CN103173227B

CN103173227B - Form the compositions used by polarization film and polarization film

Info

Publication number: CN103173227B
Application number: CN201210552907.XA
Authority: CN
Inventors: 幡中伸行
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2011-12-20
Filing date: 2012-12-18
Publication date: 2016-12-28
Anticipated expiration: 2032-12-18
Also published as: KR20130071367A; JP2020057020A; TW201727292A; CN103173227A; JP2018084845A; TWI724121B; JP6343866B2; TWI585472B; TW201331643A; JP2013148883A; JP6983213B2; KR102089807B1

Abstract

It is an object of the invention to provide a kind of polarization film that can manufacture and form slim and that the there is heigh clarity compositions used by polarization film and formed by the compositions formed used by this polarization film.The solution of the present invention is to provide containing polymerizable liquid crystal compound, polymerism non-liquid crystal compound, dichroism pigment, Photoepolymerizationinitiater initiater and solvent, and meet following (A) and (B) essential condition forms the compositions used by polarization film and the polarization film formed by the compositions formed used by this polarization film.(A) polymerizable liquid crystal compound and polymerism non-liquid crystal compound all contain polymerizable group；(B) in the coated film obtained by the compositions formed used by polarization film, contained polymerizable liquid crystal compound does not haves phase-separated state, but shows nematic liquid crystal phase and smectic liquid crystal phase.

Description

Form the compositions used by polarization film and polarization film

Technical field

The present invention relates to form the compositions used by polarization film and by the compositions system formed used by this polarization film The polarization film produced and manufacture method etc. thereof.

Background technology

Liquid crystal indicator in recent years, the requirement to its filming is more and more higher, meanwhile, also requires that this liquid crystal Polarizer used in showing device is more slim material.In order to realize more slim polarizer, begin one's study containing polymerization Property liquid-crystal compounds compositions institute film forming replace polyvinyl alcohol institute film forming through iodine staining in the past to apply as polarization film In liquid crystal indicator.

The polarization film that compositions containing polymerizable liquid crystal compound is formed, such as, patent documentation 1 is disclosed only by gathering The polarization film that conjunction property smectic liquid crystal compound, dichroism pigment, Photoepolymerizationinitiater initiater are formed with Inhibitors, meanwhile, specially Profit document 2 in disclose only by polymerizable liquid crystal compound, dichroism pigment, polymerization initiator, inhibitor, gelating agent and The polarization film that solvent is formed.

Prior art

Patent documentation

Patent documentation 1: No. 4719156 publications of Japanese Patent No.

Patent documentation 2: Japan Patent spy's table 2008-547062 publication

Summary of the invention

The problem that invention is to be solved

But, to polarization film, it is desirable to its more slimming and highly transparent.

It is an object of the invention to provide a kind of group that can manufacture used by slim and that there is heigh clarity polarization film Compound and the polarization film formed by the compositions formed used by this polarization film.

Solve the means of problem

The present invention includes following invention,

[1] a kind of compositions formed used by polarization film, it is characterised in that containing polymerizable liquid crystal compound, polymerization Property non-liquid crystal compound, dichroism pigment, polymerization initiator and solvent, meet following (A) essential condition and (B) be necessary Condition.

(A) polymerizable liquid crystal compound and polymerism non-liquid crystal compound all contain polymerizable group；

(B) in the coated film obtained by the compositions formed used by polarization film, contained polymerizable liquid crystal compound will not go out Existing phase-separated state, but present nematic liquid crystal phase and smectic liquid crystal phase.

(these (A) and (B) essential condition, respectively in hereinafter referred to as " (essential condition A) and " (essential condition B) ".)

[2] compositions used by polarization film of the formation described in basis [1], polymerizable liquid crystal compound is shown in formula (1) Compound.

U¹-V¹-W¹-X¹-Y¹-X²-Y²-X³-W²-V²-U² (1)

(in formula, X¹、X²And X³Separately represent the Isosorbide-5-Nitrae-phenylene that can contain substituted radical or can contain Hexamethylene-Isosorbide-5-Nitrae-the diyl of substituted group.But, X¹、X²And X³In at least one be can containing substituted radical Isosorbide-5-Nitrae- Phenylene.Constitute-the CH of hexamethylene-Isosorbide-5-Nitrae-diyl₂-can be replaced by-O-,-S-or-NR-.R represents carbon number 1 ~ 6 Alkyl or phenyl.Y¹And Y²Separately expression-CH₂CH₂-、-CH₂O-,-COO-,-OCOO-, singly-bound ,-N=N-,-CR^a =CR^b-,-C ≡ C-or-CR^a=N-。R^aAnd R^bSeparately represent hydrogen atom or the alkyl of carbon number 1 ~ 4.U¹Table Show hydrogen atom or polymerism base.U²Represent polymerism base.W¹And W²Represent independently of each other singly-bound ,-O-,-S-,-COO-or Person-OCOO-.V¹And V²Represent the alkylidene of the carbon number 1 ~ 20 that can contain substituent group independently of each other, constitute this alkylene -the CH of base₂-can be replaced by-O-,-S-or-NH-.

[3] compositions used by polarization film of the formation described in basis [1] or [2], its polymerism non-liquid crystal compound For monofunctional acrylate or polyfunctional acrylic ester.

[4] compositions used by polarization film of the formation described in any one of basis [1] ~ [3], its polymerizable liquid crystal compound The polymerizable group that the polymerizable group contained and polymerism non-liquid crystal compound contain is separately for acryloxy (CH₂=CHCOO-) or methacryloxy (CH₂=C(CH₃)COO-)。

[5] compositions used by polarization film of the formation described in any one of basis [1] ~ [4], its polymerizable liquid crystal compound The polymerizable group that the polymerizable group contained contains with polymerism non-liquid crystal compound is identical.

[6] compositions used by polarization film of the formation described in any one of basis [1] ~ [5], its polymerizable liquid crystal compound Intramolecular contains 1 ~ 2 polymerizable group, and polymerism non-liquid crystal compound molecule is contained within 2 ~ 6 polymerizable groups.

[7] compositions used by polarization film of the formation described in any one of basis [1] ~ [6], its polymerism non-liquid crystal chemical combination The content of thing, relative to polymerizable liquid crystal compound 100 mass parts, is more than 3 mass parts, below 10 mass parts.

[8] containing following (I), the manufacture method of the polarization film of (II) and (III) operation.

(I) compositions used by polarization film that formed described in any one of [1] ~ [7] is coated on base material or base material In the alignment films of upper formation, remove solvent and form the operation of coated film；

(II) polymerizable liquid crystal compound contained in the coated film formed in (I) is made to become the work of smectic liquid crystal phase state Sequence；

(III), in coated film that formed in (II), that polymerizable liquid crystal compound is smectic liquid crystal phase state, polymerization is made Property liquid-crystal compounds and polymerism non-liquid crystal compound copolymerization operation；

[9] according to the manufacture method of the polarization film described in [8], its base material is the transparent base implementing orientation process.

[10] according to the manufacture method of the polarization film described in [8] or [9], wherein, (II) operation comprises, heat treated Until the operation (I-of polymerizable liquid crystal compound display nematic liquid crystal phase state contained in the coated film formed in (I) operation 1), cool down with by middle for operation (I-1) coated film that this polymerizable liquid crystal compound is nematic liquid crystal phase state formed, until should The operation (I-2) of polymerizable liquid crystal compound display smectic liquid crystal phase.

[11] a kind of polarization film, by the manufacture method manufacture described in any one of [8] ~ [10].

[12] according to the polarization film described in [11], its X-ray diffraction measures display bragg peak.

[13] a kind of display device, containing the polarization film described in [11] or [12].

The effect of invention

The compositions used by formation polarization film according to the present invention, it is possible to produce the slim and polarization of high transparent Light film.

Accompanying drawing explanation

Fig. 1 shows the key of the method for continuous production (volume to volume (Roll to Roll) form) of the polarization film of the present invention The schematic diagram of part.

Fig. 2 shows the schematic diagram of the section constitution of the polariscopic liquid crystal indicator using the polarization film containing the present invention.

Fig. 3 shows the schematic diagram of the polariscopic layer order of the polarization film containing the present invention arranged in liquid crystal indicator.

Fig. 4 shows the schematic diagram of the polariscopic layer order of the polarization film containing the present invention arranged in liquid crystal indicator.

Fig. 5 shows the composition of the polariscopic liquid crystal indicator (embedded) using the polarization film containing the present invention Schematic diagram.

Fig. 6 contains the schematic cross-section of the circular polarization light board of the polarization film of the present invention.

Fig. 7 contains the schematic diagram of the method for continuous production of the circular polarization light board of the polarization film of the present invention.

Fig. 8 shows the schematic diagram of the composition of the EL display device of the circular polarization light board using the polarization film containing the present invention.

Fig. 9 shows the schematic diagram of the layer order of the circular polarization light board of the polarization film containing the present invention arranged in EL display device.

Figure 10 shows the schematic diagram of the composition of the EL display device of the circular polarization light board using the polarization film containing the present invention.

Figure 11 shows the composition of the polariscopic projection-type liquid crystal display device using the polarization film containing the present invention Schematic diagram.

The explanation of symbol

1 transparent base

2 optical alignment films

3 polarization films

4 phase separation layers

100 polarization films

210 the 1st cylinder 210A core

220 the 2nd cylinder 220A core

230 the 3rd cylinder 230A core

240 the 4th cylinder 240A core

211A, 211B apparatus for coating

212A, 212B drying oven

213A polarized light UV irradiation unit

213B light irradiation device

300 auxiliary cylinders

10 liquid crystal indicators

11 antireflection layers

12a, 12b polarization film

13a, 13b phase retardation film

14a, 14b base material

15 color filters

16 transparency electrodes

17 liquid crystal layers

18 interlayer dielectrics

19 backlight modules

20 black matrix"s

21 thin film transistor (TFT)s

22 pixel electrodes

23 septs

24 liquid crystal indicators

30 EL display devices

31 circular polarization light board

33 base materials

34 interlayer dielectrics

35 pixel electrodes

36 luminescent layers

37 cathode electrodes

38 desiccant

39 caps

40 thin film transistor (TFT)s

41 ribs

42 thin film sealing films

110 circular polarization light board

111 light sources

112 the 1st lens arras

112a lens

113 the 2nd lens arras

114 polarized light conversion elements

115 compound lenses

121,123,132 dichroic mirrors

122 reflecting mirrors

140R, 140G, 140B liquid crystal panel

142,143 polarizeies

150 cross colour splitting prisms

170 projecting lens

180 projection screens

It is embodied as form

The present invention forms the compositions used by polarization film (the most sometimes referred to as " this compositions ".), containing polymerization Property liquid-crystal compounds, polymerism non-liquid crystal compound, dichroism pigment, polymerization initiator, solvent.Passed through by this compositions The polarization film that aftermentioned manufacture method is formed is (following, sometimes referred to as " this polarization film ".), can manufacture and be applicable not only to liquid Crystal device, the circular polarization light board applying also for organic EL display is (following, sometimes referred to as " this circular polarization light board ".) First, this compositions is illustrated.

The polymerizable liquid crystal compound of the present invention contains polymerizable group, and the coated film formed by this compositions will not Phase-separated state occurs, is the liquid-crystal compounds with the characteristic being shown as nematic liquid crystal phase and smectic liquid crystal phase.

By following manner, the coated film formed by this compositions, confirms whether it meets (essential condition B).At glass baseplate Upper this compositions of coating, this compositions of coating is not polymerized at polymerizable liquid crystal compound and polymerism non-liquid crystal compound Under the conditions of implement heat treated and/or reduced pressure treatment, remove solvent.Then, the coated film that heating glass substrates is formed, Confirm whether the polymerizable liquid crystal compound contained in this coated film is separated, if display nematic liquid crystal phase.Afterwards, Slowly cool down the coated film of heating, confirm whether the polymerizable liquid crystal compound contained in this coated film is separated, be No display smectic liquid crystal phase.The texture being identified through such as micropolariscope of nematic liquid crystal phase and smectic liquid crystal phase is seen Examine, X-ray diffraction measures or Differential Scanning Calorimeter measures and carries out.By the most various microscopical surface observations or transmissometer Nephelometric turbidity unit measure confirm its whether formed separated.

The smectic liquid crystal that polymerizable liquid crystal compound shows preferred high order smectic phase mutually.High order smectic phase referred to herein has Smectic B, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase and near Brilliant L phase, wherein, preferably smectic B, smectic F phase and smectic I phase.The smectic liquid crystal that polymerizable liquid crystal compound shows is mutually During these high order smectic phases, it is possible to produce higher polarization film of ordered orientation degree.Meanwhile, above-mentioned ordered orientation Du Genggao This polarization film obtain from hexagonal phase (hexatic) or the Bradley that crystallizes equal higher order structure in X-ray diffraction measures Lattice peak.

As polymerizable liquid crystal compound, it is preferably 40 ~ 200 by the temperature of nematic liquid crystal phase phase in version to smectic liquid crystal phase DEG C compound, the compound of more preferably 60 ~ 140 DEG C.

As preferred polymerizable liquid crystal compound, such as, for example there are the compound shown in formula (1) (hereinafter sometimes referred to " compound (1) ").

U¹-V¹-W¹-X¹-Y¹-X²-Y²-X³-W²-V²-U² (1)

[in formula (1), X¹、X²And X³Separately representing can be containing the Isosorbide-5-Nitrae-phenylene of substituted radical or permissible Hexamethylene-Isosorbide-5-Nitrae-diyl containing substituted radical.But, X¹、X²And X³In at least 1 be can containing substituted radical 1, 4-phenylene.Constitute-the CH of hexamethylene-Isosorbide-5-Nitrae-diyl₂-, can be replaced by-O-,-S-or-NR-.R represent carbon number 1 ~ The alkyl of 6 or phenyl.

Y¹And Y²Separately expression-CH₂CH₂-、-CH₂O-,-COO-,-OCOO-, singly-bound ,-N=N-,-CR^a= CR^b-,-C ≡ C-or-CR^a=N-。R^aAnd R^bSeparately represent hydrogen atom or the alkyl of carbon number 1 ~ 4.

U¹Represent hydrogen atom or polymerizable group.

U²Represent polymerizable group.

W¹And W²Separately represent singly-bound ,-O-,-S-,-COO-or-OCOO-.

V¹And V²Separately represent the alkylidene of the carbon number 1 ~ 20 that can contain substituted radical, constitute this Asia -the CH of alkyl₂-can be replaced by-O-,-S-or-NH-.

In compound (1), X¹、X²And X³In, preferably at least 2 is can be containing the Isosorbide-5-Nitrae-phenylene of substituent group.

Can be containing the Isosorbide-5-Nitrae-phenylene of substituted radical, preferably without substituted radical.Can be containing the ring of substituted radical Hexane-Isosorbide-5-Nitrae-diyl preferably can contain the anti-of substituted radical containing the trans-cyclohexane-Isosorbide-5-Nitrae-diyl of substituted radical Formula-preferred unsubstituted group of hexamethylene-Isosorbide-5-Nitrae-diyl.

Can containing substituted radical Isosorbide-5-Nitrae-phenylene or can containing substituted radical hexamethylene-Isosorbide-5-Nitrae-diyl appoint Meaning substituted radical such as example there are the alkyl of the carbon numbers 1 ~ 4 such as methyl, ethyl and butyl；Cyano group；Halogen atom etc..

The Y of compound (1)¹Preferably-CH₂CH₂-,-COO-or singly-bound, Y²Preferably-CH₂CH₂-or-CH₂O-。

U²It it is polymerizable group.U¹It is hydrogen atom or polymerizable group, preferred polymeric group.Preferably U¹And U²All For polymerizable group, likewise it is preferred that be optical polymerism group.Optical polymerism group herein refers to by absorbing luminous energy participation The group of polymerization.Even if the polymerizable liquid crystal compound containing optical polymerism group can also be polymerized under more cryogenic conditions, It is favourable on this point.As optical polymerism group, preferably free radical polymerizable group.Free-radical polymerised group refers to Enough living radicals by being produced by polymerization initiator described later participate in the group of polyreaction.

In compound (1), U¹And U²Polymerizable group can be each different, but the most identical.As polymerism base Group, such as, for example there are vinyl, ethyleneoxy, 1-chlorovinyl, isopropenyl, 4-vinyl phenyl, acryloxy, methyl-prop Alkene acyloxy, Oxyranyle and oxetanylmethoxy etc..Wherein, preferably acryloxy, methacryloxy and second Alkenyloxy group, more preferably acryloxy and methacryloxy.

As V¹And V²Alkylidene, such as example there are methylene, ethylidene, trimethylene, 1,3-butylidene, 1, 4-butylidene, 1,5-pentylidene, 1,6-hexylidene, 1,7-heptamethylene, 1,8-are octylene, 1,10-decylene, 1,14-sub-14 Alkyl and 1,20-alkylene eicosyl etc..V¹And V²The preferably alkylidene of carbon number 2 ~ 12, more preferably carbon number 6 ~ 12 Alkylidene.

As such as can for example there are containing substituted radical arbitrary in the alkylidene of the carbon number 1 ~ 20 of substituted radical Cyano group and halogen atom etc., but the preferred unsubstituted group of this alkylidene, the most unsubstituted group and the alkylene of straight-chain Base.

W¹And W²Separately preferred singly-bound or-O-.

As the concrete example of compound (1), such as, for example there are the compound etc. that formula (1-1) ~ formula (1-23) represents respectively.This Time in the concrete example of the compound (1) of sample containing hexamethylene-Isosorbide-5-Nitrae-diyl, its preferred trans body of hexamethylene-Isosorbide-5-Nitrae-diyl.

Polymerizable liquid crystal compound can individually or mix two or more in this compositions.Mix for two or more Time, preferably at least a kind is compound (1), and more preferably two or more is compound (1).Mix 2 kinds of polymerizable liquid crystals Mixed proportion during compound is usually 1:99 ~ 50:50, preferably 5:95 ~ 50:50, more preferably 10:90 ~ 50:50.

The polymerization temperature of this compositions is generally below the temperature that polymerizable liquid crystal compound phase in version is smectic phase.Permissible The polymerization temperature of this compositions is controlled by adjusting the ingredient of this compositions.Obtain polymerizable liquid crystal chemical combination the most in advance Phase transition is the temperature of smectic phase, adjusts the composition outside polymerizable liquid crystal compound, makes this compositions can be less than its phase It is polymerized under the temperature conditions of transition temperature.Time in this compositions containing polymerizable liquid crystal compound of more than two kinds, obtain these 2 kinds The temperature that mixture phase in version is smectic phase of above polymerizable liquid crystal compound, is controlled as described above.

In the compound (1) illustrated, preferred formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1- 8), the compound that formula (1-13), formula (1-14) and formula (1-15) represent.These compounds are by the polymerizable liquid crystal with other Compound or the interaction of polymerism non-liquid crystal compound, can be easily below smectic phase temperature at phase in version Under temperature conditions, i.e. it is adequately retained under the mesomorphic state of high order smectic phase and is polymerized.

The content ratio of the polymerizable liquid crystal compound in this compositions, relative to solid constituent 100 matter of this compositions Amount part, generally in 70 ~ 99.5 mass parts, preferably 80 ~ 99 mass parts, more preferably 80 ~ 94 mass parts, the most preferably 80 ~ 90 Mass parts.The content ratio of compound (1) within the above range time, latter compounds (2) to tend to orientation high, therefore excellent Choosing.Solid constituent herein is to remove the total amount of composition after solvent in the present compositions.

Polymerizable liquid crystal compound passes through such as, Lub et al.Recl.Trav.Chim.Pays-Bas, and 115,321- 328 (1996), or the known method manufacture described in Japanese Patent No. 4719156 etc..

The polymerism non-liquid crystal compound of the present invention is it is meant that containing polymerizable group, even and if during variations in temperature also Do not have the compound of the mesomorphic state being between solid and liquid.

Polymerism non-liquid crystal compound preferably (i) will not colored by themselves (absorption to visible ray), (ii) have with The intermiscibility that polymerizable liquid crystal compound mixes equably, and, (iii) will not hinder the liquid that polymerizable liquid crystal compound shows The formation of crystalline state.

As polymerism non-liquid crystal compound, such as, for example there are monofunctional acrylate and polyfunctional acrylic ester.Single Sense means containing 1 polymerizable group, multifunctional means containing multiple polymerizable groups.From polymerizable liquid crystal compound Can be carried out continuously with the polyreaction of polymerism non-liquid crystal compound and set out, preferably polyfunctional acrylic ester.The non-liquid of polymerism The quantity of the polymerizable group that crystallization compound contains, preferably 1 to 6, more preferably 2 to 6.

Polymerizable group contained by polymerizable group contained by preferred polymeric liquid-crystal compounds and polymerism non-liquid crystal compound Identical.

It addition, by the compound of at least one selected in polymerizable liquid crystal compound and polymerism non-liquid crystal compound During containing plural polymerizable group, at least 1 polymerizable group that preferred polymeric liquid-crystal compounds contains, liquid non-with polymerism At least 1 polymerizable group that crystallization compound contains is identical.

As polymerism non-liquid crystal compound preferably, for example there are and there is above-mentioned (i), (ii) and the feature of (iii), Intramolecular contains 1 to 6, preferably 2 monofunctional acrylate to 6 polymerizable groups and polyfunctional acrylic ester. It addition, because above-mentioned monofunctional acrylate and polyfunctional acrylic ester are non-liquid crystal liquid crystal property, preferably without mesomorphic structure. Meanwhile, the nematic liquid crystal phase of contained polymerizable liquid crystal compound and near in without interference with the coated film obtained by this compositions In the range of brilliant liquid crystalline phase, intramolecular can contain urethane structure, amino structure, epoxy construction, ethylene glycol structure and polyester Structure.

Polymerism non-liquid crystal compound can be used alone or mix two or more in this compositions.

Monofunctional acrylate is that its intramolecular contains one by acryloxy (CH₂=CH-COO-) and metering system Acyloxy (CH₂=C(CH₃)-COO-) and in groups in select group (following, be sometimes designated as (methyl) acryloxy.) change Compound.When polymerism non-liquid crystal compound is monofunctional acrylate, preferred polymeric liquid-crystal compounds also contains (methyl) third Alkene acyloxy.

As the monofunctional acrylate containing 1 (methyl) acryloxy, for example there are (methyl) acrylic acid carbon atom The Arrcostab of several 4 to 16, the β carboxyalkyl ester of (methyl) acrylic acid carbon number 2 to 14, (methyl) acrylic acid carbon number 2 Alkyl-substituted phenyl ester to 14, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group Polyethylene Glycol (methyl) acrylic acid Ester and (methyl) isobornyl acrylate etc..

Polyfunctional acrylic ester, it is common that its intramolecular contains 2 compounds to 6 methacryloxies.Polymerism When non-liquid crystal compound is polyfunctional acrylic ester, preferred polymeric liquid-crystal compounds also contains (methyl) acryloyl group epoxide.

As 2 functional acrylates containing 2 (methyl) acryloxies, such as, for example there are 1,3 butylene glycol two (first Base) acrylate；1,3 butylene glycol (methyl) acrylate；1,6-hexanediol two (methyl) acrylate；Ethylene glycol bisthioglycolate (first Base) acrylate；Diethylene glycol two (methyl) acrylate；Neopentyl glycol two (methyl) acrylate；Triethylene glycol two (first Base) acrylate；TEG two (methyl) acrylate；Polyethyleneglycol diacrylate；Double (acryloxies of bisphenol-A Ethyl) ether；Ethoxylated bisphenol A bis-(methyl) acrylate；Ethoxylated neopentylglycol two (methyl) acrylate；Ethyoxyl Change neopentyl glycol two (methyl) acrylate and 3-methyl pentanediol two (methyl) acrylate etc..

As the polyfunctional acrylic ester containing 3 to 6 (methyl) acryloxies, for example there are trimethylolpropane tris (methyl) acrylate；Tetramethylolmethane three (methyl) acrylate；Three (2-ethoxy) isocyanuric acid ester three (methyl) acrylic acid Ester；Ethoxylated trimethylolpropane three (methyl) acrylate；Propoxylation trimethylolpropane tris (methyl) acrylate； Tetramethylolmethane four (methyl) acrylate；Dipentaerythritol five (methyl) acrylate；Dipentaerythritol six (methyl) acrylic acid Ester；Tripentaerythritol four (methyl) acrylate；Tripentaerythritol five (methyl) acrylate；Tripentaerythritol six (methyl) third Olefin(e) acid ester；Tripentaerythritol seven (methyl) acrylate；Tripentaerythritol eight (methyl) acrylate；

Tetramethylolmethane three (methyl) acrylate and the reactant of anhydride；Dipentaerythritol five (methyl) acrylate and acid The reactant of acid anhydride；

Tripentaerythritol seven (methyl) acrylate and the reactant of anhydride；

Caprolactone modification trimethylolpropane tris (methyl) acrylate；Caprolactone modification tetramethylolmethane three (methyl) propylene Acid esters；Caprolactone modification three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate；Caprolactone modification tetramethylolmethane four (methyl) acrylate；Caprolactone modification dipentaerythritol five (methyl) acrylate；Caprolactone modification dipentaerythritol six (first Base) acrylate；Caprolactone modification tripentaerythritol four (methyl) acrylate；Caprolactone modification tripentaerythritol five (methyl) Acrylate；Caprolactone modification tripentaerythritol six (methyl) acrylate；Caprolactone modification tripentaerythritol seven (methyl) third Olefin(e) acid ester；Caprolactone modification tripentaerythritol eight (methyl) acrylate；Caprolactone modification tetramethylolmethane three (methyl) acrylic acid Ester and the reactant of anhydride；Caprolactone modification dipentaerythritol five (methyl) acrylate and the reactant of anhydride, with in Radix Chloranthi Serrati Ester modified tripentaerythritol seven (methyl) acrylate and anhydride etc..It addition, the polyfunctional acrylic ester of above-mentioned expression is concrete In example, (methyl) acrylate means acrylate or methacrylate.Meanwhile, caprolactone modification mean from Between alcohol position and (methyl) acryloxy of (methyl) acrylate compounds, introduce the open loop body of caprolactone or open Cyclopolymer.

Such polyfunctional acrylic ester can use commercial goods.As such commercial goods, such as, for example there are A- DOD-N、A-HD-N、A-NOD-N、APG-100、APG-200、APG-400、A-GLY-9E、A-GLY-20E、A-TMM-3、A- TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, HD-N, NOD-N, NPG, TMPT (Xin Zhong village chemistry strain formula meeting Society's system), " ARONIX M-220 ", with " M-325 ", with " M-240 ", with " M-270 " " M-309 " together " M-310 " together, with " M- 321 ", with " M-350 ", with " M-360 ", with " M-305 ", with " M-306 ", with " M-450 ", with " M-451 ", with " M-408 ", with " M-400 ", same " M-402 ", same " M-403 ", same " M-404 ", same " M-405 ", same " M-406 " (Toagosei Co., Ltd System), " EBECRYL11 " " 145 " together, with " 150 ", with " 40 ", with " 140 ", same " 180 ", DPGDA, HDDA, TPGDA, HPNDA, PETIA, PETRA, TMPTA, TMPEOTA, DPHA, EBECRYL series (DAICEL CYTEC(ダィセ Le サィテッ Network) strain Formula commercial firm system) etc..

As preferred polyfunctional acrylic ester, such as, for example there are the chemical combination that following formula (4-1) ~ (4-14) is respectively shown in Thing.

The content of the polymerism non-liquid crystal compound in this compositions, relative to the gross mass of this compositions, usually 0.1 ~ 20 mass %, preferably 1 ~ 10 mass %, more preferably 3 ~ 7 mass %.More preferably relative to solid constituent 100 mass of this compositions Part is 0.1 ~ 19 mass parts, the most preferably 1 ~ 15 mass parts, particularly preferred 4 ~ 10 mass parts.Further, relative to poly- Conjunction property liquid-crystal compounds 100 weight portion, more than particularly preferred 3 mass parts, below 10 mass parts.Polymerism non-liquid crystal compound Content if within the above range, can in the coated film obtained by this compositions the taking of contained polymerizable liquid crystal compound In the case of tropism not multilated, make polymerizable component (polymerizable liquid crystal compound and the non-liquid of polymerism in this compositions Crystallization compound) copolymerization, so preferably.Although it is respective also with polymerizable liquid crystal compound and polymerism non-liquid crystal compound Kind is different and different, but when the content of polymerism non-liquid crystal compound is more more than above-mentioned scope, this polarization film saturating Bright property has the tendency of decline, so the most preferred.

Dichroism pigment is the character that the absorbance with molecular long axis direction is different from the absorbance of short-axis direction Pigment.If having above-mentioned character, dichroism pigment can be dyestuff, it is also possible to be pigment, can also be multipleization simultaneously The mixture of compound.

As above-mentioned dichroism pigment, preferably 300 ~ 700nm scope has maximum absorption wavelength (λ MAX).As this The dichroism pigment of sample, such as, for example there are acridine pigment, piperazine pigment, anthocyanidin, naphthalene pigment, azopigment and anthraquinone Pigment etc., wherein preferred azopigment.As azopigment, such as, for example there are monoazo pigment, bisazo pigment, trisazo-color Element, four azopigments and azopigment etc., preferably bisazo pigment and trisazo-pigment.

As azopigment, such as, for example there are the compound (hereinafter sometimes referred to " compound (2) ") shown in formula (2).

A¹(-N=N-A²)_p-N=N-A³ (2)

[in formula (2), A¹And A³Separately represent the phenyl that can contain substituted radical, substituted radical can be contained Naphthyl or can be containing 1 valency heterocyclic radical of substituted radical.A²Expression can containing substituted radical to phenylene, Ke Yihan Naphthalene-Isosorbide-5-Nitrae-the diyl of substituted group or can be containing the divalent heterocyclic radical of substituted radical.P represents the integer of 1 ~ 4.P be 2 with On integer time, multiple A²Can be identical, it is also possible to different.]

As the heterocyclic radical of 1 valency, such as, for example there are by quinoline, thiazole, benzothiazole, thieno thiazole, imidazoles, benzo miaow The heterocyclic compounds such as azoles, azoles and benzothiazole remove the group of 1 hydrogen atom.2 hydrogen atoms are removed from heterocyclic compound Group be divalent heterocyclic radical, the concrete example of this heterocyclic compound is described above.

As A¹And A³In phenyl, naphthyl and the heterocyclic radical of 1 valency and A²In to phenylene, naphthalene-Isosorbide-5-Nitrae-diyl And the substituted radical that the heterocyclic radical of divalent arbitrarily contains, such as example there are the alkyl of carbon number 1 ~ 4；Methoxyl group, ethyoxyl And the alkoxyl of the carbon number 1 ~ 4 such as butoxy；The fluoro-alkyl of the carbon numbers such as trifluoromethyl 1 ~ 4；Cyano group；Nitro；Halogen Element atom；(substituted-amino refers to have 1 or 2 for the replacement such as amino, diethylamino and pyrrolidinyl or unsubstituted amino The amino of the alkyl of individual carbon number 1 ~ 6, or 2 replace alkyl and be bound to each other to form the ammonia of alkylidene of carbon number 2 ~ 8 Base.Unsubstituted amino is-NH₂-.) it addition, carbon number 1 ~ 6 alkyl concrete example and compound (1) phenylene etc. arbitrarily The substituent group institute illustrated example having is identical.

In compound (2), the compound that preferably following formula (2-1) ~ formula (2-6) is respectively shown in.

[in formula (2-1) ~ (2-6), B¹~B²⁰Separately represent hydrogen atom, the alkyl of carbon number 1 ~ 6, carbon number (definition of substituted-amino and unsubstituted amino is with above-mentioned for alkoxyl, cyano group, nitro, replacement or the unsubstituted amino of 1 ~ 4 Equally), chlorine atom or trifluoromethyl.

N1 ~ n4 separately represents the integer of 0 ~ 3.

When n1 is more than 2, multiple B²Can the most identical can also be each different,

When n2 is more than 2, multiple B⁶Can the most identical can also be each different,

When n3 is more than 2, multiple B⁹Can the most identical can also be each different,

When n4 is more than 2, multiple B¹⁴Can the most identical can also be each different.]

As above-mentioned anthraquinone pigment, the compound that preferred formula (2-7) represents.

[in formula (2-7), R¹~R⁸Separately represent hydrogen atom ,-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr halogen is former Son.

R^xRepresent alkyl or the aryl of carbon number 6 ~ 12 of carbon number 1 ~ 4.]

As above-mentioned piperazine pigment, the compound that preferred formula (2-8) represents.

[in formula (2-8), R⁹~R¹⁵Separately represent hydrogen atom ,-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr halogen Atom.R^xRepresent alkyl or the aryl of carbon number 6 ~ 12 of carbon number 1 ~ 4.]

As above-mentioned acridine pigment, the compound that preferred formula (2-9) represents.

[in formula (2-9), R¹⁶~R²³Separately represent hydrogen atom ,-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr halogen Atom.R^xRepresent alkyl or the aryl of carbon number 6 ~ 12 of carbon number 1 ~ 4.]

In formula (2-7), formula (2-8) and formula (2-9), as R^xThe alkyl of the carbon number 1 ~ 4 represented, such as, for example there are Methyl, ethyl, propyl group, butyl, amyl group and hexyl etc., as the aryl of carbon number 6 ~ 12, such as, for example there are phenyl, toluene Base, xylyl and naphthyl etc..

As above-mentioned anthocyanidin, compound that preferred formula (2-10) represents and the compound that formula (2-11) represents.

[in formula (2-10), D¹And D²The base that separately any one of expression (2-10a) ~ formula (2-10d) represents Group.

N5 represents the integer of 1 ~ 3.]

[in formula (2-11), D³And D⁴The separately group shown in expression (2-11a) ~ any one of formula (2-11h).

N6 represents the integer of 1 ~ 3.]

The content of dichroism pigment in this compositions, relative to content 100 mass parts of polymerizable liquid crystal compound, excellent Select more than 0.1 mass parts, below 30 mass parts, more than more preferably 0.1 mass parts, below 20 mass parts, further preferred 0.1 matter More than amount part, below 10 mass parts, more than particularly preferred 0.1 mass parts, below 5 mass parts.The content of dichroism pigment is such as Fruit within the range, can the orientation not multilated of contained polymerizable liquid crystal compound in the coated film obtained by this compositions In the case of, make this polymerizable liquid crystal compound and polymerism non-liquid crystal compound polymerization, so preferably.Dichroism pigment Content is too much, probably can hinder the orientation of polymerizable liquid crystal compound.Accordingly it is also possible to the content of dichroism pigment is determined For making polymerizable liquid crystal compound be maintained in the range of mesomorphic state.

Dichroism pigment can use commercially available material.

This compositions contains polymerization initiator.This polymerization initiator is the polymerization that can cause polymerizable liquid crystal compound etc. The compound of reaction.As polymerization initiator, the Photoepolymerizationinitiater initiater of living radical preferably can be produced by the effect of light.

Photoepolymerizationinitiater initiater, such as, for example there are Benzoinum compound, benzophenone cpd, benzene alkyl ketone compound, acyl Base phosphine oxide compound, triaizine compounds, iodine salt and sulfonium salt etc..

Benzoinum compound, such as, for example there are Benzoinum, Benzoinum methyl ether, Benzoinum ethylether, benzoin isobutyl propyl group Ether, benzoin isobutyl butyl ether etc..

Benzophenone cpd, such as, for example there are benzophenone, o-benzoyl base benzoic acid methyl ester, 4-phenyl hexichol first Ketone, 4-benzoyl-4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6-front threes Base benzophenone etc..

Benzene alkyl ketone compound, such as, for example there are diethoxy acetophenone, 2-methyl-2-morpholine-1-(4-methylthio phenyl Base) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl Propane-1-ketone, 1,2-diphenyl-2,2-dimethoxy-ethane-1-ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) Phenyl] propane-1-ketone, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) The oligomer etc. of propane-1-ketone.

Acylphosphine oxide compound, such as example there are 2,4,6-trimethylbenzoyl diphenyl phosphine oxides and double (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide etc..

Triaizine compounds, such as, for example there are 2, double (trichloromethyl)-6-(4-the methoxyphenyl)-1,3,5-triazines of 4-, 2, Double (trichloromethyl)-6-(4-methoxyl group the naphthyl)-1,3,5-triazines of 4-, 2, double (trichloromethyl)-6-(the 4-methoxy styrene of 4- Base)-1,3,5-triazines, 2, double (trichloromethyl)-6-(2-(5-methylfuran-2-base) the vinyl)-1,3,5-triazines of 4-, 2,4- Double (trichloromethyl)-6-(2-(furan-2-base) vinyl)-1,3,5-triazines, 2, double (trichloromethyl)-6-(2-(the 4-diethyl of 4- Base amino-2-methyl phenyl) vinyl)-1,3,5-triazines, 2, double (trichloromethyl)-6-(2-(3,4-Dimethoxyphenyl) of 4- Vinyl)-1,3,5-triazines etc..

Polymerization initiator can use commercial goods.As commercially available polymerization initiator, such as, for example there are " ィ Le ガキュァ(Irgacure)907”、“ィルガキュァ184”、“ィルガキュァ651”、“ィルガキュァ819”、“ィルガキュァ 250 ", " ィ Le ガキュァ 369 " (チバジャパ Application (strain))；" セィ Network ォ mono-Le BZ ", " セィ Network ォ mono-Le Z ", " セィ Network ォ mono-Le BEE " (Seiko chemistry (strain))；" カャキュァ mono-(kayacure) BP100 " (Japan's chemical medicine (strain))； " カャキュァ mono-UVI-6992 " (ダゥ society system)；" ァデカォプトマ mono-SP-152 ", " ァデカォプトマ mono-SP- 170 " ((strain) ADEKA)；" TAZ-A ", " TAZ-PP " (Japan シィベ Le ヘグ Na one society)；And " TAZ-104 " (three and ケミカ Le society) etc..

In this compositions, the content of polymerization initiator suitably can be adjusted according to the kind of polymerizable liquid crystal compound and amount thereof Joint, is commonly angled relative to content 100 mass parts of polymerizable liquid crystal compound, is 0.1 ~ 30 mass parts.Preferably 0.5 ~ 10 mass parts, More preferably 0.5 ~ 8 mass parts.The content of polymerization initiator, can be in the coating obtained by this compositions if within the range In film in the case of the orientation not multilated of contained polymerizable liquid crystal compound, make polymerizable liquid crystal compound and the non-liquid of polymerism Crystallization compound copolymerization, so preferably.

This compositions contains solvent.It is preferably able to be completely dissolved polymerizable liquid crystal compound, the non-liquid of polymerism as solvent Crystallization compound and the solvent of dichroism pigment.Likewise it is preferred that show inert solvent when this compositions polyreaction.

As solvent, such as, for example there are, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, Ethylene glycol methyl ether, second two The alcoholic solvents such as alcohol butyl ether and propylene glycol monomethyl ether；Ethyl acetate, butyl acetate, Ethylene glycol methyl ether acetas, γ-fourth Lactone or the ester solvent such as methyl proxitol acetate and ethyl lactate；Acetone, methyl ethyl ketone, Ketocyclopentane, hexamethylene The ketone solvents such as ketone, 2-heptanone and methyl iso-butyl ketone (MIBK)；The aliphatic hydrocarbon solvents such as pentane, hexane and normal heptane；Toluene and The nitrile solvents such as aromatic hydrocarbon solvents, acetonitrile such as dimethylbenzene；The ether solvents such as oxolane and dimethoxy-ethane；Chloroform and chlorine The chlorinated solvents etc. such as benzene.These solvents can be used alone, it is also possible to multiple combinations are also used.

The content of solvent is relative to total amount preferably 50 ~ 98 mass % of this compositions.In other words, consolidating in this compositions Body composition preferably 2 ~ 50 mass %.When solid constituent is more than 2 mass %, it is intended to be easier to obtain this polarization film, so excellent Choosing.During it addition, this solid constituent is below 50 mass %, owing to the viscosity of this compositions is low, the thickness of this polarization film is the most equal One, have in this polarization film and be difficult to that uneven tendency occurs, so preferably.Meanwhile, such solid constituent, according to make The thickness of this polarization film made determines.

This compositions can such as example there are control polymerism containing the composition outside mentioned component as such composition The polyreaction auxiliary agent of the polyreaction of liquid-crystal compounds etc..

This compositions can contain sensitizer further.As sensitizer, preferably photosensitizer.As this sensitizer, Such as example there are the xanthone based compound such as xanthone and thiaxanthone (such as 2,4-diethyl thioxanthone, 2-isopropyl thiophene Ton ketone etc.), the anthracene compound such as anthracene and the anthracene (such as, dibutoxy anthracene etc.) containing alkoxyl；Phenothiazine and rubrene etc..

When this compositions contains sensitizer, can more promote the polymerizable liquid crystal compound contained in this compositions and gather The polyreaction of conjunction property non-liquid crystal compound.The usage amount of such sensitizer, relative to the total amount of polymerizable liquid crystal compound 100 mass parts, preferably 0.1 ~ 30 mass parts, more preferably 0.5 ~ 10 mass parts, further preferred 0.5 ~ 8 mass parts.

In order to make polyreaction stably carry out, this compositions appropriateness can contain polymerization inhibitor.By containing polymerization inhibitor, can control The polyreaction of polymerizable liquid crystal compound processed and polymerism non-liquid crystal compound carry out degree.

As above-mentioned polymerization inhibitor, such as, for example there are containing hydroquinone and the hydroquinone containing alkoxyl, catechu containing alkoxyl Phenol (such as butyl catechol etc.), pyrogallic acid, the free radical such as 2,2,6,6-tetramethyls-piperidino epoxide free radical is caught Catch agent, phenylmercaptan. class, betanaphthyl amine and betanaphthol class etc..

Time in this compositions containing polymerization inhibitor, its content relative to polymerizable liquid crystal compound 100 mass parts, preferably 0.1 ~ 30 mass parts, more preferably 0.5 ~ 10 mass parts, further preferred 0.5 ~ 8 mass parts.The content of polymerization inhibitor is if in this scope In, the situation of the orientation of the polymerizable liquid crystal compound that can contain in not upsetting the compositions formed used by this polarization film Under be polymerized, therefore this polymerizable liquid crystal compound can more fully be maintained at mesomorphic state and is polymerized.

This compositions preferably comprises levelling agent.The mobility of this levelling agent this compositions of adjustable, has and makes to be coated with this The function that coated film that compositions obtains is more smooth, such as, for example there are surfactant etc..This levelling agent is further preferred, with poly- Acrylate compounds be main constituent levelling agent and with the compound containing fluorine atom as main constituent levelling agent institute in groups At least one of middle selection.It addition, polyacrylic acid ester compounds herein is without polymerizable group.

Polyacrylic acid ester compounds is the levelling agent of main constituent, such as, for example there are " BYK-350 ", " BYK-352 ", " BYK- 353 ", " BYK-354 ", " BYK-355 ", " BYK-358N ", " BYK-361N ", " BYK-380 ", " BYK-381 " and " BYK- 392 " [BYK Chemie society] etc..

As containing the fluorine atom compound levelling agent as main constituent, such as example there are " Mega-fac (メガ Off ァッ Network) R-08 ", with " R-30 ", with " R-90 ", with " F-410 ", with " F-411 ", with " F-443 ", with " F-445 ", with " F-470 ", With " F-471 ", with " F-477 ", with " F-479 ", with " F-482 " and with " F-483 " [DIC (strain)]；" Surflon (サ mono-Off ロ Application) S-381 ", with " S-382 ", with " S-383 ", with " S-393 ", with " SC-101 ", with " SC-105 ", " KH-40 " and " SA-100 " [AGC セィミケミカ Le (strain)]；" E1830 ", " E5844 " [(strain) Daikin Fine Chemical (ダィキ Application Off ァィ Application ケミカ Le) institute]；" ェ Off トップ EF301 ", with " EF303 ", with " EF351 " and with " EF352 " [Rhizoma Sparganii マテリァ Le electronics chemical conversion (strain)] etc..

Time in this compositions containing levelling agent, its content relative to polymerizable liquid crystal compound 100 mass parts, preferably 0.3 More than mass parts, below 5 mass parts, more than further preferred 0.5 mass parts, below 3 mass parts.The content of levelling agent is above-mentioned In the range of, polymerizable liquid crystal compound can be made the most parallel-oriented, and tend to make this polarization film obtained more flat Sliding, so preferably.Relative to polymerizable liquid crystal compound, when the content of levelling agent exceedes above-mentioned scope, this polarized light obtained Film easily occurs uneven, so the most preferred.It addition, this compositions can contain two or more levelling agent.

Then, illustrate for the method being formed this polarization film by this compositions.First, this compositions is coated in In the alignment films formed on base material or on base material.In the alignment films that preferred coated is formed on base material.The most saturating as base material Bright base material.

Transparent base refers to the base material with the transparency of the degree that can pass through light, especially visible ray.This transparency is Relative to the light in the range of wavelength 380 ~ 780nm, its transmitance characteristic more than 80%.This transparent base of concrete conduct, Such as example there are glass baseplate or plastic basis material.It addition, as the plastics of composition plastic basis material, such as example there are polyethylene, gather The polyolefin such as propylene, norbornene-based polymer；Annular ethylene series resin；Polyvinyl alcohol；Polyethylene terephthalate；Poly- Methacrylate；Polyacrylate；The fibers such as Triafol T, cellulose diacetate and cellulose acetate propionate Element ester；PEN；Merlon；Polysulfones；Polyether sulfone；Polyether-ketone；The plastics such as polyphenylene sulfide and polyphenylene oxide.Its In, from easily being bought and transparency significantly, particularly preferred cellulose esters, annular ethylene series resin, poly-carbon by market Acid esters, polyethylene terephthalate or polymethacrylates.Such transparent base is used when manufacturing this polarization film Material, be difficult to cause when transport, this transparent base of keeping breakage, easily operated from the viewpoint of, this transparent base can paste Attached support base material etc..Meanwhile, as described later, this polarization film when manufacturing circular polarization light board, plastic basis material phase place is sometimes given Difference property.At this point it is possible to give plastic basis material phase contrast by stretch processing.It addition, explanation gives transparent base phase place subsequently The method of difference property.

Cellulose esters is at least some of thing formed through acid esterification of institute's hydroxyl in cellulose.Such cellulose Formed by ester, cellulose ester membrane the most easily buys.Commercially available three cellulose acetate membrane has such as, " Off ジタッ Network film " (Fuji's description Off ィ Le system (strain))；" KC8UX2M ", " KC8UY " and " KC4UY " (U ニカミノ Le タォプト (strain)) etc..This The three cellulose acetate membrane that sample is commercially available, can be further used as transparent base after giving phase contrast directly or according to needs.With Time, the transparent substrate surface formed can be implemented non-glare treated, hard coat process, antistatic process or antireflection and process It is re-used as transparent base on surface after processing to use.

Annular ethylene series resin refers to by the polymerization of the cyclic olefins such as such as norborene or multi-ring norborneol dilute system monomer Thing or the thing of copolymer (annular ethylene series resin) composition, this annular ethylene series resin can partly contain open loop structure.With Time, the annular ethylene series resin containing ring opening moiety can be hydrogenated.Further, this annular ethylene series resin, from inconspicuous Affect increase hygroscopicity transparent, inconspicuous to set out, can be cyclic olefin and chain olefin or vinylation aromatic compound The copolymer of (styrene etc.).Its intramolecular of this annular ethylene series resin can introduce polar group simultaneously.

When annular ethylene series resin is cyclic olefin and chain olefin or the copolymerization of the aromatic compound containing vinyl During thing, this chain olefin is ethylene or propylene etc., simultaneously vinylation aromatic compound be styrene, α-methyl styrene and Alkyl-substituted styrene etc..In such copolymer, derive from the content ratio of construction unit of cyclic olefin relative to ring-type The full construction unit of olefin-based resin, at 50 moles of below %, in the scope of such as 15 ~ 50 moles of about %.Work as cycloolefin When resin is the terpolymer that cyclic olefin obtains with vinylation aromatic compound with chain olefin, such as, from chain The content ratio of the construction unit of alkene, is come at 5 ~ 80 moles of about % relative to the full construction unit of this annular ethylene series resin It is 5 ~ 80 moles of about % from the content ratio of the construction unit of vinylation aromatic compound.The ring of such terpolymer Shape olefin-based resin, when manufacturing this annular ethylene series resin, has the advantage that the usage amount of high price cyclic olefin is fewer.

Annular ethylene series resin the most commercially buys.As commercially available annular ethylene series resin, such as, for example there are " Topas " [Ticona society (German)]；" ァ mono-ト Application " [JSR (strain)]；" ゼォノァ (ZEONOR) " and " ゼォネッ Network ス (ZEONEX) " [Japan ゼォ Application (strain)]；" ァペ Le " [Mitsui Chemicals (strain) system] etc..Such annular ethylene series resin example Masking mode as known to by solvent casting process or extrusion by melting etc. prepares film (annular ethylene series resin film).Meanwhile, also The annular ethylene series resin film of commercially available film-forming state can be used.Such as lift as such commercially available annular ethylene series resin film Example has " ェスシ mono-Na " and " SCA40 " [hydrops chemical industry (strain)]；“ゼォノァフィルム”[ォプテス (strain)]；" ァ mono-ト Application Off ィ Le system " [JSR (strain)] etc..

Then, the method for the phase contrast of simple declaration imparting plastic basis material.Plastic basis material, by known drawing process Its phase contrast can be given.Such as, getting out plastic basis material and be wound into the cylinder (spool body) of cylinder, plastic basis material is continuous Ground exports from such spool body uncoiling, and the plastic basis material that uncoiling exports is transported to heating furnace.The design temperature of heating furnace exists Near the glass transition temperature of plastic basis material in the range of (DEG C) ~ [glass transition temperature+100] (DEG C), preferably vitrification The scope of (DEG C) ~ [glass transition temperature+50] (DEG C) near transition temperature.In this heating furnace, toward the advance side of plastic basis material To or during the stretching of vertical with advance side direction, adjust carriage direction or tension force, be allowed to tilt with arbitrary angle, carry out list The hot-stretch of axle or twin shaft processes.Stretching multiplying power generally in the range of about 1.1 ~ 6 times, preferably about 1.1 ~ 3.5 times Scope.Meanwhile, as the method stretched at incline direction, if the side continuously axis of orientation tilted with desired angle Method is i.e. not particularly limited, and can use known drawing process.Such drawing process can enumerate such as Japanese Patent Laid-Open The method that clear 50-83482 publication or Japanese Patent Laid-Open 2-113920 publication are recorded.

The thickness of transparent base, from having the weight of energy practical operation degree and may insure that it has the sufficient transparency Set out, the thinnest, but excessive thin meeting tend to intensity decline, machinability low.The suitable thickness of glass baseplate is such as 100 About ~ 3000 μm, preferably 100 ~ 1000 μm.The suitable thickness of plastic basis material about such as 5 ~ 300 μm, preferably 20 ~ 200 μm. When this polarization film is used as aftermentioned circular polarization light board, transparent when using especially as the circular polarization light board of mobile machine purposes Base material thickness, the thinnest, when using glass baseplate, preferred thickness is about 100 ~ 500 μm, thickness when using plastic basis material About preferably 20 ~ 100 μm.It addition, when giving plastic basis material phase contrast by stretching, before the thickness after stretching is by stretching Thickness and stretching ratio determine.

On the base material used when manufacturing this polarization film, it is preferably formed as alignment films.Now, this compositions is coated in orientation On film.So this alignment films preferably has is coated with this compositions without the solvent resistance dissolved.The most preferably removing solvent With make the heat treated of liquid crystal aligning has thermostability.As such alignment films, it is possible to use orientation polymer shape Become.

As above-mentioned orientation polymer, such as there can be exemplified intramolecular have the polyamide of amido link or gelatin class, Intramolecular has polyimides and hydrolysate i.e. polyamic acid, polyvinyl alcohol, the alkyl-modified polyvinyl alcohol of imide bond, gathers Acrylamide, polyazole, polymine, polystyrene, polyvinyl pyrrolidone, polyacrylic acid or polyacrylate etc. Polymer.Wherein, preferably polyethylene alcohol.Formed alignment films these orientation polymer can be used alone, it is also possible to 2 kinds with On be used in mixed way.

Orientation polymer, as the orientation polymer composition dissolved in a solvent (containing orientation polymer Solution), by being coated on base material, alignment films can be formed on the substrate.As this solvent, such as, for example there are, water；First The alcoholic solvents such as alcohol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether； Ethyl acetate, butyl acetate, ethylene glycol, methylether acetate, gamma-butyrolacton, methyl proxitol acetate and lactic acid second The ester solvents such as ester；The ketone such as acetone, methyl ethyl ketone, Ketocyclopentane, Ketohexamethylene, methyl amyl ketone and methyl iso-butyl ketone (MIBK) are molten Agent；The aliphatic hydrocarbon solvents such as pentane, hexane and heptane；The nitrile solvents such as the aromatic hydrocarbon solvents such as toluene and dimethylbenzene, acetonitrile； The ether solvents such as oxolane and dimethoxy-ethane；The chlorine such as chloroform and chlorobenzene replaces hydrocarbon solvent etc..These organic solvents can To be used alone, it is also possible to multiple be applied in combination.

Simultaneously in order to form alignment films, as orientation polymer composition, it is possible to use commercially available aligning film material.As At marketed aligning film material, such as example there are サ Application ェバ mono-(registered trade mark, Nissan Chemical Industries (strain) is made) or ォプトマ mono-(registered trade mark, JSR (strain)) etc..

As the method forming alignment films on above-mentioned base material, such as example there are be coated with on above-mentioned base material above-mentioned orientation gather Polymer composition or commercially available aligning film material, then, by annealing, can form alignment films on above-mentioned base material.Such The thickness of the alignment films arrived is such as in the scope of the scope of 10nm ~ 10000nm, preferably 10nm ~ 1000nm.

In order to above-mentioned alignment films being given orientation anchorage force, the most preferably carry out rub (friction).By giving Orientation anchorage force can make polymerizable liquid crystal compound be orientated with desired direction.

As the method giving orientation anchorage force by friction, such as, for example there are the rotation getting out be wound with friction cloth Friction roll, on base material formed alignment films formation coated film laminate be placed on platform, be transported to the friction being rotating Cylinder, makes the method that this alignment films formation coated film contacts with the friction roll being rotating.

At the same time it can also be use so-called optical alignment film.Optical alignment film refers to, generally passing through will be containing having photoreactivity The compositions (following sometimes referred to as " formation compositions used by light redirecting layer ") of the polymer of group or monomer and solvent It is coated on base material, base material is formed light orientation and lures aliquation, irradiated by polarized light (preferably polarized light UV) and give light and be orientated Lure aliquation to be orientated anchorage force, thus be formed with the alignment films of light redirecting layer.Photoreactive group is the irradiation (illumination by light Penetrate) and produce the group of liquid crystal aligning ability.Concrete, it is to be irradiated by light to occur the induction of product molecule to be orientated or different Structure reaction, dimerization reaction, photo-crosslinking, or photolysis reactions are such, cause the base of the photoreaction of liquid crystal aligning ability Group.In this photoreactive group, there is dimerization reaction or photo-crosslinking, have excellent orientation and form polarization film Time be maintained at smectic liquid crystal state, so preferably.As there is the above photoreactive group reacted, preferably comprise unsaturated bond Particularly double bond, particularly preferably containing by carbon-to-carbon double bond (C=C key), carbon-to-nitrogen double bond (C=N key), nitrogen-nitrogen double bond (N=N Key) and carbon-oxygen double bond (C=O key) in groups at least one group of selecting.

As the photoreactive group containing C=C key, such as, for example there are vinyl, polyene-based, base, stibazole The miscellaneous base of base, class, chalcone derivative base and cinnamoyl etc..As the photoreactive group containing C=N key such as example there are containing Aromatic series Schiff's base and the isostructure group of aromatic series hydrazone.As the photoreactive group containing N=N key, such as, for example there are idol Pyridyl, azo naphthyl, heteroaromatic azo group, bisazo base and methyl etc. or with azoxybenzide. etc. for basic structure The group made.As the photoreactive group containing C=O, such as, for example there are benzophenone base, coumarin base, anthraquinonyl and horse Carry out imide etc..These groups can contain alkyl, alkoxyl, aryl, allyloxy, cyano group, alkoxy carbonyl group, hydroxyl, sulphur The substituted radical such as acidic group and halogenated alkyl.

Wherein, the photoreactive group of light dimerization reaction, preferably cinnamoyl and chalcone derivative base preferably can occur, because The polarizing light irradiation amount necessary when its light is orientated is fewer, and, it is readily obtained heat stability and time stability is excellent Light redirecting layer.Furthermore, it is understood that as the terminal part of the polymer containing photoreactive group, particularly preferably this polymer lateral chain Point there is the cinnamoyl constituting cinnamic acid structure.

As the solvent of the compositions formed used by light redirecting layer, preferably dissolve the polymer with photoreactive group with And the solvent of monomer, as this solvent, such as, for example there are the solvent for above-mentioned orientation polymer composition.

Relative to the compositions formed used by light redirecting layer, the polymer containing photoreactive group or the concentration of monomer Can enter according to the thickness of the polymer containing this photoreactive group or the kind of monomer and optical alignment film to be manufactured Row suitably regulation, but when representing with solid component concentration, preferably at least 0.2 mass %, the model of particularly preferred 0.3 ~ 10 mass % Enclose.Meanwhile, in the range of the characteristic of inconspicuous infringement optical alignment film, said composition can comprise polyvinyl alcohol or polyimides Deng macromolecular material or photosensitizer.

As the method that the compositions formed used by light redirecting layer is coated on base material, can use spin-coating method, squeezing and pressing method, The rubbing methods such as rotogravure application method, mould cladding process, bar type cladding process and applicator method, or the print process such as flexo method etc. is known Method.During it addition, manufacture this polarization film, when implementing continuous print manufacture method by aftermentioned volume to volume form, this coating process Generally use the print processes such as rotogravure application method, mould cladding process or flexo method.

It addition, carry out rubbing or during polarizing light irradiation, if covered, multiple regions that differently-oriented directivity is different can be formed (pattern).

In the alignment films formed on above-mentioned base material or on base material, apply this compositions and remove solvent, obtaining coated film. As coating method (coating process), such as, for example there are and by the compositions used by orientation polymer or formation light redirecting layer The method that the method that is coated on base material is identical.

Then, by not gathering at the polymerizable liquid crystal compound contained by coated film and polymerism non-liquid crystal compound Remove solvent under conditions of conjunction, form coated film.As the method for removing, such as, for example there are natural seasoning, aeration-drying method, add Heated drying and hypobaric drying method etc..Afterwards, contained polymerizable liquid crystal compound display smectic liquid crystal phase in this coated film is made. Now, preferably by the characteristic of this polymerizable liquid crystal compound, first make its mesomorphic state display nematic liquid crystal mutually after, then make this to Row liquid crystal phase transition is smectic liquid crystal phase.The transformation of liquid crystalline phase as mentioned above, uses first by the polymerism contained by coated film Liquid-crystal compounds is heated to showing the temperature of more than nematic liquid crystal phase temperature, then is cooled to show by this polymerizable liquid crystal compound The methods such as the temperature showing smectic liquid crystal phase.

Polymerizable liquid crystal compound display smectic liquid crystal phase or the temperature of nematic liquid crystal phase in above-mentioned coated film, such as front institute State, try to achieve beforehand through the texture of this compositions is observed.

When polymerizable liquid crystal compound and polymerism non-liquid crystal compound polymerization, in order to make polymerizable liquid crystal compound intact Be maintained at smectic liquid crystal phase, as this polymerizable liquid crystal compound, be preferably used containing polymerizable liquid crystal chemical combination of more than two kinds This compositions of thing.This compositions using the content ratio that have adjusted this polymerizable liquid crystal compound of more than two kinds has such Advantage, its via nematic liquid crystal formed mutually smectic liquid crystal mutually after, even if at a temperature of original display crystallization mutually, it is also possible to temporarily Supercooled state can be in, thus be easily maintained at the mesomorphic state of high order smectic phase.Containing 2 kinds of polymerizable liquid crystal chemical combination During thing, the content ratio of 2 kinds of polymerizable liquid crystal compounds is usual at 1:99 ~ 50:50, and preferably 5:95 ~ 50:50, more preferably 10:90 ~ 50:50。

Then the polymerization process of polymerizable liquid crystal compound and polymerism non-liquid crystal compound is illustrated.

Polymerizable liquid crystal compound in coated film become smectic liquid crystal mutually after, be maintained at this smectic liquid crystal phase, one Limit, by irradiation energy in coated film, makes polymerizable liquid crystal compound and polymerism non-liquid crystal compound polymerization.Due to this Compositions contains polymerization initiator, preferably can irradiate the energy making polymerization initiator activate, and preferred energy such as example there are light.Make For irradiating light, according to the kind of polymerization initiator contained in this coated film, or polymerizable liquid crystal compound and the non-liquid of polymerism The kind (especially with the kind being polymerized base of this polymerizable liquid crystal compound) of crystallization compound and amount thereof, suitably visible Light, ultraviolet light and laser institute are middle in groups to be selected light or is carried out by active electron beam.Wherein, from being easily controlled polyreaction Carrying out or polymerization in the device that relates to be the most widely used setting out, preferably ultraviolet light.It is therefore preferable that select in advance Select polymerizable liquid crystal compound, polymerism non-liquid crystal compound and the kind of polymerization initiator contained in this compositions, with Can be polymerized by ultraviolet light.Simultaneously when polymerization, ultraviolet irradiates simultaneously can also be cold by suitable chiller But coated film is to control polymerization temperature.If by using such cooling way, it is possible to carry out polymerism liquid at lower temperatures Crystallization compound and the polymerization of polymerism non-liquid crystal compound, even if the material then having above-mentioned base material to use thermostability relatively low also may be used With the advantage being suitably formed this polarization film.It addition, during polymerization, by covering or developing, it is also possible to obtain patterned partially Shake light film.

By above-mentioned etc polymerization, the high order that above-mentioned polymerizable liquid crystal compound is maintained at smectic phase, the most illustrates Under the mesomorphic state of smectic phase, polymerization forms this polarization film.Polymerizable liquid crystal compound is maintained at the mesomorphic state of smectic phase and gathers Close this polarization film obtained, along with the effect of above-mentioned dichroism pigment, i.e. protect with conventional host and guest's build polarization film Hold the polarization film making the polymerizations such as polymerizable liquid crystal compound obtain at nematic mesomorphic state to compare, have polarization property more High advantage.Compare with the polarization film only applying dichroism pigment or lysotropic liquid crystal further, have intensity higher excellent Point.

The thickness of this polarization film so formed preferably scope below 10 μm more than 0.5 μm, further preferred 1 μm Below above 5 μm.Therefore, formed used by this polarization film the thickness of coated film, be this polarization film considering to obtain Determine after thickness.It addition, the thickness of this polarization film, it is through interfering film thickness gauge or laser microscope or contact pin type film thickness gauge Measure.

The transparency can pass through the assessment of turbidity (Haze) value.Preferably turbidity value is below 5%, and more preferably less than 2%.

Meanwhile, this polarization film so formed is as it has been described above, particularly preferably X-ray diffraction obtains bragg peak in measuring 's.As obtaining this polarization film of such bragg peak, include, for example display and derive from hexagonal phase or crystallization phase This polarization film of diffraction maximum.

Above the manufacture method of this polarization film is provided a brief description, when business manufactures this polarization film, it is desirable to It it is the method that can manufacture this polarization film with continuous print.Such method for continuous production is the method using volume to volume form, root It is referred to as according to occasion " this manufacture method ".It addition, this manufacture method illustrates centered by the base material situation as transparent base.

This manufacture method comprises such as,

Prepare transparent base and be wound on the operation of the 1st cylinder of gained in the 1st core,

The operation of transparent base is sent continuously by the 1st cylinder,

Operation over the transparent substrate is applied continuously by forming the compositions used by above-mentioned light redirecting layer,

Remove the solvent in the compositions used by formation light redirecting layer of coating, be formed continuously the first painting over the transparent substrate The operation of cloth film,

By this coated film being carried out polarized light UV irradiation, being formed continuously light redirecting layer, forming the operation of optical alignment film,

On this optical alignment film, the operation of this compositions of continuously coating,

It is coated with by being dried under conditions of not being polymerized at polymerizable liquid crystal compound and polymerism non-liquid crystal compound This compositions of cloth, is formed continuously the operation of the second coated film on this optical alignment film,

The mesomorphic state making in this coated film contained polymerizable liquid crystal compound become smectic liquid crystal mutually after, be maintained at Smectic liquid crystal phase, by making polymerizable liquid crystal compound be polymerized, is continuously available the operation of polarization film,

The laminate containing transparent base, optical alignment film and polarization film being continuously available is wound around the 2nd core, Operation to the 2nd cylinder.

This manufacture method is illustrated with reference to Fig. 1 at this.

The 1st cylinder 210 that transparent base winds around the 1st core 210A such as, can easily purchase in market.As The transparent base bought by market with the form of such cylinder, such as example there are in the transparent base having been illustrated that by Cellulose esters, annular ethylene series resin, Merlon, polyethylene terephthalate or polymethacrylates institute film forming Deng.Meanwhile, when this polarization film uses as circular polarization light board, the transparent base imparting phase contrast in advance also easily exists Market buys, such as, for example there are by cellulose esters, Merlon or the become phase retardation film of annular ethylene series resin etc..

Then, above-mentioned 1st cylinder 210 transparent base is sent.The method sending transparent base is at the 1st cylinder 210 Core 210A in suitable rotary apparatus is set, by this rotary apparatus rotate the 1st cylinder 210.In addition it is also possible to the 1st Cylinder 210 sends the direction of transparent base, arranges suitable auxiliary cylinder 300, is sent by the rotary apparatus of this auxiliary cylinder 300 Go out transparent base.It is further possible to the 1st core 210A and auxiliary cylinder 300 are arranged rotary apparatus simultaneously, sending Transparent base gives the tension force of its appropriateness simultaneously.

The transparent base sent by above-mentioned 1st cylinder 210, through apparatus for coating 211A, by this apparatus for coating 211A Coating in its surface forms the compositions used by light redirecting layer.Continuous print coating described above forms the group used by light redirecting layer This apparatus for coating 211A of compound, it is common that the printing dress of the coatings such as rotogravure application method, mould cladding process, flexo method can be carried out Put.

Through the film of apparatus for coating 211A, carry it to drying oven 212A, heated by this drying oven 212A, from Applied said composition removes solvent, is formed continuously the first coated film over the transparent substrate.As drying oven 212A such as Hot air type drying oven etc. can be used.The design temperature of drying oven 212A, the formation light according to being coated with by apparatus for coating 211A is taken In the compositions used by layer, the solvent-laden kind of institute etc. determine.Drying oven 212A can be divided into multiple region simultaneously, draws Point multiple regions each can set different temperature, it is also possible to multiple drying ovens of configuration series connection, its respective design temperature Can be different.

Through the first coated film that heating furnace 212A is formed continuously, continuously through polarized light UV irradiation unit 213A, can The surface of the surface of the first coated film or transparent base side is irradiated by through polarized light UV, forms light redirecting layer, form light Alignment films.

The base material being so formed continuously and the laminate of optical alignment film, then pass through through apparatus for coating 211B, by this group After compound is coated on optical alignment film, by polymerizable liquid crystal compound contained in drying oven 212B, shape cost composition Present the second coated film of smectic liquid crystal phase.Drying oven 212B is except for removing in this compositions being coated with on optical alignment film Solvent, is additionally operable to give this compositions thermal energy, makes contained polymerizable liquid crystal compound in this compositions be turned mutually by nematic liquid crystal Become smectic liquid crystal phase.In order to make polymerizable liquid crystal compound be smectic liquid crystal phase by nematic liquid crystal phase in version, drying oven 212B Multistage heat treated can be carried out.That is, drying oven 212B can be divided into multiple region in the same manner as drying oven 212A, draws Point multiple regions each set different temperature, it is also possible to multiple drying ovens of configuration series connection, its each design temperature different.

Via the film of above-mentioned drying oven 212B, solvent contained in this compositions is fully removed, poly-in the second coated film Conjunction property liquid-crystal compounds is maintained at smectic liquid crystal phase, is transported to light irradiation device 213B.Light by this light irradiation device 213B Irradiate, make polymerizable liquid crystal compound be maintained at smectic liquid crystal phase, together with polymerism non-liquid crystal compound by photopolymerization even Continue on optical alignment film, form this polarization film.

This polarization film being so formed continuously is as comprising the laminate of transparent base and optical alignment film around volume 2 Core 220A winds, and obtains the form of the 2nd cylinder 220.When obtaining 2 cylinder being wound with this polarization film formed, can be suitable Sept is used to wind together.

Irradiate as it has been described above, transparent base sequentially passes through 1 cylinder/apparatus for coating 211A/ drying oven 212A/ polarized light UV Device 213A/ apparatus for coating 211B/ drying oven 212B/ light irradiation device 213B, on optical alignment film over the transparent substrate continuously Manufacture this polarization film.

Meanwhile, this manufacture method display of Fig. 1 is from the method for continuous production of transparent base to this polarization film but it also may Such as, transparent base is made to pass sequentially through 1 cylinder/apparatus for coating 211A/ drying oven 212A/ polarized light UV irradiation unit 213A, The laminate of the base material being formed continuously and optical alignment film is centered around in core, by this laminate with the form manufacture of cylinder, this layer Long-pending body is sent by this cylinder, and this laminate sent passes sequentially through apparatus for coating 211B/ drying oven 212B/ light irradiation device 213B, produces this polarization film.

This polarization film obtained by this manufacture method, it is shaped as membranaceous and is strip.This this polarization film is used When aftermentioned liquid crystal indicator etc., desired size can be cut into use according to the scale etc. of this liquid crystal indicator.

Above, to this polarization film centered by the form of the laminate of transparent base/optical alignment film/this polarization film Constitute and manufacture method illustrates, but as the laminate containing this polarization film, can peel off from such laminate Optical alignment film or transparent base, it is also possible to be to be laminated with the layer outside transparent base/optical alignment film/this polarization film or film Form.As these layers and film, as it was previously stated, this polarization film can contain phase retardation film further, it is possible to further Ground is containing anti-reflection layer or brightness enhancement film.

Meanwhile, can be by transparent base self as phase retardation film, it is thus achieved that phase retardation film/optical alignment film/this polarized light The circular polarization light board of the form of film or elliptical polarization tabula rasa.Such as use 1/4 wavelength plate that uniaxial tension obtains as phase place During difference film, by setting the direction of illumination of the polarized light UV carriage direction relative to transparent base as substantially 45 °, can be right by rolling up Volume mode manufactures circular polarization light board.As 1/4 wavelength plate that used when manufacturing above-mentioned circular polarization light board, preferably have for can The characteristic that the interior phase difference value of meeting light shortens along with wavelength and diminishes.

Meanwhile, by using 1/2 wavelength plate as phase retardation film, its slow axis of the setting absorption axle with polarization film is made The linear polarization plate cylinder that angle staggers, forms 1/4 wavelength further in the side relative with the face forming this polarization film Plate, can obtain broadband circular polarization light board.

This polarization film may be used in various display device.Display device is the device containing display element, Contain the light-emitting component as luminous source or light-emitting device.As display device, such as, for example there are liquid crystal indicator, have Organic electro luminescent (EL) display device, inorganic EL (EL) display device, electron emission display (such as field emission Display device (FED), surface field emission display (SED)), Electronic Paper (use the display dress of e-inks or electrophoresis element Put, plasm display device, projection type image display apparatus (such as grating light valve (GLV) display device, containing numeral lenticule set The display device of standby (DMD)) and piezoelectric ceramics display etc..Liquid crystal indicator include transmissive liquid crystal display device, half Transmissive liquid crystal display device, reflection-type liquid-crystal display device, direct view liquid crystal display device and projection type liquid crystal's display dress Any one put etc..These display devices can be the display device showing 2 dimension images, it is also possible to is to show standing of 3 d image Body display device.

This polarization film can show in particularly organic electroluminescent (EL) display device or inorganic EL (EL) The display device of showing device effectively uses.

Fig. 2 and Fig. 5 is to represent that the liquid crystal indicator using this polarization film (is referred to as " this liquid below according to occasion Crystal device ".) 10 the generalized schematic of section constitution.Liquid crystal layer 17 is clipped between 2 plate substrate 14a and base material 14b.

Figure 10 is that the EL display device representing and using this polarization film (is referred to as below according to occasion that " this EL shows dress Put ") the generalized schematic of section constitution.

Figure 11 is the generalized schematic of the composition representing the projection-type liquid crystal display device using this polarization film.

First this liquid crystal indicator 10 shown Fig. 2 illustrates.

Liquid crystal layer 17 side of base material 14a is configured with color filter 15.Color filter 15 is arranged in and clamps the pixel of liquid crystal layer 17 On the position that electrode 22 is relative, black matrix" 20 is arranged on the position relative with the border between pixel electrode.Transparency electrode 16 It is configured at liquid crystal layer 17 side, to cover color filter 15 and black matrix" 20.It addition, can between color filter 15 and transparency electrode 16 With containing protecting film layer (not shown in the diagram).

Liquid crystal layer 17 side of base material 14b, is configured with thin film transistor (TFT) 21 and pixel electrode 22 regularly.Pixel electrode 22 Clip liquid crystal layer 17, be arranged in the position relative with color filter 15.It is configured with between thin film transistor (TFT) 21 and pixel electrode 22 and contains There is the interlayer dielectric 18 of connecting hole (not shown in the diagram).

As base material 14a and base material 14b, use glass baseplate and plastic basis material.Such glass baseplate or plastics Base material, uses and the material of the identical material of Exemplary materials of the transparent base of use when manufacturing this polarization film.Meanwhile, this polarization The transparent base of light film can double as base material 14a and base material 14b.Manufacture the color filter 15 and thin film transistor (TFT) formed on base material When 21, need the preferred glass baseplate of occasion or the quartz substrate of high-temperature heating operation.

Thin film transistor (TFT) uses most suitable material according to the material of base material 14b.As thin film transistor (TFT) 21, such as, illustrate There is low-temperature polycrystalline silicon transistor, the glass baseplate formed on the high temperature polysilicon silicon transistor formed in quartz substrate, glass baseplate Or the amorphous silicon transistor formed on plastic basis material.For making this liquid crystal indicator smaller, can on base material 14b shape The driving IC of Cheng Gan.

Liquid crystal layer 17 it is configured with between transparency electrode 16 and pixel electrode 22.In order to make between base material 14a and base material 14b Maintain a certain distance, liquid crystal layer 17 is configured with sept 23.Though it addition, illustrate column spacer in Fig. 2, this sept is also Being not limited to column, as long as certain distance can be made to keep between base material 14a and base material 14b, shape can be any.

The face contacted with liquid crystal layer 17 in the layer that base material 14a and base material 14b are formed, can be respectively configured can make liquid crystal with The oriented layer of desired direction orientation.It addition, this polarization film can be placed in inside liquid crystal cell, i.e. connecing with liquid crystal layer 17 Contacting surface side configures this polarization film.Such form is referred to as " embedded (in cell) formula ".

Each component is with base material 14a, color filter 15 and black matrix" 20, transparency electrode 16, liquid crystal layer 17, pixel electrode 22, interlayer dielectric 18 and thin film transistor (TFT) 21 and the sequential laminating of base material 14b.

In such base material 14a and base material 14b accompanying liquid crystal layer 17,14a and the outside of base material 14b, it is provided with Polarizer 12a and 12b, the polarizer that at least a part of which is 1 comprises this polarization film.

Further, it is preferable to lamination phase separation layer (such as 1/4 wavelength plate or optical compensation films) 13a and 13b.Polarizer In 12a and 12b, by being inserted by this polarization film in polarizer 12b, this liquid crystal indicator 10 can be given by incident illumination It is transformed to the function of rectilinearly polarized light.It addition, according to liquid-crystal compounds contained in the structure of liquid crystal indicator or liquid crystal layer 17 Kind, phase retardation film 13a and 13b can not be configured, when transparent base is phase retardation film, use containing this polarization film During (ellipse) circular polarization light board, owing to this phase retardation film as phase separation layer, therefore can also omit the phase separation layer of Fig. 2 13a and/or 13b.Polariscopic smooth emitting side (outside) containing this polarization film can arrange polarized light further Film.

Meanwhile, polariscopic outside containing this polarization film (when this polarization film is provided with polarization film further, Outside it), for preventing the reflection of exterior light from can arrange antireflection film.

As it has been described above, polarizer 12a or 12b of this liquid crystal indicator of Fig. 2 10 can use this polarization film.

By being arranged in polarizer 12a and/or 12b by this polarization film, it is finally reached this liquid crystal display dress Put the effect of 10 further slimmings.

When this polarization film is in polarizer 12a or 12b, its laminated order is not particularly limited.To this with reference to Fig. 2 A that dotted line surrounds and the expanded view explanation of part B.

Fig. 3 is the enlarged cross section schematic diagram of the part A of Fig. 2.(A1) display polarizer 100 of Fig. 3 makes as polarizer 12a Used time, arrange by the order of this polarization film 3, optical alignment film 2 and transparent base 1 in phase separation layer 13a side.Meanwhile, Fig. 3 (A2) the order setting of transparent base 1, optical alignment film 2 and this polarization film 3 is pressed in display in phase separation layer 13a side.

Fig. 4 is the expansion schematic diagram of the part B of Fig. 2.(B1) display polarizer 100 of Fig. 4 uses as polarizer 12b Time, the order pressing transparent base 1, optical alignment film 2 and this polarization film 3 in phase retardation film 13b side is arranged.Meanwhile, Fig. 4 (B2) display polarizer 100 is when using as polarizer 12b, press in phase separation layer 13b side this polarization film 3, optical alignment film 2 with And the order of transparent base 1 is arranged.

The outside of polarizer 12b, is provided with the backlight module 19 as luminous source.Backlight module 19 is containing light source, leaded light Body, reflecting plate, diffusion sheet and visual angle tab.As light source, such as example there are electroluminescent, cold-cathode tube, hot cathode tube, Light emitting diode (LED), laser light source and mercury lamp etc..Meanwhile, light source characteristic can be compareed, select the kind of this polarization film Class.

When this liquid crystal indicator 10 is transmissive liquid crystal display device, white with produce from light source in backlight module 19 Coloured light incidence light conductor, is reflected plate conversion light path and spreads in diffusion sheet.Diffusion light is adjusted to expectation by visual angle tab Directivity, by backlight module 19 incident polarization mirror 12b.

As the incident illumination of no polarization, the polarizer 12b of only a certain rectilinearly polarized light permeate crystal panel.This straight line Polarized light is transformed to circularly polarized light or elliptically polarized light by phase separation layer 13b, successively through base material 14b, pixel electrode 22 Deng arrival liquid crystal layer 17.

According to the presence or absence of potential difference between the transparency electrode 16 relative with pixel electrode 22 herein, contained in liquid crystal layer 17 The state of orientation change of liquid crystal molecule, controls the brightness of the light penetrated by this liquid crystal indicator 10.When liquid crystal layer 17 is at polarization When light is directed through its state of orientation, this polarized light permeate crystal layer 17, transparency electrode 16, the light of certain particular range of wavelengths Arriving polarizer 12a through color filter 15, liquid crystal indicator can show the color high-high brightness that color filter determines.

On the contrary, when liquid crystal layer 17 is when changing the state of orientation that polarized light passes it through, permeate crystal layer 17, transparent electrical The light of pole 16 and color filter 15 is absorbed in polarizer 12a.By this, this pixel display black.In these 2 states Between state of orientation time, this liquid crystal indicator 10 brightness of the light penetrated is also above-mentioned in the middle of both, and the most now pixel shows Show Neutral colour.

When this liquid crystal indicator 10 is transflective liquid crystal display device, the polarization photosphere of this polarization film is preferably used The side thing (circular polarization light board) that lamination 1/4 wavelength plate is become further.Now, pixel electrode 22 is formed containing transparent material Transmissive portions, the reflecting part that light reflecting material is formed, display image as above-mentioned transmissive liquid crystal display device in transmissive portions. On the other hand, at reflecting part, exterior light is injected in liquid crystal indicator, 1/4 ripple being had further by this polarization film The effect of long slab, the circularly polarized light through this polarization film passes through liquid crystal layer 17, reflects through pixel electrode 22, thus be used for showing Show.

Then, this EL display device 30 to this polarization film of use, illustrate with reference to Fig. 8.In this EL display device When using this polarization film, preferably this polarization film is made circular polarization light board (be sometimes referred to as below " this circularly polarized light Plate ".) use afterwards.This circular polarization light board generally has 2 embodiments.Therefore, the composition etc. of this EL display device 30 is being carried out Before explanation, 2 embodiments to this circular polarization light board, illustrate with reference to Fig. 6.

(A) of Fig. 6 represents the schematic cross-section of the 1st embodiment of this circular polarization light board 110.1st embodiment is Polarizer 100 arranges on this polarization film 3 this circular polarization light board 110 of phase separation layer (phase retardation film) 4 further.Fig. 6 (B) represent the schematic cross-section of the 2nd embodiment of this circular polarization light board 110.2nd embodiment is as manufacturing partially The transparent base used during galvanometer 100, uses the transparent base 1 (phase retardation film 4) imparting phase contrast in advance, the most transparent Base material 1 is this circular polarization light board 110 self having both and having the function as phase separation layer 4.

Herein, the manufacture method of this circular polarization light board 110 is illustrated.2nd embodiment of circular polarization light board 110 is such as Upper described, manufacture in this manufacture method of this polarization film 100, the transparent of phase contrast can be had been assigned in advance by using Base material 1, i.e. phase retardation film manufacture as transparent base.1st embodiment of circular polarization light board 110, by this manufacture Laminating phase retardation film on this polarization film that method B is fabricated by 3, forms phase separation layer 4.It addition, by this manufacturer Method B, when manufacturing this polarization film 100 with the form of the 2nd cylinder 220, can be exported this polarized light by the 2nd cylinder 220 uncoiling Film 100, after being cut to the size of regulation, phase retardation film that this polarization film after cutting 100 is fitted；But can also be ready to The 3rd cylinder that phase retardation film winds around core, manufactures continuously and is shaped as membranaceous and this circular polarization light board 110 of strip.

Method for continuous production to the 1st embodiment of circular polarization light board 110, illustrates with reference to Fig. 7.Such manufacture Method is made up of following operation:

This polarization film 100 is being exported simultaneously, by wrapped around the 3rd of phase retardation film by the above-mentioned 2nd continuous uncoiling of cylinder 220 The continuous uncoiling of cylinder 230 exports the operation of above-mentioned phase retardation film,

The polarization photosphere that this polarization film 100 of above-mentioned 2nd cylinder 220 uncoiling output is provided with is rolled with by the above-mentioned 3rd Cylinder winds off the above-mentioned phase retardation film of output and fits continuously, forms the operation of this circular polarization light board 110,

This circular polarization light board 110 formed, around entering the 4th core 240A, obtains the operation of the 4th cylinder 240.

Above the manufacture method of the 1st embodiment of this circular polarization light board 110 is described, the basis in polarizer 100 When polarization film 3 is fitted with phase retardation film, it is possible to use suitable binding agent, by the adhesive layer formed by this binding agent, will This polarization film 3 is fitted with phase retardation film.

Then this EL display device containing this circular polarization light board 110 is illustrated with reference to Fig. 8.

This EL display device 30 is on the base material 33 forming pixel electrode 35, by the organic function layer 36 as luminous source And cathode electrode 37 lamination is formed.In the side relative with the organic function layer 36 accompanying base material 33, it is configured with circularly polarized light Plate 31, such circular polarization light board 31 uses this circular polarization light board 110.By pixel electrode 35 being applied positive voltage, negative electrode electricity Pole 37 applies to be passed through between negative voltage, pixel electrode 35 and cathode electrode 37 DC current, and organic function layer 36 is luminous.As The organic function layer 36 of luminous source is made up of electron supplying layer, luminescent layer and hole transporting layer.Penetrated by organic function layer 36 The light gone out, through pixel electrode 35, interlayer dielectric 34, base material 33, circular polarization light board 31 (this circular polarization light board 110).Although It is the explanation that the organic EL display containing organic function layer 36 is carried out, is also applied for the inorganic EL containing inorganic functional layer Display device.

Manufacture this EL display device 30, on base material 33, first form the thin film transistor (TFT) 40 of desired shape.Make afterwards Interlayer dielectric 34 film forming, then makes pixel electrode 35 film forming with sputtering method, forms pattern, and then, lamination becomes organic function layer 36。

Then, at the reverse side of the one side being provided with thin film transistor (TFT) 40 of base material 33, circular polarization light board 31 (this circular polarization is set Tabula rasa 110).

When this circular polarization light board 110 uses as circular polarization light board 31, to its laminated order with reference to the dotted line of Fig. 8 The expanded view of C portion illustrates.When this circular polarization light board 110 uses as circular polarization light board 31, this this circular polarization light board 110 Middle phase separation layer 4 is arranged in base material 33 side.(C1) of Fig. 9 is that the 1st embodiment of this circular polarization light board 110 is as circularly polarized light The expanded view that plate 31 uses, (C2) of Fig. 9 is that the 2nd embodiment of this circular polarization light board 110 uses as circular polarization light board 31 Expanded view.

Then the component outside this polarization film 31 (circular polarization light board 110) of this EL display device 30 is carried out briefly Bright.

As base material 33, such as, for example there are sapphire glass base material, quartz glass base material, soda glass base material and oxidation The ceramic base materials such as aluminum；The metal bases such as copper；Plastic basis material etc..Although it is not shown in the figure that heat biography can be formed on base material 33 The property led film.As heat conductivity film, such as, for example there are diamond thin (DLC etc.) etc..When pixel electrode 35 is reflection-type, light to The direction outgoing reverse with base material 33.Therefore transparent material it is not only, it is possible to use the non-permeable material such as rustless steel.Base material can Be a separately formed, it is also possible to be the lamination base material multiple base materials binded with adhesive.Meanwhile, these base materials do not limit In tabular, it is also possible to be film.

Polysilicon transistors etc. such as can be used as thin film transistor (TFT) 40.Thin film transistor (TFT) 40 is arranged at pixel electrode 35 End, its size is about 10 ~ 30 μm.It addition, the size of pixel electrode 35 is left in 20 μ m 20 μm ~ 300 μ m 300 μm Right.

Thin film transistor (TFT) 40 distribution electrode it is provided with on base material 33.The resistance of distribution electrode is low, itself and pixel electrode 35 electricity Have the function of suppression resistance value after connection, general this distribution electrode use containing Al, Al and transition metal (removing Ti), In Ti or titanium nitride (TiN) any a kind or of more than two kinds.

Interlayer dielectric 34 is set between thin film transistor (TFT) 40 and pixel electrode 35.Interlayer dielectric 34 can be SiO₂Deng oxygen The inorganic material such as SiClx, silicon nitride is through sputtering or the material of vacuum evaporation film forming, use SOG (スピ Application オ Application グラス；Rotation Painting formula glass method) film etc. of the resin system material such as silicon oxide layer, photoresist, polyimides and acrylic resin of being formed has Any one of the material of insulating properties.

Rib 41 is formed on interlayer dielectric 34.Rib 41 is configured at the periphery (adjacent pixels of pixel electrode 35 Between).As the material of rib 41, such as, for example there are acrylic resin and polyimide resin etc..The thickness of rib 41 More than preferably 1.0 μm, below 3.5 μm, more than more preferably 1.5 μm, below 2.5 μm.

Then to the pixel electrode 35 as transparency electrode, the organic function layer 36 as luminous source and cathode electrode 37 shape The EL element become illustrates.Organic function layer 36 each at least contains hole transporting layer and the luminescent layer of 1 layer, the most successively Transfer layer, luminescent layer, hole transporting layer and hole injection layer is injected containing electronics.

As pixel electrode 35, such as example there are ITO (Indium sesquioxide. of doped tin), IZO (Indium sesquioxide. of doping zinc), IGZO、ZnO、SnO₂And In₂O₃Deng, particularly preferred ITO or IZO.The thickness of pixel electrode 35, as long as fully note hole The thickness entered, preferably about 10 ~ 500nm.

Pixel electrode 35 can pass through vapour deposition method (preferably sputtering method) and be formed.As sputter gas, it is not particularly limited, can make By the noble gases such as Ar, He, Ne, Kr and Xe or the mixed gas of these gases.

As the constituent material of cathode electrode 37 can use K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, The metallic elements such as Zn and Zr, in order to improve the job stability of electrode, are preferably used by illustrating 2 kinds of one-tenth of selection in metallic element Divide or the alloy body of 3 kinds of compositions.As alloy body, the most such as Ag Mg (Ag:1 ~ 20at%), Al Li (Li:0.3 ~ 14at%), In Mg (Mg:50 ~ 80at%) and Al Ca (Ca:5 ~ 20at%) etc..

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

Hole injection layer has to be made to be injected hole by pixel electrode 35 and becomes easy function, and hole transporting layer has conveying The function in hole and the function of obstruction electronics, referred to as electric charge injection layer or charge transport layer.

Thickness, the hole injection layer of luminescent layer is merged thickness and the thickness of electronics injection transfer layer with hole transporting layer Degree is not particularly limited, though can be different according to forming method, but preferably about 5 ~ 100nm.Hole injection layer or cavity conveying Layer can use various organic compound.When forming hole injection transfer layer, luminescent layer and electronics injection transfer layer, from permissible The point forming homogenizing thin film considers, it is possible to use vacuum vapour deposition.

Organic function layer 36 as luminous source, it is possible to use utilize the material of luminescence (fluorescence) of singlet exciton, profit With the material of the luminescence (phosphorescence) of triplet excitons, containing utilize singlet exciton luminescence (fluorescence) material with utilize three lines The material of the material of the luminescence (phosphorescence) of state exciton, the material formed by Organic substance, containing the material formed by Organic substance With the material of material formed by inorganic matter, macromolecular material, low molecule material, containing macromolecular material and low molecule material Material etc..But it is not limited to this, uses the organic function layer 36 as various material known to used by EL element May be used in this EL display device 30.

Space between cathode electrode 37 and cap 39 is configured with desiccant 38, because organic function layer 36 is weak to Wet.Absorb moisture by desiccant 38 and be possible to prevent the deterioration of organic function layer 36.

Figure 10 represents the skeleton diagram of the section constitution of other modes of this EL display device 30.This this EL display device 30 has There is the closed construction employing thin film sealing film 41, it is also possible to obtained emergent light by the reverse side of array base material.

As thin film sealing film 41, being preferably used on the film of electrochemical capacitor evaporation has the DLC film of DLC (diamond like carbon). DLC film has and is very difficult to by the characteristic of moisture penetration, and moisture-proof characteristic is higher.Meanwhile, DLC film etc. directly can be deposited with at electrode The surface of 37 is formed.It is also possible to resin film and metallic film multilamellar lamination form thin film sealer 41.

As mentioned above, it is provided that a kind of polarization film (this polarization film) with novelty that the present invention relates to, Yi Jihan There is the display device (this liquid crystal indicator and this EL display device) with novelty of this polarization film.

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

Figure 11 is the skeleton diagram representing the projection-type liquid crystal display device using this polarization film.

Polarizer 142 and/or the polarizer 143 of this projection-type liquid crystal display device use this polarization film.

As luminous source light source (such as high voltage mercury lamp) by 111 injection light shafts, first pass around the 1st lens arra 112, the 2nd lens arra 113, polarized light conversion element 114, compound lens 115, it is achieved the brightness in Reflect light line area of beam equal One change is photochemical with polarization.

Specifically, light source 111 light shafts penetrated, be formed as the 1st rectangular lens arra by lenticule 112a 112 are divided into multiple small light shafts.Configure the 2nd lens arra 113 and compound lens 115, so that divided light Bundle irradiates the entirety of 3 liquid crystal panels 140R, 140G, 140B as lighting object, therefore, each liquid crystal panel light incident side respectively Surface is integrally formed the most homogeneous illumination.

Polarization 114 is made up of polarized beam separation array, is arranged in the 2nd lens arra 113 saturating with compound Between mirror 115.Thus, the random polarized light from light source can be converted to the polarized light with specific polarization light direction in advance, Reduce in the polariscopic light loss of aftermentioned light incident side, it is achieved improve the effect of picture brightness.

Brightness homogenization as above and polarize photochemical light, via reflecting mirror 122, pass sequentially through dichroic mirror 121, 123,132 3 primary colors of RGB are separated, separate to red channel, green channel, blue channel, be incident to liquid crystal panel respectively 140R、140G、140B。

In liquid crystal panel 140R, 140G, 140B, being configured with polarizer 142 at its light incident side respectively, exiting side is configured with partially Galvanometer 143.This polarizer 142, polarizer 143 can use this polarization film.

The polarizer 142 configured in each light path of RGB and polarizer 143, be configured to respective absorption axle orthogonal.Each light path Each liquid crystal panel 140R, 140G, 140B of middle configuration, is had the polarized light state of each pixel controlled by picture signal It is transformed to the function of light quantity.

This polarization film 100 is by selecting to be suitable for the kind of dichroism pigment of respective channel, as blue channel, green The polarization film that in chrominance channel and red channel, in arbitrary light path, durability is all excellent is all useful.

According to the view data of liquid crystal panel 140R, 140G, 140B, enter according to the absorbance transmission different with each pixel Penetrate the optical image that light is made, synthesize in cross colour splitting prism 150, by projecting lens 170, projection screen 180 amplifies and throws Shadow.

As Electronic Paper, can enumerate and be orientated, by optical anisotropy and dye molecule, the dress that such molecule carries out showing Put；Moved by electrophoresis, particle, crystal grain rotates, the particle of phase change etc carries out the device that shows；Entered by one end of film The mobile device carrying out showing of row；The device shown is carried out by the color development/phase change of molecule；It is absorbed into by the light of molecule The device of row display；Be combined with hole by electronics and be produced from the device etc. that luminescence is indicated.More specifically, can enumerate micro- Capsule-type electrophoresis, horizontal motion electrophoresis, vertically-moving electrophoresis, spherical twist ball type, magnetic twist ball type, cylinder reverse ball Type, charged toner, electronic powder fluid, magnetophoresis type, magnetic heat seeking, electrowetting, light scattering (transparent/nebulousurine change), cholesteric liquid Crystalline substance/optical conductive layer, cholesteric liquid crystal, bistability nematic liquid crystal, Ferroelectric liquid Crystals, dichromatic pigment liquid crystal decentralized, can Dynamic film, according to the colour changing of leuco dye, photochromic, electrochromism, electro-deposition, flexible organic EL etc..Electronic Paper not only can be answered For text or the personal use of image, apply also for advertisement and show (label) etc..According to this polarization film, electronics can be reduced The thickness of paper.

As 3 d display device, micro-polarized light of motion the most (Japanese Patent Laid-Open 2002-185983 publication) The method of alternately arranged different phase retardation film as film (μ Pol), when the blooming of the present invention uses as polarization film, Pattern can be readily formed by printing, ink-jet, photoetching technique etc., it is therefore possible to shorten the manufacturing process of display device, and not Need phase retardation film again.

Embodiment

Hereinafter, described in detail the present invention further by embodiment.In following embodiment " % " and " part ", as long as Record the most especially, represent quality % and mass parts.

In the present embodiment, use following polymerizable liquid crystal compound.

Compound (1-6) (compound that following formula (1-6) represents)

Compound (1-6) is by Lub et al.Recl.Trav.Chim.Pays-Bas, 115,321-328 (1996) The method synthesis recorded.

(mensuration of phase transition temperature)

The phase transition temperature of compound (1-6), is by obtaining the phase transition temperature by compound (1-6) institute film forming and true Fixed, its operation is as follows.

In the alignment films formed on glass baseplate, being formed by film formed by compound (1-6), limit is heated, and limit is by polarization The texture of light microscope (BX-51, Olympus society system) is observed and is determined phase transition temperature.By compound (1-6) institute film forming, can be true After fixed its is warming up to 120 DEG C, during cooling, it is changed into nematic phase 112 DEG C of phases, is changed into smectic C 110 DEG C of phases, 94 DEG C of phases are changed into smectic B.

Compound (1-7) (compound that following formula (1-7) represents)

Compound (1-7) synthesizes with reference to the synthesis of above-claimed cpd (1-6).

(mensuration of phase transition temperature)

Mensuration mode as the phase transition temperature measuring compound (1-6) determines the phase in version temperature of compound (1-7) Degree.After compound (1-7) is warming up to 140 DEG C, during cooling, it is changed into nematic phase 133 DEG C of phases, is changed into 118 DEG C of phases Smectic C, is changed into smectic B 78 DEG C of phases.

Embodiment 1

(preparations of this compositions etc.)

Mixing following compositions, stirs 1 hour at 80 DEG C, obtains this compositions (forming the compositions used by polarization film)

Polymerizable liquid crystal compound；Compound (1-6) 75 parts

Compound (1-7) 25 parts

Dichroism pigment；Compound (2-1-1) 2.5 parts

The D10 pigment that No. 3687130 publications of Japanese Patent No. are recorded

Polymerization initiator；

1-hydroxycyclohexylphenylketone

((ィ Le ガキュァ 184: Ciba company limited (チバスペシャ Le ティケミカ Le ズ society) system)

6 parts

Levelling agent: BYK 361N (BYK-Chemie society system) 1.5 parts

Polymerism non-liquid crystal compound；Polyfunctional acrylic ester (4-5) 5.0 parts

Solvent: Ketocyclopentane 250 parts

(mensuration of phase transition temperature)

In the same manner as compound (1-6) and compound (1-7), obtain this compositions that mode is prepared as described above The phase transition temperature of the polymerizable liquid crystal compound contained by.It is warming up to 140 DEG C, during cooling, is changed into nematic 109 DEG C of phases Phase, does not forms phase-separated state, is changed into smectic C 98 DEG C of phases, does not forms phase-separated state, the phase in version when 74 DEG C For smectic B, do not form phase-separated state.

1. the formation of alignment films

Glass baseplate is used as transparent base.

On this glass baseplate, by spin-coating method pva coating (the fully saponified type of polyvinyl alcohol 1000, and light pure medicine work Industry Co., Ltd. system) 2 mass % aqueous solutions (formed compositions) used by oriented layer, the dried film forming thickness 100nm. Then, the surface to the film obtained is implemented friction treatment and is formed oriented layer, making polarization film.Friction treatment uses semi-automatic rubbing Wipe device (trade name: LQ-008 type, Joyo Engineering Co., Ltd.'s system), by cloth (trade name: YA-20-RW, lucky river chemical industry strain Formula commercial firm system), in pressure away from 0.15mm, rotating speed 500rpm, carry out under conditions of 16.7mm/s.Through such friction treatment, Obtain being formed with the laminate 1 of alignment films on glass baseplate.

2. the formation of polarization film

In the alignment films of laminate 1, form the compositions used by above-mentioned polarization film, at 120 DEG C by spin-coating method coating Hot plate on heat drying 1 minute, be rapidly cooled to room temperature, above-mentioned alignment films formed coated film.In such coated film The mesomorphic state of contained polymerizable liquid crystal compound is smectic B.Then, with UV irradiation unit (SPOT CURE SP-7；ゥシォ Electric Co., Ltd system), by light exposure 2000mJ/cm²To coated film irradiation ultraviolet radiation under (313nm benchmark), this painting In cloth film, contained polymerizable liquid crystal compound is maintained under above-mentioned mesomorphic state polymerization, this coated film make polarization film.This Time by laser microscope (society of Olympus Co., Ltd OLS3000) mensuration polarization film thickness, be 1.6 μm.

3.X ray diffraction determination

For the polarization film obtained, use X-ray diffraction device X ' Pert PRO MPD (スペ Network トリス Co., Ltd. System) carry out X-ray diffraction mensuration.Use Cu as target, produce under conditions of x-ray tube current 40mA, x-ray tube voltage 45kV Raw X-ray is incident, with 2 in the range of sweep limits 2 θ=4.0 ~ 40.0 ° by differently-oriented directivity by fixing divergent slit 1/2 ° The step width of θ=0.01671 ° is scanned the result measured, and obtains half peak breadth (FWHM)=about near 2 θ=20.24 ° The sharp-pointed bragg peak of 0.1718 °.Meanwhile, entering by the direction parallel and vertical with differently-oriented directivity with polarization film surface Penetrate and also obtain comparable results.It is about according to the lattice period (order cycle) (d) that peak position is obtainedIt can thus be appreciated that formed The structure of reflection high order smectic phase.

4. the mensuration of dichroic ratio (DR)

It is determined by the following procedure dichroic ratio.

Use the folding being provided with the subsidiary polarizer on spectrophotometer (Shimadzu Corporation UV-3150) The device of device, by dijection collimation method, measures maximum absorption wavelength at transmission axial absorbance (A¹) and absorb direction of principal axis Absorbance (A²).This folding device is provided with the mesh screen blocking 50% light quantity in reference side.With the axial extinction of the transmission measured Degree (A¹) and absorb axial absorbance (A²) value calculate than (A²/A¹), as dichroic ratio.Dichroic ratio is the highest, then polarized light The characteristic of film is the most excellent.Absorb axial absorbance (A²) maximum absorption wavelength and the measurement result of dichroic ratio of this wavelength Displayed in Table 1.

5. the mensuration of turbidity value

For confirming this polariscopic transparency, with transmissometer (HZ-2；スガ testing machine (strain) makes) measure turbidity value.It is surveyed Determine result displayed in Table 1.

Embodiment 2 ~ 8, reference example 1, comparative example 1 ~ 2 in addition to changing kind and the content of polymerism non-liquid crystal compound, Other cost composition the most processed.Meanwhile, comparative example 3 making group under conditions of being added without polymerism non-liquid crystal compound Compound, after being coated with and being moved quickly to after drying on the hot plate of 70 DEG C at 120 DEG C, makes polarization film under UV exposes. The result measured respectively is displayed in Table 1.

In embodiment 9 ~ 15, dichroism pigment changes following structural formula (2-3-1) into, except polymerism non-liquid crystal compound Outside kind changes with content, other makes polarization film similarly to Example 1.The result measured respectively is displayed in Table 1.

Table 1

There is not phase-separated state in embodiment 1 ~ 15, demonstrates the dichroism of good parallel-oriented property and height.Good Good parallel-oriented property is because polymerizable liquid crystal compound display nematic liquid crystal phase, and the dichroism of height is because polymerism Liquid-crystal compounds display smectic liquid crystal phase.

Industrial utilizability

This polarization film is suitable as display device (display).Accordingly, it is capable to manufacture the basis of such polarization film Compositions industrially has height use value.

Claims

1. a polarization film, is formed by the compositions formed used by polarization film, it is characterised in that described compositions contains poly- Conjunction property liquid-crystal compounds, polymerism non-liquid crystal compound, dichroism pigment, polymerization initiator and solvent, and below meeting (A) essential condition and (B) essential condition, described polymerizable liquid crystal compound is maintained at smectic phase,

(B) polymerizable liquid crystal compound contained in the coated film obtained by the compositions formed used by polarization film does not haves Phase-separated state, and be as cooling and transferred to smectic liquid crystal phase mutually mutually by nematic liquid crystal.

Polarization film the most according to claim 1, it is characterised in that polymerizable liquid crystal compound is the change shown in formula (1) Compound,

U¹-V¹-W¹-X¹-Y¹-X²-Y²-X³-W²-V²-U²(1)

In formula, X¹、X²And X³It is to represent independently of each other containing substituent group or the Isosorbide-5-Nitrae-phenylene without substituent group or contain Substituent group or the hexamethylene-Isosorbide-5-Nitrae-diyl without substituent group, but, X¹、X²And X³Among at least 1 be containing substituent group or Isosorbide-5-Nitrae-phenylene without substituent group；Constitute-the CH of hexamethylene-Isosorbide-5-Nitrae-diyl₂-replaced by-O-,-S-or-NR-or not by Replace；R represents alkyl or the phenyl of carbon number 1～6；Y¹And Y²Expression-CH independently of each other₂CH₂-、-CH₂O-、- COO-,-OCOO-, singly-bound ,-N=N-,-CR^a=CR^b-,-C ≡ C-or-CR^a=N-；R^aAnd R^bRepresent hydrogen independently of each other Atom or the alkyl of carbon number 1～4；U¹Represent hydrogen atom or polymerism base；U²Represent polymerism base, W¹And W²Phase Represent singly-bound ,-O-,-S-,-COO-or-OCOO-independently mutually；V¹And V²Represent independently of each other containing substituent group or not The alkylidene of the carbon number 1～20 containing substituent group, constitutes-the CH of this alkylidene₂-replaced by-O-,-S-or-NH-or not It is replaced.

Polarization film the most according to claim 1 and 2, it is characterised in that polymerism non-liquid crystal compound is simple function third Olefin(e) acid ester or polyfunctional acrylic ester.

Polarization film the most according to claim 1, it is characterised in that the polymerizable group that polymerizable liquid crystal compound contains The polymerizable group contained with polymerism non-liquid crystal compound is independently of one another acryloxy (CH₂=CHCOO-) or first Base acryloxy (CH₂=C (CH₃)COO-)。

Polarization film the most according to claim 1, it is characterised in that the polymerizable group that polymerizable liquid crystal compound contains The polymerizable group contained with polymerism non-liquid crystal compound is identical group.

Polarization film the most according to claim 1, it is characterised in that polymerizable liquid crystal compound intramolecular contains 1～2 Polymerizable group, polymerism non-liquid crystal compound molecule is contained within 2～6 polymerizable groups.

Polarization film the most according to claim 1, it is characterised in that the content of polymerism non-liquid crystal compound is relative to poly- Conjunction property liquid-crystal compounds 100 mass parts, is more than 3 mass parts, below 10 mass parts.

8. the manufacture method of a polarization film, it is characterised in that containing following (I), (II) and (III) operation:

(I) compositions used by polarization film that formed described in any one of claim 1～7 is coated on base material or base material In the alignment films of upper formation, remove solvent and form the operation of coated film；

(II) polymerizable liquid crystal compound contained in the coated film formed in (I) operation is made to become the work of smectic liquid crystal phase state Sequence；

(III), in coated film that formed in (II) operation, that polymerizable liquid crystal compound is smectic liquid crystal phase state, polymerization is made Property liquid-crystal compounds and polymerism non-liquid crystal compound copolymerization operation.

The manufacture method of polarization film the most according to claim 8, it is characterised in that base material implements orientation process Transparent base.

The manufacture method of the polarization film the most according to Claim 8 or described in 9, it is characterised in that (II) operation comprises, and adds Heat treatment is until polymerizable liquid crystal compound contained in the coated film of formation in (I) operation shows the operation of nematic liquid crystal phase (I-1), cool down, directly with by middle for operation (I-1) coated film that this polymerizable liquid crystal compound is nematic liquid crystal phase state formed Operation (I-2) to this polymerizable liquid crystal compound display smectic liquid crystal phase.

11. 1 kinds of polarization films, it is characterised in that by the manufacture method manufacture described in any one of claim 8～10.

12. polarization films according to claim 11, its X-ray diffraction shows bragg peak in measuring.

13. 1 kinds of display devices, it includes the polarization film described in claim 11 or 12.