymerization, by appropriate cooling device while ultraviolet light, by covering to drying Film is cooled down also can control polymerization temperature.By using such cooling device, if polymerism liquid can be implemented at lower temperatures The polymerization of crystallization compound, even if then using the material that the heat resistance in above-mentioned base material is relatively low, also having validly to form The advantage of this light polarizing film.And, during photo polymerization, by being sheltered and being developed, can also be obtained define pattern sheet it is inclined Light film.

By carrying out photo polymerization as above, polymerizable liquid crystal compound is keeping Nematic liquid crystalline phase, smectic crystal Phase, it is preferably exemplified as height smectic crystal phase in the state of be polymerized, form this light polarizing film.Polymerism Liquid-crystal compounds is polymerized and obtained this light polarizing film in the state of smectic crystal phase is kept, with conventional host-guest （Host-guest）Type light polarizing film, i.e. make polymerizable liquid crystal chemical combination in the state of the mesomorphic state for keeping Nematic liquid crystalline phase Thing etc. is polymerized and obtained light polarizing film compares, and has the advantages that polarization property is high.Further, be only coated with lyotropic dichroic The light polarizing film of property pigment compares, and has the advantages that excellent strength.

The thickness of this light polarizing film being preferably formed is more than 0.5 μm, less than 10 μm of scope, more preferably 1 μ More than m, less than 5 μm.Therefore, this light polarizing film formation thickness of coated film can consider the thickness of obtained this light polarizing film come really It is fixed.And, the thickness of this light polarizing film is obtained by the measure of interference formula film thickness gauge, laser microscope or contact pin type film thickness gauge.

Additionally, this light polarizing film for so being formed in X-ray diffraction measure as described above, particularly preferably can obtain Bradley This light polarizing film at lattice peak.As such this light polarizing film for obtaining bragg peak, can enumerate as：Show from hexagonal phase or This light polarizing film of the diffraction maximum of crystalline phase.

Further, the muted color phasic property of so this light polarizing film of manufacture is excellent.Herein, the excellent light polarizing film of muted color phasic property Refer to, L^*a^*b^*（Lab）Chromaticity coordinates a in colour system^*Value and b^*Value meets following formula（1F）And formula（2F）Relation polarisation Film.And, these chromaticity coordinates a^*Value and b^*Value is obtained for example, by the assay method for illustrating in the embodiment of the present application.

- 3≤colourity a^*≤3（1F）

- 3≤colourity b^*≤3（2F）

Can also respectively by chromaticity coordinates a described herein^*Value and b^*Value is referred to as " colourity a^*" and " colourity b^*”.This^*And b^* All close 0（zero）, then more can determine whether to show the light polarizing film of neutral form and aspect.In possessing the display device of such light polarizing film, The good white displays that can not coloured.

Additionally, in the form and aspect of light polarizing film, extinction axle is orthogonal to intersect to be overlapped into 2 light polarizing films, as described above Obtain form and aspect now, calculate " orthogonal（Intersect vertically）a^*" and " orthogonal b^*" when, further preferably such orthogonal a^*And it is straight Hand over b^*Following formula is met respectively（1F’）And formula（2F’）Relation.In the display device for possessing light polarizing film, these orthogonals a^*And it is straight Hand over b^*It is to show that whether the form and aspect of black display are neutral index.This orthogonal a^*And orthogonal b^*All close 0（zero）, then The good black display that more can not coloured.

- 3≤orthogonal a^*≤3（1F’）

- 3≤orthogonal b^*≤3（2F’）

3. the continuous manufacture method of this light polarizing film

The summary of the manufacture method of this light polarizing film is this concludes the description of, but when commercially manufacturing this light polarizing film, pursuit can be even The method for manufacturing this light polarizing film continuously.Such continuous manufacture method is the method by volume to volume form, according to circumstances, is claimed Be " this manufacture method ".And, in this manufacture method, it is illustrated centered on the situation with base material as transparent base.Base When material is transparent base, final obtained article becomes the polarizer with transparent base He this light polarizing film（Hereinafter, according to circumstances Referred to as " this polarizer "）.

This manufacture method for example, has

The operation of 1st roller of the preparation by transparent base in the 1st core,

The operation of continuously sending the transparent base from the 1st roller,

Be continuously formed on the transparent base alignment films operation,

Continuously be coated with the oriented layer light polarizing film formation composition operation,

The light polarizing film formation composition that coating is made under conditions of by not being polymerized in polymerizable liquid crystal compound is dried, Be continuously formed in the alignment films be dried overlay film operation,

The polymerizable liquid crystal compound included in overlay film that is dried is set to become Nematic liquid crystalline phase, be preferably smectic type liquid After crystalline phase, in the state of the smectic crystal phase is kept, it is polymerized by making the polymerizable liquid crystal compound, is continuously made Light polarizing film, as the polarizer operation and

Continuously in the 2nd core, the operation of the 2nd roller will be obtained by the obtained polarizer.Herein with reference to Fig. 1, especially It is to situation of the optical alignment film as alignment films is illustrated into this manufacture method.

1st roller 210 of the transparent base in the 1st core 210A for example can easily be obtained from market.As can With the transparent base obtained from market with the form of such roller, can include among exemplified transparent base, It is made up of cellulose esters, annular ethylene series resin, polyethylene terephthalate, Merlon or polymethacrylates Film etc..Additionally, when this light polarizing film is used as into circularly polarizing plate, the transparent base that phase difference is imparted in advance can also be from market Easily obtain, the phase retardation film being such as made up of cellulose esters or annular ethylene series resin can be enumerated.

Then, from the 1st roller 210 by transparent base debatching.Method by transparent base debatching is by the described 1st Appropriate whirligig is set in core 210A of roller 210, the rotation of the 1st roller 210 is carried out by the whirligig by nationality 's.In addition it is also possible to be to set up appropriate help roll 300 in the side that transparent base is carried from the 1st roller 210, by described The whirligig of help roll 300 is by the form of transparent base debatching.Further, can also be by the 1st core 210A and auxiliary Help in roller 300 and be set along whirligig, while transparent base is given with the tension force of appropriateness, while by the shape of transparent base debatching Formula.

When by apparatus for coating 211A, nationality is by the apparatus for coating 211A for transparent base from the 1st roller 210 debatching Light redirecting layer formation composition is coated with its surface.In order to continuously be coated with light redirecting layer formation composition like this, As described above, by the apparatus for coating 211A, implementing the print processes such as gravure coating process, die type rubbing method, flexographic printing process.

Drying oven 212A is carried to through the transparent base of apparatus for coating 211A, thus drying oven 212A is heated nationality, The 1st is continuously formed on transparent base and is dried overlay film.As drying oven 212A, it is possible to use such as hot air type drying oven etc..It is dry The design temperature of dry stove 212A can be wrapped according in the light redirecting layer formation composition being coated with by apparatus for coating 211A Species for the solvent for containing etc. is determining.Furthermore, it is possible to be that drying oven 212A is divided into multiple regions, multiple regions of division can be with It is the respectively different form of design temperature, or by multiple drying oven arranged in series, the design temperature of each drying oven is distinguished The drying oven of different forms.

Nationality by from heating furnace 212A by and be continuously formed the 1st and be dried overlay film, then, by polarised light UV irradiation units 213A is dried irradiation polarised light UV on the surface of the surface of overlay film side or transparent base side the 1st, and the described 1st is dried overlay film forms （Light）Alignment films.Now, can also make the differently- oriented directivity D2 institute of the carrying direction D1 of transparent base and the optical alignment film for being formed into Angular cross.Fig. 2 is to represent differently- oriented directivity D2 of optical alignment film and removing for transparent base formed after polarised light UV irradiations The schematic diagram of the relation of fortune direction D1.That is, Fig. 2 is represented：Carrying direction D1 and the orientation side of optical alignment film from transparent base To D2 observations when the surface of the 1st laminate after polarised light UV irradiation unit 213A, their angulations are shown as big About 45 °.

So it has been continuously formed the transparent base of optical alignment film（1st laminate）, then, nationality is by from apparatus for coating 211B Pass through, after being coated with light polarizing film formation composition on optical alignment film, pass through from drying oven 212B.Nationality from drying oven 212B by leading to Cross, the polymerizable liquid crystal compound included in light polarizing film formation composition forms Nematic liquid crystalline phase, preferably smectic type liquid Crystalline phase, forms the 2nd and is dried overlay film.

From the transparent base that the drying oven 212B is passed through, the solvent contained in light polarizing film formation composition is fully removed Go, be Nematic liquid crystalline phase, the preferably liquid of smectic crystal phase keeping the 2nd to be dried the polymerizable liquid crystal compound in overlay film In the state of crystalline state, light irradiation device 213B is carried to.It is described poly- by the light irradiation carried out with light irradiation device 213B Conjunction property liquid-crystal compounds carries out photo polymerization in the state of the mesomorphic state is kept, and this is continuously formed in alignment films partially Light film, is obtained this polarizer.

This light polarizing film being so continuously formed can be rolled up with the form comprising transparent base and the laminate of alignment films It is wound in the 2nd core 220A, the form of the 2nd roller 220 is obtained.When this light polarizing film winding for being formed is obtained into 2 roller, it is possible to use Appropriate pad together winds.

Thus, by making transparent base with 1 roller/apparatus for coating 211A/ drying oven 212A/ polarised light UV irradiation units The order of 213A/ apparatus for coating 211B/ drying oven 212B/ light irradiation device 213B passes through, optical alignment film over the transparent substrate On be continuously formed this light polarizing film, manufacture this polarizer.

Additionally, in this manufacture method shown in Fig. 1, although show the continuous system from transparent base to this light polarizing film Method is made, but, for example, it is also possible to be by making transparent base with 1 roller/apparatus for coating 211A/ drying oven 212A/ polarised lights The order of UV irradiation unit 213A passes through, by the 1st laminate being continuously formed in core, with the form of roller manufacture the 1 laminate, from the roller by the 1st laminate debatching, makes the 1st laminate of debatching with apparatus for coating 211B/ drying oven 212B/ light The order of irradiation unit 213B passes through, and manufactures this polarizer.

By this polarizer obtained in this manufacture method, it is the article for being shaped as film-form and long ruler-like.This is partially In the case of light film is used for liquid crystal indicator described later etc., institute can be cut into according to size of the liquid crystal indicator etc. Need size and then use.

More than, although this is risen centered on the situation of the form of the laminate of transparent base/optical alignment film/this light polarizing film The composition and manufacture method of partially device is illustrated, but it is also possible to by from this polarizer peel off optical alignment film and transparent base come This light polarizing film of prepared individual layer.Further, it is also possible to be arranged in this polarizer with transparent base/optical alignment film/this light polarizing film Layer in addition or the form of film lamination.Used as these layers and film, as already mentioned, this light polarizing film can be further equipped with phase Potential difference film, can be further equipped with anti-reflection layer or brightness enhancement film.

Additionally, by making transparent base sheet as phase retardation film, may also be arranged to phase retardation film/optical alignment film/this polarisation The circularly polarizing plate or elliptical polarization plate of the form of film.For example, during using 1/4 wavelength plate of uniaxial tension as phase retardation film, It is slightly at 45 ° as the carrying direction relative to transparent base by the direction of illumination for setting polarised light UV, can be made by volume to volume Circularly polarizing plate.It is preferred that 1/4 wavelength plate used in so manufacture circularly polarizing plate is with phase difference value in the face to visible ray 1/4 wavelength plate of the characteristic diminished as wavelength shortens.

Additionally, making the angle initialization by its slow axis and the extinction axle of light polarizing film as phase retardation film using 1/2 wavelength plate Linear polarization plate roller as staggering, by forming 1/ further with the opposition side in the face for defining the light polarizing film 4 wavelength plates, may also be fabricated which broadband circularly polarizing plate.

4. the purposes of this light polarizing film

This light polarizing film can be used for various display devices.Display device refers to the device with display element, including as send out The light-emitting component or light-emitting device of light source.As display device, can enumerate as：Liquid crystal indicator, organic electroluminescent（EL） Display device, inorganic EL（EL）Display device, electron emission display（Such as field emission display device（FED）, table Surface conduction electron emission display（SED））, Electronic Paper（Display device, the plasma of e-inks or electrophoresis element are used Display device, projection type image display apparatus（Such as grating light valve（GLV）Display device, with digital micro-mirror part（DMD）It is aobvious Showing device）And piezoelectric ceramics display device etc..Liquid crystal indicator includes through type liquid crystal indicator, semi-transmission type liquid crystal Any one of showing device, reflection-type liquid-crystal display device, direct view liquid crystal display device and projection-type liquid crystal display device etc.. These display devices can be the display device for showing 2 dimension images, or the 3 d display device for showing 3 d image.

This light polarizing film can particularly effectively be used for organic electroluminescent（EL）Display device or inorganic EL（EL）It is aobvious The display device of showing device.

Fig. 3 is represented using the liquid crystal indicator of this light polarizing film（Hereinafter, according to circumstances it is referred to as " this liquid crystal display dress Put ".）The schematic diagram of 10 section constitution.Liquid crystal layer 17 is sandwiched in 2 substrate 14a and substrate 14b.

Fig. 6 and Figure 10 are to represent the EL display devices for having used this light polarizing film（Hereinafter, be according to circumstances referred to as " this EL show Showing device ".）Section constitution schematic diagram.

Figure 11 is the schematic diagram of the composition for representing the projection-type liquid crystal display device for having used this light polarizing film.

First, this liquid crystal indicator 10 to showing in figure 3 is illustrated.

Colour filter 15 is configured in the side of liquid crystal layer 17 of substrate 14a.Colour filter 15 clips liquid crystal layer 17, is configured in and picture The opposite position of plain electrode 22, stain matrix 20 is configured in the opposite position in border between pixel electrode.Transparency electrode 16 It is configured to cover colour filter 15 and stain matrix 20 the side of liquid crystal layer 17 is standby.And, can between colour filter 15 and transparency electrode 16 With with coating（It is not shown）.

Thin film transistor (TFT) 21 and pixel electrode 22 are regularly configured on the side of liquid crystal layer 17 of substrate 14b.Pixel electricity Pole 22 clips liquid crystal layer 17 and is configured in the position opposite with colour filter 15.Configure between thin film transistor (TFT) 21 and pixel electrode 22 With connecting hole（It is not shown）Interlayer dielectric 18.

As substrate 14a and substrate 14b, using glass substrate and plastic base.Such glass substrate and plastic base Can adopt and the base material as the exemplified base material phase same material for the transparent base in the manufacture of this light polarizing film.This Outward, the transparency carrier 1 of this light polarizing film can have substrate 14a and substrate 14b concurrently.The colour filter 15 and thin that manufacture is formed on substrate During film transistor 21, when needing high-temperature heating operation, preferred glass substrate or quartz base plate.

Thin film transistor (TFT) can adopt most suitable thin film transistor (TFT) according to the material of substrate 14b.As thin film transistor (TFT) 21, the high temperature polysilicon silicon transistor for being formed on a quartz substrate, the low-temperature polysilicon silicon wafer for being formed on the glass substrate can be included Body pipe, the unformed silicon transistor formed on glass substrate or plastic base.In order that this liquid crystal indicator is more small-sized Change, driving IC can be formed on substrate 14b.

Liquid crystal layer 17 is configured between transparency electrode 16 and pixel electrode 22.In order to keep between substrate 14a and substrate 14b Distance it is certain, pad 23 is configured in liquid crystal layer 17.And, the pad of column is illustrated in Fig. 3, but the pad is not limited In column, as long as the distance between substrate 14a and substrate 14b can be made to keep certain, its shape is just arbitrarily.

Each component with substrate 14a, colour filter 15 and stain matrix 20, transparency electrode 16, liquid crystal layer 17, pixel electrode 22, The sequential lamination of interlayer dielectric 18 and thin film transistor (TFT) 21 and substrate 14b.

Among clipping the substrate 14a and substrate 14b of such liquid crystal layer 17, the polarizer is set in the outside of substrate 14b 12a and 12b, among them, at least one has used this polarizer.

Further, preferred phase separation layer（For example, 1/4 wavelength plate or optical compensating film）13a and 13b laminations.It is polarized Among device 12a and 12b, by configuring this light polarizing film on polarizer 12b, incident light can will be made to be changed into rectilinearly polarized light Function is given to this liquid crystal indicator 10.And, according to the liquid crystal included in the structure and liquid crystal layer 17 of liquid crystal indicator The species of compound, it is also possible to do not configure phase retardation film 13a and 13b, using transparency carrier be phase retardation film, comprising this light polarizing film Circularly polarizing plate when, because the phase retardation film being made into phase separation layer, thus can also omit Fig. 3 phase separation layer 13a and/or 13b.The light emitting side of this polarizer（Outside）On light polarizing film can be further set.

Additionally, in the outside of this polarizer（When further light polarizing film being set in this light polarizing film, on the outside of it）Can match somebody with somebody Putting prevents the antireflection film of external light reflection.

As described above, this polarizer can be used in the polarizer 12a or 12b of this liquid crystal indicator 10 of Fig. 3.It is logical Cross and this polarizer is arranged on the polarizer 12a and/or 12b, there is the effect of the slimming of achievable this liquid crystal indicator 10 Really.

When this polarizer is used for into polarizer 12a or 12b, its lamination order is not particularly limited.With reference to the dotted line bag of Fig. 3 The A for enclosing and the partial enlarged drawing of B are explained.

Fig. 4 is the amplification schematic cross-section of the part A of Fig. 3.When this polarizer 100 is used as into polarizer 12a, Fig. 4's （A1）Show the arranging feelings being arranged in order with this light polarizing film 3, optical alignment film 2 and transparent base 1 from phase separation layer 13a sides Condition.Additionally, Fig. 4（A2）Show from phase separation layer 13a sides with the order of transparent base 1, optical alignment film 2 and this light polarizing film 3 The arranging situation of configuration.

Fig. 5 is the enlarged diagram of the part B of Fig. 3.When this polarizer 100 is used as into polarizer 12b, Fig. 5's（B1）In, From phase retardation film 13b sides being arranged in order with transparent base 1, optical alignment film 2 and this light polarizing film 3.This polarizer 100 is used as During polarizer 12b, Fig. 5's（B2）In, from phase retardation film 13b sides with the order of this light polarizing film 3, optical alignment film 2 and transparent base 1 Configure.

The backlight module 19 as light emitting source is configured in the outside of polarizer 12b.Backlight module 19 includes light source, leaded light Body, reflecting plate, diffusion sheet and angle of visual field adjustment sheet.As light source, can include electroluminescent, cold-cathode tube, thermionic-cathode tube, send out Optical diode（LED）, LASER Light Source and mercury lamp etc..Furthermore, it is possible to select this light polarizing film according to the characteristic of such light source Species.

When this liquid crystal indicator 10 is transmission type liquid crystal display device, the white that the light source from backlight module 19 sends Light injects light conductor, changes light path by reflecting plate and spreads in diffusion sheet.Diffusion light is adjusted to tool by angle of visual field adjustment sheet Inject polarizer 12b from backlight module 19 after desired directionality.

Among the incident light of non-polarized light, only polarizer 12b of the rectilinearly polarized light of a direction through liquid crystal panel.This Rectilinearly polarized light is transformed to circularly polarized light or elliptically polarized light by phase separation layer 13b, sequentially through substrate 14b, pixel electrode 22 grades reach liquid crystal layer 17.

According to potential difference is whether there is between pixel electrode 22 herein and the transparency electrode 16 opposite with it, include in liquid crystal layer 17 Liquid crystal molecule state of orientation change, can control from this liquid crystal indicator 10 transmitting light brightness.Liquid crystal layer 17 is in During the state of orientation for then passing through polarised light conversion, the polarised light passes through liquid crystal layer 17, transparency electrode 16, a certain specific wavelength The light transmission colour filter 15 of scope reaches polarizer 12a, and liquid crystal indicator most shows brightly the color determined by colour filter.

In turn, liquid crystal layer 17 is in when making state of orientation that polarised light is directed through, through liquid crystal layer 17, transparency electrode 16 and colour filter 15 light be polarized device 12a absorption.Thus, this pixel shows black.In the orientation shape of the centre of this 2 states In state, also become to be shown between both centres, therefore this pixel from the brightness of the light of the transmitting of this liquid crystal indicator 10 Neutral colour.

When this liquid crystal indicator 10 is semitransparent liquid crystal display, this light polarizing film of this polarizer is preferably used in Side further makes the article of 1/4 wavelength plate lamination（Circularly polarizing plate）.Now, pixel electrode 22 has and is formed by transparent material Through portion and the reflecting part that formed by the material of reflected light, in through portion, in the same manner as the transmission type liquid crystal display device Display image.On the other hand, in reflecting part, outer light injects liquid crystal indicator, by be further equipped with this light polarizing film 1/4 The effect of wavelength plate, through the circularly polarized light of this light polarizing film liquid crystal layer 17 is passed through, and is reflected by pixel electrode 22 and is used to show Show.

Then, this EL display devices 30 using this light polarizing film are illustrated with reference to Fig. 6.In this EL display devices, During using this light polarizing film, preferably this light polarizing film is made into circularly polarizing plate（Hereinafter, according to circumstances it is referred to as " this circularly polarizing plate ".）So After use.There are 2 embodiments in this circularly polarizing plate.Therefore, before composition for illustrating this EL display devices 30 etc., to this 2 embodiments of circularly polarizing plate are illustrated with reference to Fig. 7.

Fig. 7's（A）It is the schematic diagram of the 1st embodiment for representing this circularly polarizing plate 110.This 1st embodiment is at this Phase separation layer is further set in this light polarizing film 3 in the polarizer 100（Phase retardation film）4 this circularly polarizing plate 110.Fig. 7 's（B）To represent the schematic diagram of the 2nd embodiment of this circularly polarizing plate 110.This 2nd embodiment is by using imparting in advance The transparent base 1 of phase difference（Phase retardation film 4）As the transparent base 1 used when manufacturing this polarizer, transparent base 1 is made Itself become this circularly polarizing plate 110 for the article for having the function as phase separation layer 4 concurrently.

As this circularly polarizing plate including this light polarizing film, if because of the 2nd embodiment of above-mentioned circularly polarizing plate, then constituting It is easy so preferably, now, preferably by 1/4 wavelength plate as transparent base, further, using 1/4 wavelength plate as transparent base Material, the preferred necessary condition for meeting following (A1) and (A2).

(A1) the extinction axle of the light polarizing film is about 45 ° with the slow axis angulation of 1/4 wavelength plate；

(A2) it is 100～150nm's by the value of the front retardation of 1/4 wavelength plate of the light measurement of wavelength 550nm Scope

Herein, the manufacture method with regard to this circularly polarizing plate 110 illustrated in advance.With the circularly polarizing plate having been described above 110 the 2nd embodiment is the same, in this manufacture method of manufacture this polarizer 100, by using imparting phase difference in advance The transparent base 1 of property is used as transparent base 1, i.e. can be manufactured using phase retardation film.1st embodiment party of this circularly polarizing plate 110 Formula can form phase separation layer 4 by fitting phase retardation film in this light polarizing film 3 manufactured by this manufacture method B.And, Can be from the 2nd roller 220 is by this when manufacturing this polarizer 100 in the way of the 2nd roller 220 according to this manufacture method B Partially the debatching of device 100, is cut into given size, the mode of phase retardation film of then fitting on this polarizer 100 of cutting, by standard Standby the 3rd roller by phase retardation film in core, can also be continuously manufactured by being shaped as film-form and this circle of long ruler-like is inclined Vibration plate 110.

Method with regard to being continuously manufactured by the 1st embodiment of this circularly polarizing plate 110, illustrates with reference to Fig. 8.It is such Manufacture method by,

From the 2nd roller 220 continuously by the debatching of this polarizer 100, while the 3rd roller that wrapped around from phase retardation film 230 continuously by the operation of the phase retardation film debatching,

By the light polarizing film arranged on this polarizer 100 from the 2nd roller 220 debatching and from the 3rd roller debatching Operation that the phase retardation film continuously fits to form this circularly polarizing plate 110,

By this circularly polarizing plate 110 for being formed in the 4th core 240A, the operation that the 4th roller 240 is obtained is constituted.

More than, the manufacture method of the 1st embodiment of this circularly polarizing plate 110 is illustrated, but in the laminating polarizer When this light polarizing film in 100 3 and phase retardation film, it is possible to use appropriate adhesive, via the bonding formed by described adhesive Layer, this light polarizing film of fitting 3 and phase retardation film.

Then, this EL display devices to possessing this circularly polarizing plate 110 are illustrated referring again to Fig. 6.

This EL display devices 30 are on the substrate 33 for defining pixel electrode 35, by the organic function layer as light emitting source 36 and the display device of the lamination of cathode electrode 37.With the opposition side of organic function layer 36 on, be configured with circularly polarizing plate 31, Sandwich substrate 33, using this circularly polarizing plate 110 as such circularly polarizing plate 31.By applying just on pixel electrode 35 Voltage, apply on cathode electrode 37 negative voltage, apply between pixel electrode 35 and cathode electrode 37 DC current, You Jigong Ergosphere 36 lights.It is made up of electron transfer layer, luminescent layer and hole transmission layer etc. as the organic function layer 36 of light emitting source.From having The light of the transmitting of machine functional layer 36 passes through pixel electrode 35, interlayer dielectric 34, substrate 33, circularly polarizing plate 31（This circularly polarizing plate 110）.Although illustrating to the organic EL display with organic function layer 36, the inorganic EL with inorganic functional layer Display device is equally applicable.

In order to manufacture this EL display devices 30, first, thin film transistor (TFT) 40 is formed with desired shape on substrate 33. Then the film forming of interlayer dielectric 34, then pixel electrode 35 pattern is formed by sputtering film-forming.Afterwards, by organic function layer 36 laminations.

Then, on the face contrary with the face of the thin film transistor (TFT) 40 for arranging substrate 33, circularly polarizing plate 31 is set（This circle Polarization plates 110）.

When this circularly polarizing plate 110 is used as into circularly polarizing plate 31, the local of the C that its lamination order is surrounded with reference to the dotted line of Fig. 6 Enlarged drawing is illustrated.When this circularly polarizing plate 110 is used as into circularly polarizing plate 31, the phase separation layer 4 in described circularly polarizing plate 110 It is configured in the side of substrate 33.Fig. 9's（C1）It is the amplification that the 1st embodiment of this circularly polarizing plate 110 is used as circularly polarizing plate 31 Figure, Fig. 9's（C2）It 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 of this EL display devices 30（Circularly polarizing plate 110）Component in addition is illustrated.

As substrate 33, sapphire glass substrate, quartz glass substrate, soda-lime glass substrate and aluminum oxide etc. can be included Ceramic substrate；The metal substrates such as copper；Plastic base etc..Although it is not shown, but heat conductivity film can be formed on substrate 33.Make For heat conductivity film, diamond thin can be included（DLC etc.）Deng.When pixel electrode 35 is made into reflection-type, to substrate 33 Rightabout launching light.Therefore, transparent material not only can be used, it is also possible to use the non-permeable material such as stainless steel.Substrate can be with Independently form, it is also possible to multiple substrates is fitted by bonding agent and is formed as laminated substrate.Additionally, these substrates are not limited to plate Shape, can also be film.

As thin film transistor (TFT) 40, can be using such as polycrystal silicon transistor.Thin film transistor (TFT) 40 is arranged at pixel electricity The end of pole 35, its size is 10 ~ 30 μm of degree.And, the size of pixel electrode 35 is the μ m 300 of 20 μ m 20 μm ~ 300 μm degree.

The wire electrode of thin film transistor (TFT) 40 is set on substrate 33.Wire electrode resistance is low, there is electric with pixel electrode 35 The function of connecting and suppress relatively low by resistance value, generally this wire electrode are used containing Al, Al and transition metal（But remove Ti）, Ti or titanium nitride（TiN）Any one kind or two or more wire electrode.

Interlayer dielectric 34 is provided between thin film transistor (TFT) 40 and pixel electrode 35.As long as interlayer dielectric 34 is to make SiO₂Deng the inorganic based material such as silica, silicon nitride by the article of sputtering or vacuum evaporation and film forming, by SOG（Spin coating glass Glass, spin-on-glass）The resin based materials such as the silicon oxide layer of formation, photoresist, polyimides and acrylic resin The interlayer dielectric with insulating properties of film etc., it is possible to be it is above-mentioned any one.

Rib 41 is formed on interlayer dielectric 34.Rib 41 is configured in the periphery of pixel electrode 35（Neighbor it Between）.As the material of rib 41, acrylic resin and polyimide resin etc. can be included.It is preferred that the thickness of rib 41 be 1.0 μm with Above, less than 3.5 μm, more preferably more than 1.5 μm, less than 2.5 μm.

Then, to by the pixel electrode 35 as transparency electrode, the organic function layer 36 as light emitting source and cathode electrode 37 EL elements for constituting are illustrated.Organic function layer 36 has at least 1 layer of hole transmission layer and luminescent layer respectively, for example, There is successively electron injection transport layer, luminescent layer, hole transmission layer and hole injection layer.

As pixel electrode 35, can enumerate as：ITO（Tin indium oxide）、IZO（Indium zinc oxide）、IGZO、ZnO、SnO₂And In₂O₃Deng, but particularly preferably ITO and IZO.As long as the thickness of pixel electrode 35 is with can fully carry out the certain of hole injection Thickness above, the preferably degree of 10 ~ 500nm.

Pixel electrode 35 can pass through vapour deposition method（Preferably sputtering method）Formed.As sputter gas, it is not particularly limited, Can be using inert gas or their mixed gas such as Ar, He, Ne, Kr and Xe.

As the composition material of cathode electrode 37, can be using such as：K、Li、Na、Mg、La、Ce、Ca、Sr、Ba、Al、Ag、In、 The metallic elements such as Sn, Zn and Zr, but in order that the job stability raising of electrode, preferably uses from by exemplified metal unit The 2 kinds of compositions selected in element or the alloy system of 3 kinds of compositions.As alloy system, preferably such as AgMg（Ag：1~20at%）、Al·Li （Li：0.3~14at%）、In·Mg（Mg：50~80at%）And AlCa（Ca：5~20at%）Deng.

Cathode electrode 37 is formed by vapour deposition method and sputtering method etc..The thickness of cathode electrode 37 is more than 0.1nm, preferably 1~500nm。

Hole injection layer has to be made to become easy function from the injection of pixel electrode 35 hole, and hole transmission layer has transmission The function in hole and the function of obstruction electronics, also referred to as electric charge injection layer and charge transport layer.

The thickness of the thickness, the gross thickness of hole injection layer and hole transmission layer and electron injection transport layer of luminescent layer does not have Especially limit, although also according to the different and different of forming method, but the preferably degree of 5 ~ 100nm.Hole injection layer and sky Various organic compounds can be used in the transport layer of cave.In the shape of hole injection/transport layer, luminescent layer and electron injection transport layer Cheng Zhong, can use from the aspect of homogeneous film vacuum vapour deposition from being formed.

Can use using the luminous of singlet exciton as the organic function layer 36 of light emitting source（Fluorescence）Organic functions Layer, lighting using triplet excitons（Phosphorescence）Organic function layer, comprising using the luminous of singlet exciton（Fluorescence）Have Machine functional layer and lighting using triplet excitons（Phosphorescence）Organic function layer organic function layer, by having that organic matter is formed The organic function layer of machine functional layer, the functional layer formed comprising the organic function layer formed by organic matter and by inorganic matter, high score Sub- material, low molecule material, the organic function layer comprising macromolecular material and low molecule material etc..It is however not limited to this, at this The organic function layer 36 as various materials known to EL element can have been used in EL display devices 30.

Drier 38 is configured in the space of cathode electrode 37 and closure 39.This is because organic function layer 36 is to humidity It is sensitive.Moisture is absorbed by drier 38, the deterioration of organic function layer 36 is prevented.

Figure 10 is the skeleton diagram of the section composition of the other forms for representing this EL display devices 30.This this EL display device 30 With the sealing structure for having used diaphragm seal film 42, or even launching light can be all obtained from the opposing face of array base palte.

As diaphragm seal film 42, it is preferably used on the film of electrochemical capacitor and has been deposited with DLC（Diamond-like-carbon）DLC Film.DLC film has the characteristic of penetrability extreme difference, and moisture-proof characteristic is high.Additionally, DLC film etc. can be straight on the surface of cathode electrode 37 Connect evaporation to be formed.Furthermore, it is possible to be multilayer by resin film and metallic film lamination, diaphragm seal film 42 is formed.

As above, there is provided be related to the new light polarizing film of the present invention（This light polarizing film）And possess the new display device of this light polarizing film （This liquid crystal indicator and this EL display devices）.

Finally, the projection-type liquid crystal display device using this light polarizing film is illustrated.

Figure 11 is the skeleton diagram for showing the projection-type liquid crystal display device for having used this light polarizing film.

As the polarizer 142 and/or the polarizer 143 of the projection-type liquid crystal display device, using this light polarizing film.

From the light source as light emitting source（For example, high-pressure sodium lamp）The light shafts nationality of 111 transmittings is by first by the 1st lens array Row 112, the 2nd lens arra 113, polarization light conversion element 114, compound lens 115, carry out the brightness on reflection light area of beam Homogenization and polarization light.

Specifically, the light shafts nationality from the transmitting of light source 111 is formed as the 1st rectangular lens by micro lens 112a Array 112 is divided into a plurality of small light shafts.Possess the 2nd lens arra 113 and compound lens 115 so that divided light Wire harness irradiates respectively all as 3 liquid crystal panels 140R, 140G, 140B of lighting object, therefore, each liquid crystal panel light incident side It is substantially homogeneous that surface integrally becomes illumination.

Polarization light conversion element 114 is made up of polarization beam splitter array, is configured in the 2nd lens arra 113 and is combined Between lens 115.Thus the random polarization launched from light source is converted in advance the polarised light with specific polarization direction, is subtracted Few light loss in the aftermentioned light incident side polarizer, plays a part of to make the brightness of picture to improve.

The light of brightness homogenization executed as described above and polarization light via the nationality of speculum 122 by be separated into RGB3 primary colors point Look mirror 121,123,132 is separated into successively red channel, green channel, blue channel, inject respectively liquid crystal panel 140R, 140G、140B。

In liquid crystal panel 140R, 140G, 140B, the polarizer 142 is configured in its light incident side, configure in emitting side and be polarized Device 143.This light polarizing film can be used in this polarizer 142, the polarizer 143.

The polarizer 142 and the polarizer 143 that configure in each light paths of RGB are configured to into the vertical phase of respective extinction axle Hand over.In each light path configure each liquid crystal panel 140R, 140G, 140B have according to picture signal by each pixel controlled it is inclined The light state that shakes is converted into the function of light quantity.

By select be suitable to corresponding passage dichroism pigment species, even if this polarizer 100 blue channel, The light polarizing film of excellent in te pins of durability is also served as in the light path such as green channel and red channel and useful.

According to the view data of liquid crystal panel 140R, 140G, 140B, by making incidence with different light transmittances to each pixel Light transmission and made by optical imagery, synthesized by cross colour splitting prism 150, put on projection screen 180 by projection lens 170 Big projection.

As Electronic Paper, can include by the molecule as optical anisotropy and dye molecule orientation to be shown The Electronic Paper shown, the Electronic Paper shown by electrophoresis, Particles Moving, particle rotation, particle as phase change, pass through Move come the Electronic Paper for being shown, the Electronic Paper shown by the color development/phase change of molecule, pass through in one end of film The electricity that the light absorbs of molecule are shown come the Electronic Paper for being shown, the self-luminous sent by electronics and hole bonding Sub- paper etc..More specifically, microcapsule-type electrophoresis, horizontal motion electrophoresis, vertically-moving electrophoresis, spherical torsion can be included Ball, magnetic reverse ball, cylinder and reverse ball mode, charged toner, electronics powder fluid, magnetophoretic, magnetic strength heat, electricity moistening, light scattering (transparent/white opacity change), cholesteryl liquid crystal/optical conductive layer, cholesteryl liquid crystal, bistability nematic crystal, lures by force electricity Property liquid crystal, 2 chromotropism pigment liquid crystal dispersion methods, movable film, by the color development colour killing of leuco dye, photochromic, electroluminescent Discoloration, electro-deposition and elastic organic EL etc..Electronic Paper is applied not only to the text and image of individual, it may also be used for advertisement shows (mark Board) etc..By this light polarizing film, the lower thickness of Electronic Paper can be made.

As 3 d display device, it is proposed that make mutually different phase retardation film as such as small polarization explicit representation The method (Japanese Patent Laid-Open 2002-185983 publication) of arrangement, if but using this light polarizing film, because by printing, ink-jet Printing, photoetching etc. easily form pattern, and the manufacturing process that can make display device shortens, and becomes not needing phase retardation film.

[embodiment]

Hereinafter, the present invention is further described according to embodiment.As long as nothing separately illustrates that " % " and " part " in example is Quality % and mass parts.

In the present embodiment, using following dichroism pigments (1).

The preparation of compound (1-1) (compounds represented by following (1-1))

Compound (1-1) is synthesized by following proposal.

Compound [compound (1B)] 5.00g represented by hybrid (1B), 4-HBA ethyl ester 4.63g, diformazan Aminopyridine (DMAP) 0.23g and chloroform 25g, under lucifuge nitrogen atmosphere, stir 10 minutes at 5 DEG C.Obtained mixed Close time-consuming 5 minutes in liquid and instill Diisopropylcarbodiimide (IPC) 2.58g, further stirring 4 hours.In the reaction for obtaining Addition methyl alcohol 75g, crystallization in liquid, filtering to take to crystallize.After further using the methyl alcohol wash crystallization of equivalent, by vacuum drying, Obtain compound (1-1) 6.78g.On the basis of compound (1B), yield is 87%.

Compound (1-1)¹H-NMR(CDCl₃)：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) (compounds represented by following (1-7))

Compound (1-7) is synthesized by following proposal.

Mixing cpd (1B) 5.00g, 4- butoxy phenol 4.63g, DMAP0.23g and chloroform 25g, in lucifuge nitrogen Under atmosphere, stir 10 minutes under 5 °C.Instill IPC2.58g within time-consuming 5 minutes in obtained mixed liquor, further stirring 4 is little When.Addition methyl alcohol 75g, crystallization in the reactant liquor for obtaining, filtering to take to crystallize.Crystallization is set to be dissolved in 50g dimethyl acetamides In, insoluble matter is filtered by diatomite.Reclaim filtrate water crystallization.Obtained crystallization is further dissolved in into 50g tetrahydrofurans In be filtered to remove after insoluble matter, add heptane, crystallization, by vacuum drying, obtain compound (1-7) 4.66g.With chemical combination On the basis of thing (1B), yield is 60%.

Compound（1-7）'s¹H-NMR（CDCl₃）：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, using following polymerizable liquid crystal compounds.

Compound（4-6）（Following formula（4-6）Represented compound）

Compound（4-6）By Lub et al.Recl.Trav.Chim.Pays-Bas, 115,321-328（1996）Note The method synthesis of load.

[measure of phase transition temperature]

By obtaining by compound（4-6）The phase transition temperature of the film of composition and confirm compound（4-6）Phase in version Temperature.Its operation is as follows.

Formed by compound on the glass substrate for define alignment films（4-6）The film of composition, is heated by one side, on one side Use polarization microscope（BX-51, Olympus society system）The texture for carrying out is observed and confirms phase transition temperature.Will be by compound （4-6）After the film of composition is warming up to 120 DEG C, cooling when, 112 DEG C at phase in version be nematic phase, the phase in version at 110 DEG C For smectic C, phase in version is smectic B at 94 DEG C.

Compound（4-8）（Following formula（4-8）Represented compound）

Compound（4-8）With reference to above-claimed cpd（4-6）Synthetic method synthesizing.

[measure of phase transition temperature]

With compound（4-6）Phase transition temperature determine similarly confirm compound（4-8）Phase transition temperature.By chemical combination Thing（4-8）After being warming up to 140 DEG C, in cooling, phase in version is nematic phase at 131 DEG C, and phase in version is smectic A at 80 DEG C Phase, phase in version is smectic B at 68 DEG C.

Compound（4-22）（Following formula（4-22）Represented compound）

Compound（4-22）With reference to the synthetic method synthesis of No. 4719156 records of Japanese Patent No..

[measure of phase transition temperature]

With compound（4-6）Phase transition temperature determine similarly confirm compound（4-22）Phase transition temperature.To change Compound（4-22）After being warming up to 140 DEG C, in cooling, phase in version is nematic phase at 106 DEG C, and phase in version is at 103 DEG C Smectic C, phase in version is smectic B at 86 DEG C.

Compound（4-25）（Following formula（4-25）Represented compound）

Compound（4-25）With reference to the synthetic method synthesis of No. 4719156 records of Japanese Patent No..

[measure of phase transition temperature]

With compound（4-6）Phase transition temperature determine similarly determine compound（4-25）Phase transition temperature.To change Compound（4-25）After being warming up to 140 DEG C, in cooling, phase in version is nematic phase at 119 DEG C, and phase in version is at 100 DEG C Smectic C, phase in version is smectic B at 77 DEG C.

Embodiment 1

[light polarizing film formation composition（A）Preparation]

Mixing following compositions, by stirring 1 hour at 80 DEG C, are obtained light polarizing film formation composition（A）.And, this " the compound of the dichroism pigment that place uses（1-7）" refer to the formula（1-7）Represented compound, as other two to Color pigment and the compound that uses also correspond to the numbering of its formula.Below it is also identical.

2- dimethylamino -2- benzyl -1-（4- morpholino phenyls）- 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 determinations

On the glass substrate, by spin-coating method pva coating（The fully saponified type of polyvinyl alcohol 1000, and the pure medicine work of light Industry Co. Ltd. system）The 2 mass % aqueous solution（Oriented layer formation composition）, after drying, form the film of thickness 100nm.Connect , by implementing friction treatment on the surface of obtained film oriented layer is formed.Using 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）, in the depth of cup Friction treatment is carried out under conditions of degree 0.15mm, revolution 500rpm, 16.7mm/s.Pass through spin coating in such alignment films for making Method is coated with light polarizing film formation composition（A）, heat drying is quickly cooled to room temperature after 1 minute in 120 DEG C of the heating plate, Formed in the oriented layer and be dried overlay film.Then, using UV irradiation units（SPOT CURE SP-7；The prosperous motor strain formula of excellent will Commercial firm's system）, by with light exposure 2000mJ/cm²（365nm benchmark）Irradiation ultraviolet radiation on overlay film is being dried, is keeping described poly- The polymerizable liquid crystal compound polymerization for being dried and being included in overlay film is made in the state of the mesomorphic state of conjunction property liquid-crystal composition, by The overlay film that is dried forms light polarizing film.The thickness of light polarizing film now passes through laser microscope（Olympus Co., Ltd's system OLS3000）Determine, be as a result 1.7 μm.X-ray diffraction device X ' Pert PRO MPD are used to this light polarizing film（Spectris strain formula Commercial firm's system）Similarly carry out X-ray diffraction measure, as a result, obtain full width at half maximum (FWHM) near 2 θ=20.2 °（FWHM）=about 0.17 ° Sharp diffraction maximum（Bragg peak）.Additionally, also obtaining same result from friction vertical direction incidence.Obtain from peak position The order cycle（d）For aboutConfirmation defines the structure of reflection height smectic phase.

2. the making of the optical alignment film on transparent membrane

Using triacetylcellulose film（KC8UX2M, Konica Minolta（Strain）System）As transparent base, by bar type Rubbing method coating makes following formula（3）Represented light orientation polymer is dissolved in 5% solution of toluene, is dried at 120 DEG C It is obtained and is dried overlay film.Here is dried on overlay film irradiates the prepared optical alignment films of polarised light UV.Polarised light UV process uses UV irradiation dresses Put（SPOT CUR SP-7；Ushio Electric Inc's system）, determine under wavelength 365nm, under conditions of intensity 100mJ Carry out.

3. the making of light polarizing film

Pass through bar type rubbing method on the film for having attached optical alignment film prepared above（#5 17mm/s）Coating light polarizing film Formation composition（A）, heat drying is cooled to room temperature after 1 minute in 120 DEG C of drying oven.Then, irradiated using UV Device（SPOT CUR SP-7；Ushio Electric Inc's system）, by shining forming the layer formed with composition by light polarizing film Penetrate light exposure 2000mJ/cm²（365nm benchmark）Ultraviolet, in the mesomorphic state for keeping the polymerizable liquid crystal compound The polymerizable liquid crystal compound polymerization for being dried and being included in overlay film is made under state, light polarizing film is formed by the overlay film that is dried.This When light polarizing film thickness pass through laser microscope（Olympus Co., Ltd OLS3000）Determine, be as a result 1.6 μm.This Article obtained in sample is the polarizer comprising light polarizing film and transparent base.

4. degree of polarization, light transmittance, color molybdenum determination

It is following to determine brightness correction degree of polarization, brightness correction light transmittance, colourity in order to confirm the serviceability of the polarizer a^*Value, colourity b^*Value, orthogonal a^*And orthogonal b^*。

Using in spectrophotometer（Shimadzu Corporation UV-3150）On be provided with the folding with the polarizer Device（Folder）Device, the axial printing opacity of printing opacity in the range of wavelength 380nm ~ 780nm is determined by reference beam method Rate（T¹）And the axial light transmittance of extinction（T²）.The folder is provided with the mesh that light quantity is blocked 50% in reference side.Make Use following formula（Formula 1）And（Formula 2）, singleton transmittance, the degree of polarization of each wavelength are calculated, further according to 2 degree of JIS Z8701 The visual field（Illuminant-C）Brightness correction is carried out, brightness correction singleton transmittance is calculated（Ty）And brightness correction degree of polarization（Py）. Additionally, waiting color function using illuminant-C, L is calculated by the singleton transmittance for similarly determining^*a^*b^*（CIE）Color in colour system Degree a^*And b^*.Further, color function is waited using illuminant-C, L is calculated by the orthogonal light transmittance for similarly determining^*a^*b^*（CIE）Table color Orthogonal a in system^*And orthogonal b^*.Colourity a^*, colourity b^*, orthogonal a^*And orthogonal b^*Value closer to 0, more can determine whether as muted color Phase.These results are shown in table 4.

Singleton transmittance（%）=（T1+T2）/2…（Formula 1）

Degree of polarization（%）=（T1-T2）/（T1+T2）×100…（Formula 2）

Embodiment 2

1. the making of light polarizing film

Metal wire except changing the rod of rod coater（ワ ノ ヤ mono-）Wide and coating speed（#715mm/s）In addition, Light polarizing film is made similarly to Example 1.By laser microscope（Olympus Co., Ltd OLS3000）Determine now The thickness of light polarizing film, is as a result 1.8 μm.

2. degree of polarization, light transmittance, color molybdenum determination

The brightness for determining the light polarizing film for making by method similarly to Example 1 corrects singleton transmittance（Ty）And regard Gamma correction degree of polarization（Py）And colourity a^*, colourity b^*, orthogonal a^*And orthogonal b^*, as a result it is shown in table 4.

[the light polarizing film formation composition of embodiment 3（B）Preparation]

Mixing following compositions, by stirring 1 hour at 80 DEG C, are obtained light polarizing film formation composition（B）.

2- dimethylamino -2- benzyl -1-（4- morpholino phenyls）- 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

Except by light polarizing film formation composition（A）It is changed to light polarizing film formation composition（B）, further bar type is coated with The metal live width of the rod of machine and coating speed are changed into（#5 25mm/s）In addition, light polarizing film is made similarly to Example 1.It is logical Cross laser microscope（Olympus Co., Ltd OLS3000）The thickness of light polarizing film now is determined, is as a result 1.7 μm.

2. degree of polarization, light transmittance, color molybdenum determination

The brightness for determining the light polarizing film for making by method similarly to Example 1 corrects singleton transmittance（Ty）And regard Gamma correction degree of polarization（Py）And colourity a^*, colourity b^*, orthogonal a^*And orthogonal b^*, as a result it is shown in table 4.

Embodiment 4

1. the making of light polarizing film

Metal live width and coating speed except changing the rod of rod coater（#7 20mm/s）In addition, with embodiment 3 Similarly make light polarizing film.By laser microscope（Olympus Co., Ltd OLS3000）Measure light polarizing film now Thickness, is as a result 2.0 μm.

2. degree of polarization, light transmittance, color molybdenum determination

The brightness for determining the light polarizing film for making by method similarly to Example 1 corrects singleton transmittance（Ty）And regard Gamma correction degree of polarization（Py）And colourity a^*, colourity b^*, orthogonal a^*And orthogonal b^*, as a result it is shown in table 4.

Embodiment 5

1. the making of black light polarizing film

Except the pin width and coating speed of the rod of rod coater are changed into（#5 50mm/s）In addition with embodiment 3 Similarly make light polarizing film.By laser microscope（Olympus Co., Ltd OLS3000）Measure light polarizing film now Thickness, is as a result 2.2 μm.

2. degree of polarization, light transmittance, color molybdenum determination

The brightness for determining the light polarizing film for making by method similarly to Example 1 corrects singleton transmittance（Ty）And regard Gamma correction degree of polarization（Py）And colourity a^*, colourity b^*, orthogonal a^*And orthogonal b^*, as a result it is shown in table 4.

[the light polarizing film formation composition of embodiment 6（C）Preparation]

Mixing following compositions, by stirring 1 hour at 80 DEG C, are obtained light polarizing film formation composition（C）.

2- dimethylamino -2- benzyl -1-（4- morpholino phenyls）- 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

Except by light polarizing film formation composition（A）It is changed to light polarizing film formation composition（C）, further bar type is coated with The metal live width of the rod of machine and coating speed are changed into（#7 20mm/s）In addition, light polarizing film is made similarly to Example 1. By laser microscope（Olympus Co., Ltd OLS3000）The thickness of light polarizing film now is determined, is as a result 2.0 μm.

2. degree of polarization, light transmittance, color molybdenum determination

The brightness for determining the light polarizing film for making by method similarly to Example 1 corrects singleton transmittance（Ty）And regard Gamma correction degree of polarization（Py）And colourity a^*, colourity b^*, orthogonal a^*And orthogonal b^*, as a result it is shown in table 4.

Embodiment 7

1. the making of black light polarizing film

Metal live width and coating speed except changing the rod of rod coater（#5 50mm/s）In addition, with embodiment 6 Similarly make light polarizing film.By laser microscope（Olympus Co., Ltd OLS3000）Measure light polarizing film now Thickness, is as a result 2.2 μm.

2. degree of polarization, light transmittance, color molybdenum determination

The brightness for determining the light polarizing film for making by method similarly to Example 1 corrects singleton transmittance（Ty）And regard Gamma correction degree of polarization（Py）And colourity a^*, colourity b^*, orthogonal a^*And orthogonal b^*, as a result it is shown in table 4.

Comparative example 1

1. the making of iodo- PVA polarization plates

By average degree of polymerization about 2,400,75 μm of the thickness of 99.9 moles of more than % of saponification degree polyvinyl alcohol film with drying About 5 times of form uniaxial tension, further, in the state of tensile state is kept, impregnated in 60 DEG C of pure water after 1 minute, The mass ratio of iodine/KI/water be 0.1/5/100 the aqueous solution at 28 DEG C impregnate 60 seconds.Afterwards, in KI/boron The mass ratio of acid/water for 810.5/7.5/100 the aqueous solution at 72 DEG C impregnate 300 seconds.Then washed with 10 DEG C of pure water After washing 5 seconds, it is dried 3 minutes at 80 DEG C, the polarizer of on polyvinyl alcohol resin film iodine gas absorption quantity is obtained.

2. degree of polarization, light transmittance, color molybdenum determination

The brightness for determining the polarizer for making by method similarly to Example 1 corrects singleton transmittance（Ty）And regard Gamma correction degree of polarization（Py）And colourity a^*, colourity b^*, orthogonal a^*And orthogonal b^*, as a result it is shown in table 4.

[table 4]

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Comparative example
									Thickness（μm）	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 more slim than the conventional iodo- PVA polarizers.Additionally, embodiment 1 ~ 7 light polarizing film all shows muted color phasic property.

Embodiment 8

1. the making of the optical alignment film on phase retardation film

Using phase retardation film（Single axle drawn membrane WRF-S（Modified polycarbonate system resin）, phase difference value 137.5nm, thickness 50 μm of degree, Supreme Being people's chemical conversion（Strain）System）As transparent base, replace triacetylcellulose film（KC8UX2M, Konica Minolta （Strain）System）, the formula is made by the coating of bar type rubbing method（3）Represented light orientation polymer is dissolved in the 5% of cyclopentanone Solution, dry being obtained is dried overlay film at 120 DEG C.Here is dried on overlay film irradiates the prepared optical alignment films of polarised light UV.Using UV Irradiation unit（SPOT CURE SP-7；Ushio Electric Inc's system）, determine under wavelength 365nm, in intensity 100mJ Under the conditions of carry out polarised light UV process.Additionally, now, make the direction of illumination of polarised light UV relative to phase retardation film slow axis into 45 ° are implemented.

2. the making of circularly polarizing plate

By bar type rubbing method on the optical alignment film of phase retardation film for having attached the optical alignment film for making（#7 20mm/s） Coating light polarizing film formation composition（C）, heat drying is cooled to room temperature after 1 minute in 120 DEG C of drying oven.Then, Using UV irradiation units（SPOT CURE SP-7；Ushio Electric Inc's system）, by being formed with combination by light polarizing film Layer irradiation exposure amount 2000mJ/cm that thing is formed²（365nm benchmark）Ultraviolet, keeping the polymerizable liquid crystal compound Mesomorphic state in the state of make it is described be dried include in overlay film polymerizable liquid crystal compound polymerization, by being covered by the drying Film forms light polarizing film to make circularly polarizing plate.By laser microscope（Olympus Co., Ltd OLS3000）Determine now Light polarizing film thickness, be as a result 2.0 μm.

3. the confirmation of antireflection property

The phase retardation film side of obtained circularly polarizing plate is fitted with aluminium metal sheet via adhesive, as a result with aluminium metal sheet list The metallic luster that body is observed disappears, and obtains homogeneous black display.Understand so had by the circularly polarizing plate of this polarisation film production There is good preventing reflection characteristic.

Industrial applicability

This light polarizing film manufacture liquid crystal indicator,（It is organic）EL display devices and projection-type liquid crystal display device aspect pole For useful.

Claims (13)

1. a kind of light polarizing film, its contain formed by polymerizable liquid crystal compound polymer, be scattered in the polymer and determine During light absorbs, there is at least a kind dichroism pigment (1) of absorption maximum and in wavelength in the scope of 380～550nm of wavelength The scope of 550～700nm has at least 2 kinds dichroism pigments (2) of absorption maximum,

When being scattered in measure light absorbs in the polymer, have at least the 2 of absorption maximum in the scope of 550～700nm of wavelength Plant dichroism pigment (2) to contain：When light absorbs are determined in being scattered in the polymer in the scope of 550～600nm of wavelength Dichroism pigment (2-1) with absorption maximum and there is the dichroism of absorption maximum in the scope of 600～700nm of wavelength Pigment (2-2),

Compound of the dichroism pigment (2) represented by formula (2) is constituted,

In formula (2),

N is 1 or 2,

Ar¹And Ar³Separately for formula (AR-1)～formula (AR-4) any one represented by group,

Ar²Group represented by formula (AR2-1), formula (AR2-2) or formula (AR2-3),

A₁And A₂Separately for formula (A-1)～formula (A-9) any one represented by group, * represents bonding position,

Mc is 0～10 integer, and when there is 2 mc in same group, 2 mc can be mutually identical or different.

2. the light polarizing film according to described in claim 1, wherein, the dichroism pigment (1) is scattered in by polymerism liquid When determining light absorbs in the polymer that crystallization compound is formed, there is absorption maximum in the scope of 400～550nm of wavelength.

3. the light polarizing film recorded according to claim 1 or 2, wherein, polymerizable liquid crystal compound shows smectic crystal phase Compound.

4. light polarizing film according to claim 1, it obtains bragg peak in X-ray diffraction measure.

5. light polarizing film according to claim 1, wherein, under the chromaticity coordinates a* values and b* values in L*a*b* colour systems meets The relation of formula (1F) and formula (2F) is stated,

- 3≤colourity a*≤3 (1F)；

- 3≤colourity b*≤3 (2F).

6. light polarizing film according to claim 1, wherein, dichroism pigment (1) and dichroism pigment (2) they are azos Compound.

7. light polarizing film according to claim 1, wherein, compound structure of the dichroism pigment (1) represented by formula (1) Into,

In formula (1),

Groups of the Y represented by formula (Y1) or formula (Y2),

In formula, L is that oxygen atom or-NR-, R are hydrogen atom or the alkyl of carbon number 1～4,

R¹For formula (R¹- 1)～formula (R¹- 3) group represented by any one,

In formula, ma is 0～10 integer, and when there is 2 ma in same group, 2 ma can be mutually identical or different, * tables Show bonding position,

R²For formula (R²- 1)～formula (R²- 6) group represented by any one,

In formula, mb is 0～10 integer.

8. a kind of polarizer, it is to arrange the light polarizing film that any one of claim 1～7 records over the transparent substrate to form.

9. the manufacture method of the polarizer that a kind of claim 8 is recorded, it has

Preparation possesses over the transparent substrate the operation of the laminate of alignment films；

The operation of coating composition in the alignment films of the laminate, the composition contains polymerizable liquid crystal chemical combination Thing, be scattered in the polymer formed by the polymerizable liquid crystal compound determine light absorbs when, 380～550nm's of wavelength Scope has a kind of dichroism pigment (1) of absorption maximum, has 2 kinds of absorption maximum in the scope of 550～700nm of wavelength Dichroism pigment (2) and solvent；

The operation for making the polymerizable liquid crystal compound included in the composition be polymerized.

10. manufacture method according to claim 9, wherein, transparent base is plastic basis material, also, the alignment films are Optical alignment film.

A kind of 11. liquid crystal indicators, the light polarizing film that its any one for possessing claim 1～7 is recorded.

A kind of 12. circularly polarizing plates, it has the light polarizing film of any one record of claim 1～7 and λ/4 layer, meets following (A1) and (A2) necessary condition,

(A1) the extinction axle of the light polarizing film is about 45 ° with the slow axis angulation of λ/4 layer；

(A2) with the scope that the value of the front retardation of λ/4 layer of the light measurement of wavelength 550nm is 100～150nm.

A kind of 13. organic EL displays, it possesses the circularly polarizing plate and organic EL element of claim 12 record.