CN102220138A - Polymerization type liquid crystal composition, cholesteric type reflective film, and reflective type polarizing plate - Google Patents

Polymerization type liquid crystal composition, cholesteric type reflective film, and reflective type polarizing plate Download PDF

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CN102220138A
CN102220138A CN2011100838091A CN201110083809A CN102220138A CN 102220138 A CN102220138 A CN 102220138A CN 2011100838091 A CN2011100838091 A CN 2011100838091A CN 201110083809 A CN201110083809 A CN 201110083809A CN 102220138 A CN102220138 A CN 102220138A
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carbonatoms
liquid crystal
cholesteric
alkyl
oco
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桑名康弘
长谷部浩史
西山伊佐
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Abstract

The invention provides a polymerization type liquid crystal composition which can easily expand the reflecting wavelength choosing range of a cholesteric type reflective film and has excellent productivity. Meanwhile, the invention provides a cholesteric type reflective film using the polymerization type liquid crystal composition and having an excellent appearance and a reflective type polarizing plate. The invention provides the polymerization type liquid crystal composition and the cholesteric type reflective film formed by the polymerization type liquid crystal composition. The polymerization type liquid crystal composition is characterized in that the composition comprises one or more than two (a) liquid crystal compounds illustrated in the formula (1), one or more than two (b) liquid crystal compounds having only one polymerization functional group, one or more than two (c) liquid crystal compounds having more than two polymerization functional groups, one or more than two (d) chiral compounds having more than one polymerization functional group and one or more than two (e) polymerization initiator. R1-Z1-B-A-B-Z2-R2 (1).

Description

Polymerizable liquid crystal compound, cholesteric reflectance coating, reflection-type Polarizer
Technical field
The present invention relates to as liquid crystal device, indicating meter, optics, tinting material, safety with useful polymerizable liquid crystal compounds such as sign, laser apparatus illuminating members, and the cholesteric light polarizing film, the reflection-type Polarizer that obtain by the polymerisable liquid crystal composition.
Background technology
Utilize the exploitation of Polarizer of the selection reflection characteristic of cholesteryl liquid crystal to begin to prevail from nineteen ninety.For cholesteryl liquid crystal as Polarizer, need make the wavelength region of selecting reflection in visible-range, and by the pitch (pitch) of cholesteryl liquid crystal is made as the value of defined, thereby can obtain polarized light property.Yet, the occasion of in nematic liquid crystal, adding chipal compounds, because its pitch generally remains a constant pitch, thereby the selection that can only obtain the specific narrow range of wavelengths corresponding with it is reflected.Therefore, the someone attempts by the research cholesteric liquid crystal compositions to enlarge the wavelength region of selecting reflection.
As one of them method, disclose a kind of in the polymerizability cholesteryl liquid crystal, thereby the polymerization velocity of shadow surface by being controlled at light and non-shadow surface is controlled the method (patent documentation 1, patent documentation 2) of the amplitude of pitch in turn.This method is the absorption have light trigger that dyestuff with the absorbing wavelength eclipsed absorbing wavelength of light trigger suppress in cholesteric liquid crystal compositions contain by adding in the polymerizability cholesteric liquid crystal compositions, by consequent at light shadow surface and the difference of the polymerization velocity of non-shadow surface control pitch.Yet, in this method, obtained enlarging and selected the cholesteric reflectance coating of the wavelength region of reflection to take a long time, there is the problem on the productivity.In addition because dyestuff is not liquid crystalline cpd, therefore along with the increase of addition, exists painted to film, the problem of generation unfavorable condition easily such as orientation defective takes place.
As additive method, be that non-polymeric type causes the method (non-patent literature 1) that pitch changes easily by making the chipal compounds in the cholesteric liquid crystal compositions thereby enumerated a kind of.In this method,, make cholesteric liquid crystal compositions generation photopolymerization bit by bit, thereby pitch is disperseed from shadow surface by on shadow surface, shining the low light level.
Yet when enlarging the wavelength region of selecting reflection, in above-mentioned these methods, making the cholesteric reflectance coating can take a long time, and has the problem on the productivity.
The prior art document
Patent documentation
Patent documentation 1: No. 3224467 communiques of Japan's special permission
Patent documentation 2: No. 4271729 communiques of Japan's special permission
Non-patent literature
Non-patent literature 1:Liquid Crystal, the 34th volume, the 9th phase, 1009～1018 (2007)
Summary of the invention
The problem that invention will solve
The problem that the present invention will solve is: a kind of wavelength region of selection reflection of easy expansion cholesteric reflectance coating and the polymerizable liquid crystal compound of productivity excellence are provided, in addition, provide a kind of outstanding cholesteric reflectance coating and reflection-type Polarizer of outward appearance that uses this polymerizable liquid crystal compound.
Be used to solve the method for problem
For as disclosed dyestuff in the conventional art, along with the increase of addition can be orientated defective, the present inventor is from this point, even find to increase the addition that has the function close and can form the compound of liquid crystal with dyestuff, the orientation defective also is difficult to take place, so the present invention has been arranged.
The invention provides a kind of polymerizable liquid crystal compound, it is characterized in that: contain more than a kind or 2 kinds the represented liquid crystalline cpd of a) general formula (1), contain b more than a kind or 2 kinds) have only 1 polymerizability functional group liquid crystalline cpd, contain c more than a kind or 2 kinds) have 2 above polymerizability functional groups liquid crystalline cpd, contain d more than a kind or 2 kinds) have 1 above polymerizability functional group chipal compounds, contain e more than a kind or 2 kinds) polymerization starter; A kind of cholesteric reflectance coating also is provided, and it is the cholesteric reflectance coating that the cured article by the polymerizable liquid crystal compound of planar orientation constitutes, and this polymerizable liquid crystal compound is aforementioned polymerizable liquid crystal compound; A kind of reflection-type Polarizer also is provided, it is characterized in that: it is the reflection-type Polarizer of base material, cholesteric reflectance coating and phase retardation film stacked above one another, and this phase retardation film is aforementioned phase retardation film; A kind of reflection-type Polarizer also is provided, it is characterized in that: it is the reflection-type Polarizer of base material, cholesteric reflectance coating, phase retardation film and linear polarization film stacked above one another, and this phase retardation film is aforementioned phase retardation film.
R 1-Z 1-B-A-B-Z 2-R 2?(1)
(in the formula, R 1And R 2Represent independently that respectively fluorine atom, chlorine atom, cyano group, carbonatoms are that 1～12 alkyl or carbonatoms are 2～12 alkenyl, 1 of the hydrogen atom that contains in these groups or can be replaced by fluorine atom more than it; Z 1The expression singly-bound ,-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; Z 2The expression singly-bound ,-O-,-S-,-COO-,-OCO-,-CH 2O-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; A represents-C ≡ C-,-C=N-,-N=N-or-C=N-N=C-or following arbitrary ring structure;
Figure BSA00000466647700031
R 3Expression fluorine atom, chlorine atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group or cyano group; B represents following ring structure;
Figure BSA00000466647700032
R 4Expression fluorine atom, chlorine atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group or cyano group.)
The invention effect
Polymerizable liquid crystal compound of the present invention is by containing the compound that has the function close with dyestuff and can form liquid crystal, thereby has the feature that is difficult to be orientated defective and can enlarges the wavelength region of selecting reflection easily.In addition, polymerizable liquid crystal compound of the present invention can be made the cholesteric reflectance coating by easy method, and productivity is also excellent.Therefore, polymerizable liquid crystal compound of the present invention and cholesteric reflectance coating, reflection-type Polarizer can be applied to liquid crystal device, indicating meter, optics, tinting material, safety sign, laser apparatus illuminating member.
Description of drawings
Fig. 1 is the figure of the polarisation reflected waveband of the cholesteric reflectance coating of making among the expression embodiment 1.
Fig. 2 is the figure of the polarisation reflected waveband of the cholesteric reflectance coating of making among the expression embodiment 17.
Embodiment
Below the present invention is described in detail.
A) (the represented liquid crystalline cpd of general formula (1))
Polymerizable liquid crystal compound of the present invention has been to use the material of the represented liquid crystalline cpd of general formula (1), thereby consider the overlapping many compounds of the conjugated link(age) of preferred liquid crystalline cpd from have the viewpoint that dyestuff with the absorbing wavelength eclipsed absorbing wavelength of light trigger suppresses the absorption of the light trigger that contains the cholesteric liquid crystal compositions by interpolation.
From the viewpoint, in the represented liquid crystalline cpd of general formula (1), R 1And R 2Be preferably fluorine atom, cyano group, carbonatoms respectively independently and be 1～12 alkyl or carbonatoms and be 2～12 alkenyl, be preferably fluorine atom, carbonatoms especially and be 3～8 alkyl or carbonatoms and be 2～8 alkenyl.
Z 1Be preferably singly-bound ,-O-,-S-,-COO-,-OCO-or-OCH 2-, be preferably especially singly-bound ,-O-,-COO-or-OCO-.Z 2Be preferably singly-bound ,-O-,-S-,-COO-,-OCO-or-OCH 2-, be preferably especially singly-bound ,-O-,-COO-or-OCO-.
A is preferably-C ≡ C-,-C=N-,-N=N-,-C=N-N=C-,
Figure BSA00000466647700041
Be preferably especially-C ≡ C-,-C=N-N=C-,
Figure BSA00000466647700042
R 3Be preferably fluorine atom, chlorine atom, carbonatoms and be 1～6 alkyl, carbonatoms and be 1～6 alkoxyl group, cyano group, be preferably fluorine atom, carbonatoms especially and be 1～6 alkyl.
The B of the liquid crystalline cpd that general formula (1) is represented is preferably
Figure BSA00000466647700051
Be preferably especially
R 4Be preferably fluorine atom, carbonatoms and be 1～6 alkyl, carbonatoms and be 1～6 alkoxyl group or cyano group, be preferably fluorine atom or carbonatoms especially and be 1～6 alkyl.
General formula (1) concrete example is shown with following liquid crystalline cpd, but is not limited to these.
Figure BSA00000466647700053
Figure BSA00000466647700061
Figure BSA00000466647700071
Figure BSA00000466647700081
Figure BSA00000466647700091
(in the formula, m and n represent 0～7 integer respectively independently, and R represents that hydrogen atom, fluorine atom or carbonatoms are 1～6 alkyl.)
The containing ratio of the compound that general formula (1) is represented is preferably 0.1～20 quality %, is more preferably 0.5～10 quality %.
B) (liquid crystalline cpd that has only 1 polymerizability functional group)
The liquid crystalline cpd that uses in the polymerizable liquid crystal compound of the present invention, have only 1 polymerizability functional group is, individually or with the composition of other liquid crystalline cpds in show liquid crystal liquid crystal property.So long as have only the compound of 1 polymerizability functional group then to be not particularly limited, can use known habitual material.
For example, can enumerate: as Handbook of Liquid Crystals (D.Demus, J.W.Goodby, G.W.Gray, H.W.Spiess, V.Vill edits, the distribution of Wiley-VCH company, 1998), quarterly chemistry the 22nd phase of introduction, the liquid crystal chemistry (compile by Japanization association, 1994), perhaps the spy opens flat 7-294735 communique, Te Kaiping 8-3111 communique, Te Kaiping 8-29618 communique, Te Kaiping 11-80090 communique, Te Kaiping 11-116538 communique, Te Kaiping 11-148079 communique etc. is put down in writing, have and connected a plurality of 1,4-phenylene 1, the 4-cyclohexylidene is isostructural to be known as the rigidity position of " mesomorphic " and (methyl) acryl, vinyloxy group, the rod-like polymerizable liquid crystal compound of the polymerizability functional group that glycidyl is such; Perhaps as special open the 2004-2373 communique, the spy opens 2004-99446 communique rod-like polymerizable liquid crystal compound that put down in writing, that have dimaleoyl imino.Wherein, the rod shaped liquid crystal compound with polymerizable group makes easily that liquid crystal temperature range comprises cryogenic material before and after the room temperature and preferred.
Polymerizability functional group can enumerate vinyl, vinyloxy group, acryl, (methyl) acryl, glycidyl, glycidyl ether, oxetanyl or dimaleoyl imino etc.; consider preferred acryl or (methyl) acryl from the viewpoint of productivity.
But the concrete illustration liquid crystalline cpd as follows of the liquid crystalline cpd that uses in the polymerizable liquid crystal compound of the present invention, have only 1 polymerizability functional group, but be not limited to these.
Figure BSA00000466647700111
Figure BSA00000466647700121
(in the formula, l and m represent 1～9 integer respectively independently, and n represents 0～10 integer.)
These liquid crystalline cpds may be used alone, can also be two or more kinds in combination.
In addition, when the liquid crystalline cpd that has only 1 polymerizability functional group is the represented compound of general formula (2), preferred especially owing to can further enlarge the wavelength region of selecting reflection.
Figure BSA00000466647700131
(in the formula, L represents hydrogen atom or methyl; Sp represents that singly-bound or carbonatoms are 1～10 alkyl; X represent singly-bound ,-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; G 1Expression singly-bound, 1,4-phenylene, naphthalene-2,6-two base or 1, the 4-cyclohexylidene, the hydrogen atom more than 1 or 2 that exists in these groups can be that 1～6 alkyl, carbonatoms are that 1～6 alkoxyl group or cyano group replace by fluorine atom, chlorine atom, carbonatoms; M represent singly-bound ,-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-, G 1During the expression singly-bound, M represents singly-bound, G 1Expression 1,4-phenylene, naphthalene-2,6-two base or 1, during the 4-cyclohexylidene, M represents-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; G 2Expression hydrogen atom, phenyl, cyclohexyl, naphthyl, carbonatoms are that 1～10 alkyl, carbonatoms are 1～10 alkoxyl group, carboxyl, formamyl, cyano group, nitro or halogen atom, hydrogen atom in this phenyl, cyclohexyl or the naphthyl can not be substituted or is that 1～6 alkyl, carbonatoms are that 1～6 alkoxyl group or cyano group replace by the halogen atom more than 1 or 2, carbonatoms, hydrogen atom in this carboxyl or the formamyl can not be substituted, and can is 1～10 alkyl replacement by carbonatoms yet; Y 1And Y 2Represent independently that respectively hydrogen atom, halogen atom, cyano group, nitro, carbonatoms are that 1～6 alkyl or carbonatoms are 1～6 alkoxyl group.)
The L of the liquid crystalline cpd that general formula (2) is represented is preferably hydrogen atom.
It is 3～6 alkyl that the Sp of the liquid crystalline cpd that general formula (2) is represented is preferably singly-bound or carbonatoms, be preferably carbonatoms especially is 3～6 alkyl.
The X of the liquid crystalline cpd that general formula (2) is represented be preferably singly-bound ,-O-,-COO-,-OCO-or-OCO-CH=CH-, be preferably especially singly-bound ,-O-or-OCO-.
G 1Expression 1,4-phenylene, naphthalene-2,6-two bases or 1 are during the 4-cyclohexylidene, the M of the liquid crystalline cpd that general formula (2) is represented is preferably-O-,-COO-,-OCO-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-, be preferably especially-O-,-COO-,-OCO-.
The G of the liquid crystalline cpd that general formula (2) is represented 2Be preferably hydrogen atom, phenyl, cyclohexyl, naphthyl, carbonatoms and be 1～10 alkyl, carbonatoms and be 1～10 alkoxyl group, carboxyl, formamyl, cyano group, fluorine atom or chlorine atom, be preferably carbonatoms especially and be 1～6 alkyl, carbonatoms and be 1～6 alkoxyl group, cyano group or fluorine atom.
The Y of the liquid crystalline cpd that general formula (2) is represented 1Be preferably hydrogen atom, fluorine atom, chlorine atom, cyano group, carbonatoms and be 1～6 alkyl or carbonatoms and be 1～6 alkoxyl group, be preferably hydrogen atom, fluorine atom, carbonatoms especially and be 1～3 alkyl or carbonatoms and be 1～3 alkoxyl group.
The Y of the liquid crystalline cpd that general formula (2) is represented 2Be preferably hydrogen atom, fluorine atom, chlorine atom, cyano group, carbonatoms and be 1～6 alkyl or carbonatoms and be 1～6 alkoxyl group, be preferably hydrogen atom, fluorine atom, carbonatoms especially and be 1～3 alkyl or carbonatoms and be 1～3 alkoxyl group.
The containing ratio of the liquid crystalline cpd that general formula (2) is represented is preferably 5～80 quality %, is preferably 10～70 quality % especially.In addition, the represented liquid crystalline cpd of general formula (2) may be used alone, can also be two or more kinds in combination.
The represented liquid crystalline cpd of general formula (2), concrete example is shown with following liquid crystalline cpd, but is not limited to these.
Figure BSA00000466647700141
Figure BSA00000466647700151
(in the formula; m represents 1～6 integer; R represents that hydrogen atom, carbonatoms are that 1～10 alkyl, carbonatoms are 1～10 alkoxyl group, carboxyl, formamyl, halogen atom, cyano group or nitro; when these groups are carboxyl or formamyl; terminal hydrogen atom can not be substituted, or is 1～10 alkyl replacement by carbonatoms.)
Further, when the liquid crystalline cpd that has only 1 polymerizability functional group is the represented liquid crystalline cpd of general formula (3), preferred especially owing to can further enlarge the wavelength region of selecting reflection.
Figure BSA00000466647700162
(in the formula, L 1Expression hydrogen atom or methyl; Sp 1Expression singly-bound or carbonatoms are 1～10 alkyl; X 1And X 2Represent independently respectively singly-bound ,-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; Y 3, Y 4, Y 5And Y 6Represent independently that respectively hydrogen atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group, carboxyl, formamyl, cyano group, nitro or halogen atom; hydrogen atom in this alkyl or the alkoxyl group can be replaced by the halogen atom more than 1 or 2; hydrogen atom in this carboxyl or the formamyl can not be substituted, and can is 1～10 alkyl replacement by carbonatoms yet.)
The L of the liquid crystalline cpd that general formula (3) is represented 1Be preferably hydrogen atom.
The Sp of the liquid crystalline cpd that general formula (3) is represented 1Being preferably carbonatoms and being 1～10 alkyl, being preferably carbonatoms especially is 2～6 alkyl.
The X of the liquid crystalline cpd that general formula (3) is represented 1Be preferably-O-,-COO-,-OCO-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-, be preferably especially-O-,-COO-or-OCO-.
The X of the liquid crystalline cpd that general formula (3) is represented 2Be preferably-O-,-COO-,-OCO-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-, be preferably especially-COO-,-OCO-,-CH=CH-or-O-.
The Y of the liquid crystalline cpd that general formula (3) is represented 3, Y 4, Y 5And Y 6Be preferably hydrogen atom, carbonatoms respectively independently and be 1～6 alkyl, carbonatoms and be 1～6 alkoxyl group, carboxyl, formamyl, cyano group or fluorine atom, be preferably hydrogen atom, carbonatoms especially and be 1～3 alkyl, carbonatoms and be 1～3 alkoxyl group or cyano group.
These liquid crystalline cpds may be used alone, can also be two or more kinds in combination.
The represented liquid crystalline cpd of general formula (3), concrete example is shown with following liquid crystalline cpd, but is not limited to these.
Figure BSA00000466647700171
Figure BSA00000466647700181
(in the formula; m represents 1～10 integer; R represents that hydrogen atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group, carboxyl, formamyl, cyano group, nitro, halogen atom; these groups are that carbonatoms is that 1～6 alkyl or carbonatoms are when being 1～6 alkoxyl group; can all not replace, or replaced by the halogen atom more than 1 or 2.When these groups were carboxyl, formamyl, terminal hydrogen atom can not replace, or was 1～10 alkyl replacement by carbonatoms.)
In these formulas, R represents that preferably hydrogen atom, carbonatoms are that 1～3 alkyl, carbonatoms are 1～3 alkoxyl group or cyano group.
These liquid crystalline cpds may be used alone, can also be two or more kinds in combination.
C) (liquid crystalline cpd) with 2 above polymerizability functional groups
The liquid crystalline cpd that uses in the polymerizable liquid crystal compound of the present invention, have 2 above polymerizability functional groups is, individually or with the composition of other liquid crystalline cpds in show liquid crystal liquid crystal property.Then be not particularly limited so long as have the compound of 2 above polymerizability functional groups, can use known habitual material.
For example, can enumerate: as Handbook of Liquid Crystals (D.Demus, J.W.Goodby, G.W.Gray, H.W.Spiess, V.Vill edits, the distribution of Wiley-VCH company, 1998), quarterly chemistry the 22nd phase of introduction, the liquid crystal chemistry (compile by Japanization association, 1994), perhaps the spy opens flat 4-227684 communique, Te Kaiping 11-80090 communique, Te Kaiping 11-116538 communique, Te Kaiping 11-148079 communique, the spy opens the 2000-178233 communique, the spy opens the 2002-308831 communique, the spy opens the 2002-145830 communique, the spy opens that 2004-125842 communique etc. put down in writing, have and connected a plurality of 1,4-phenylene 1, the 4-cyclohexylidene is isostructural to be known as the rigidity position and the acryl of " mesomorphic ", (methyl) acryl, vinyloxy group, the rod-like polymerizable liquid crystal compound of the polymerizability functional group that glycidyl is such; Perhaps as special open the 2004-2373 communique, the spy opens 2004-99446 communique rod-like polymerizable liquid crystal compound that put down in writing, that have dimaleoyl imino.Wherein, the rod shaped liquid crystal compound with polymerizable group makes easily that liquid crystal temperature range comprises cryogenic material before and after the room temperature and preferred.
Polymerizability functional group can enumerate vinyl, vinyloxy group, acryl, (methyl) acryl, glycidyl, glycidyl ether, oxetanyl or dimaleoyl imino etc.; consider from the viewpoint of productivity, be preferably acryl or (methyl) acryl.
But the concrete illustration liquid crystalline cpd as follows of liquid crystalline cpd that uses in the polymerizable liquid crystal compound of the present invention, have 2 above polymerizability functional groups.
Figure BSA00000466647700201
(in the formula; m and n represent 1～10 integer respectively independently; R represents that hydrogen atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group, carboxyl, formamyl, cyano group, nitro or halogen atom; these groups are that carbonatoms is that 1～6 alkyl or carbonatoms are when being 1～6 alkoxyl group; can all not replace, or replaced by the halogen atom more than 1 or 2.When these groups were carboxyl, formamyl, terminal hydrogen atom can not replace, or was 1～10 alkyl replacement by carbonatoms.)
It is that 1～3 alkyl, carbonatoms are 1～3 alkoxyl group or cyano group that R is preferably hydrogen atom, carbonatoms.
These liquid crystalline cpds may be used alone, can also be two or more kinds in combination.
D) (chipal compounds) with at least 1 above polymerizability functional group
So long as the chipal compounds that uses in the polymerizable liquid crystal compound of the present invention, have at least 1 above polymerizability functional group then is not particularly limited, can use known habitual material.
For example, can enumerate: as the spy open flat 11-193287 communique, spy open 2001-158788 communique, special table 2006-52669 communique, spy open 2007-269639 communique, spy open that 2007-269640 communique, 2009-84178 communique etc. are put down in writing, contain chirality carbohydrate such as Isosorbide, isomannite, glucoside and have 1,4-phenylene 1, the polymerizable chiral compound of the polymerizability functional group that rigidity position such as 4-cyclohexylidene and (methyl) acryl, vinyloxy group, glycidyl are such; Open polymerizable chiral compound that flat 8-239666 communique is put down in writing, that form by the class triterpene derivative as the spy; Roll up as NATURE the 35th volume 467～469 pages of (distribution on November 30 nineteen ninety-five), NATURE the 392nd that 476～479 pages (distribution on April 2nd, 1998) etc. put down in writing, by mesomorphic base with have the polymerizable chiral compound that the isolation base at chirality position forms; Perhaps open 2007-248945 communique polymerizable chiral compound that put down in writing, that contain binaphthylyl as special table 2004-504285 communique, spy.Wherein, screw twisted power (HTP) thus big chipal compounds because to make easily polymerizable liquid crystal compound of the present invention preferred.
But the concrete illustration liquid crystalline cpd as follows of chipal compounds that uses in the polymerizable liquid crystal compound of the present invention, have at least 1 above polymerizability functional group, but be not limited to these.
Figure BSA00000466647700221
Figure BSA00000466647700231
Figure BSA00000466647700251
Figure BSA00000466647700261
(in the formula; m and n represent 1～10 integer respectively independently; R represents that hydrogen atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group, carboxyl, formamyl, cyano group, nitro, halogen atom; these groups are that carbonatoms is that 1～6 alkyl or carbonatoms are when being 1～6 alkoxyl group; can all not replace, or replaced by the halogen atom more than 1 or 2.When these groups were carboxyl, formamyl, terminal hydrogen atom can not replace, or was 1～10 alkyl replacement by carbonatoms.)
These chipal compounds may be used alone, can also be two or more kinds in combination.
E) (polymerization starter)
The polymerization starter that uses in the polymerizable liquid crystal compound of the present invention is to use in order to make polymerizable liquid crystal compound polymerization of the present invention.The Photoepolymerizationinitiater initiater that uses when carrying out polymerization by rayed can use known habitual material.
For example: 2-hydroxy-2-methyl-1-phenyl-1-acetone (" DAROCUR 1173 " that Merck ﹠ Co., Inc. produces), 1-hydroxy-cyclohexyl phenyl ketone (" gorgeous good solid 184 " that Ciba company produces), 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl-1-acetone (" DAROCUR 1116 " that Merck ﹠ Co., Inc. produces), 2-methyl isophthalic acid-[(methylthio group) phenyl]-2-morpholino base-1-acetone (" gorgeous good solid 907 " that Ciba company produces).Benzil methyl ketal (" gorgeous good solid 651 " that Ciba company produces); 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone (" gorgeous good solid 369 " that Ciba company produces); 2-(dimethylamino)-2-(4-methyl-benzyl)-1-(4-morpholino phenyl)-1-butanone (" gorgeous good solid 379 " that Ciba company produces); 2; 2-dimethoxy-1; 2-phenylbenzene-1-ethyl ketone; two (2; 4; 6-Three methyl Benzene formyl)-phenyl phosphine oxide (DAROCUR TPO); 2; 4; 6-Three methyl Benzene formyl-phenylbenzene-phosphine oxide (" gorgeous good solid 819 " that Ciba company produces); 1; 2-octane diketone; 1-[4-(thiophenyl)-2-(O-benzoyl oxime)]; ethyl ketone (" gorgeous good solid OXE01 " that Ciba company produces); 1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) (" gorgeous good solid OXE02 " that Ciba company produces); 2, the mixture of 4-diethyl thioxanthone (" KAYACURE DETX " that Japanese chemical drug company produces) and (dimethylamino)-ethyl benzoate (" the KAYACURE EPA " of the production of Japanese chemical drug company); the mixture of isopropyl thioxanthone (" CANTACURE ITX " that Wordprekinsop company produces) and (dimethylamino)-ethyl benzoate; acylphosphine oxide (" Lucirin TPO " that BASF AG produces) etc.
The containing ratio of Photoepolymerizationinitiater initiater is preferably 1～10 quality %, is preferably 2～7 quality % especially.These Photoepolymerizationinitiater initiaters may be used alone, can also be two or more kinds in combination.
In addition, the thermal polymerization that uses during as thermopolymerization can use known habitual material, for example can use: the acetyl peroxide methyl acetate, cumyl hydroperoxide, benzoyl peroxide, two (4-tert-butylcyclohexyl) peroxy dicarbonate, peroxidized t-butyl perbenzoate, methylethyl ketone peroxide, 1, two (the peroxidation uncle hexyls) 3 of 1-, 3, the 5-trimethyl-cyclohexane, to five hydrogen peroxide (p-pentahydroperoxide), tertbutyl peroxide, dicumyl peroxide, isobutyl peroxide, two (3-methyl-3 methoxyl group butyl) peroxy dicarbonate, 1, organo-peroxides such as two (tert-butyl peroxide) hexanaphthenes of 1-; 2,2 '-Diisopropyl azodicarboxylate,, 2 '-the two azonitrile compound such as (2, the 4-methyl pentane nitrile) of azo; 2,2 '-azo amidine compounds, 2 such as two (2-methyl-N-phenyl third amidine) dihydrochlorides of azo, 2 '-two { 2-methyl-N-[1 of azo, two (the methylol)-2-hydroxyethyls of 1-] propionic acid amide etc. the azo amide compound,, 2 '-azo two (2,4,4-trimethylpentane) alkyl azo-compound etc. such as.The containing ratio of thermal polymerization is preferably 1～10 quality %, is preferably 2～6 quality % especially.These thermal polymerizations may be used alone, can also be two or more kinds in combination.
Above-mentioned Photoepolymerizationinitiater initiater and above-mentioned thermal polymerization also can come and usefulness according to separately purposes, method for making.
F) (solvent)
Composition of the present invention is the material that contains aforementioned polymerizable liquid crystal compound and solvent, for the solvent that uses in the composition, as long as when on base material, being coated with the alignment films that forms on base material or the base material is not dissolved, and polymerizable liquid crystal compound of the present invention can be orientated on zero defect ground, then be not particularly limited as the solvent that uses, the preferred polymeric liquid-crystal composition shows the solvent of good solubility.
As such solvent, can enumerate as fragrant family hydrocarbon such as toluene, dimethylbenzene, isopropyl benzene, sym-trimethylbenzene; Ester series solvents such as methyl acetate, ethyl acetate, propyl acetate, butylacetate; Ketone series solvents such as methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone; Tetrahydrofuran (THF), 1, ether series solvents such as 2-dimethoxy hexane, methyl-phenoxide; N, acid amides series solvents such as dinethylformamide, N-N-methyl-2-2-pyrrolidone N-; Propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic ester, gamma-butyrolactone, chlorobenzene etc.These solvents may be used alone, can also be two or more kinds in combination.
Ratio as for solvent, because the polymerizable liquid crystal compound that uses among the present invention is undertaken by common coating, therefore as long as the state of not obvious damage coating then is not particularly limited, the solids component of polymerizable liquid crystal compound and the ratio of solvent be preferably 0.1: 99.9～and 80: 20, when considering coating, be more preferably 1: 99～60: 40.
G) (promote the tensio-active agent or the polymer of planar orientation)
Owing to polymerizable liquid crystal compound of the present invention polymerization under the state of planar orientation, therefore be used to promote the tensio-active agent or the polymer of planar orientation as required.
The tensio-active agent that uses in the polymerizable liquid crystal compound of the present invention, be used to promote planar orientation, so long as in the polymerisable liquid crystal composition solvable and when polymerizable liquid crystal compound coating is dry with the air interface of base material opposition side on the material of segregation, then just be not particularly limited, be preferably than the little tensio-active agent of liquid crystalline cpd surface tension with polymerizability functional group as the tensio-active agent that uses.As such tensio-active agent, can enumerate as: the nonionic that contains fluorine is that tensio-active agent, organosilicon methane series tensio-active agent, polyacrylic ester are tensio-active agent etc.In order to form firmer film when the polymerization, aforementioned surfactants also can have polymerizable group.
Use in the polymerizable liquid crystal compound of the present invention, be used to promote the polymer of planar orientation also to be, so long as in the polymerisable liquid crystal composition solvable and when polymerizable liquid crystal compound coating is dry with the air interface of base material opposition side on the material of segregation, then just be not particularly limited, be preferably than the little polymer of liquid crystalline cpd surface tension with polymerizability functional group as the polymer that uses.As such polymer, can enumerate as polyethylene, polypropylene, polyisobutene, paraffin, whiteruss, Chlorinated Polypropylene III, clorafin or chlorated liquid paraffin body, polyvinylidene difluoride (PVDF) etc.
Aforementioned high molecular matter average molecular weight is preferably 200～1000000, is more preferably 300～100000, is preferably 400～10000 especially.
Be used to promote that the tensio-active agent of planar orientation or high molecular containing ratio are preferably 0.01～3 quality %, be preferably 0.05～1.0 quality % especially.
H) (stablizer)
With regard to polymerizable liquid crystal compound of the present invention,, also can use general additive for evenly coating, for the cholesteric reflectance coating that obtains uniform film thickness or according to various purposes.For example can be unlikely to make the orientation of liquid crystal add additives such as flow agent, thixotropic agent, tensio-active agent, UV light absorber, infrared absorbent, oxidation inhibitor, surface treatment agent, stopper in the significantly reduced scope.
(cholesteric reflectance coating)
Cholesteric reflectance coating of the present invention be by planar orientation the cholesteric reflectance coating that constitutes of the cured article of polymerizable liquid crystal compound, this polymerizable liquid crystal compound is the material with following feature: contain more than a kind or 2 kinds a) the represented liquid crystalline cpd of general formula (1), contain b more than a kind or 2 kinds) have only the liquid crystalline cpd of 1 polymerizability functional group, contain c more than a kind or 2 kinds) have a liquid crystalline cpd of 2 above polymerizability functional groups, contain d more than a kind or 2 kinds) have a chipal compounds of 1 above polymerizability functional group, contain e more than a kind or 2 kinds) polymerization starter.
R 1-Z 1-B-A-B-Z 2-R 2 (1)
(in the formula, R 1And R 2Represent independently that respectively fluorine atom, chlorine atom, cyano group, carbonatoms are that 1～12 alkyl or carbonatoms are 2～12 alkenyl, 1 of the hydrogen atom that contains in these groups or can be replaced by fluorine atom more than it; Z 1The expression singly-bound ,-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; Z 2The expression singly-bound ,-O-,-S-,-COO-,-OCO-,-CH 2O-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; A represents-C ≡ C-,-C=N-,-N=N-or-C=N-N=C-or following arbitrary ring structure;
Figure BSA00000466647700291
R 3Expression F, Cl, chlorine atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group, cyano group; B represents following ring structure;
Figure BSA00000466647700292
R 4Expression fluorine atom, chlorine atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group or cyano group.)
The cholesteric reflectance coating of the present application is preferably the cholesteric reflectance coating of polarisation reflected waveband more than 300nm.
(method for making of cholesteric reflectance coating)
(base material)
The base material that uses in the cholesteric reflectance coating of the present invention is normally used base material in liquid crystal device, indicating meter, optics, blooming, so long as during dry after polymerizable liquid crystal compound of the present invention coating or have the stable on heating material that can tolerate heating then be not particularly limited when liquid crystal device is made.As such base material, can enumerate organic materialss such as glass baseplate, metal base, ceramic base material, plastic basis material.Especially, when base material is organic materials, can enumerate derivatived cellulose, polyolefine, polyester, polyolefine, polycarbonate, polyacrylic ester, polyarylester, polyethersulfone, polyimide, polyphenylene sulfide, polyphenylene oxide, nylon or polystyrene etc.
Plastic basis materials such as preferred polyester, polystyrene, polyolefine, derivatived cellulose, polyarylester, polycarbonate wherein.
For coating, the cementability that improves polymerizable liquid crystal compound of the present invention, can carry out surface treatment to these base materials.As surface treatment, can enumerate ozonize, Cement Composite Treated by Plasma, corona treatment, silane coupling agent processing etc.In addition, in order to regulate optical transmission rate, reflectivity, can at substrate surface organic film, inorganic oxide film, metallic film etc. be set by methods such as evaporations, perhaps, in order to give optical added value, base material also can be pick-up lens (pickup lens), post lens, CD, phase retardation film, optical diffusion film, colored filter etc.Wherein, preferred higher pick-up lens, phase retardation film, optical diffusion film, the colored filter of added value.
In addition, on the above-mentioned base material,, can carry out common orientated processing or alignment films is set in order to make polymer liquid crystal composite orientation when coating, the dry polymerizable liquid crystal compound of the present invention.As orientation process, can enumerate prolonged treatment, friction treatment, polarisation UV, visible light photo-irradiation treatment, Ion Beam Treatment etc.When using alignment films, alignment films can be used known habitual material.As such alignment films, can enumerate compounds such as polyimide, polysiloxane, polymeric amide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene oxide, polyarylester, polyethylene terephthalate, polyethersulfone, Resins, epoxy, Epocryl, acrylic resin, coumarin compound, chalcone compounds, cinnamate compound, fulgide compound, anthraquinone compounds, azo-compound, aromatic ethylene compound.The compound of handling by friction orientation is preferably by introduce the material that heating process can promote the crystallization of material after orientation process or orientation process.Preferably make in the compound of the orientation process beyond rubbing and use the light oriented material.
(coating)
As the coating method that is used to obtain cholesteric reflectance coating of the present invention, can carry out applicator method, rod and be coated with that method, spin-coating method, gravure processes, flexographic printing method, spray ink Printing formula are coated with method, mould is coated with known customary ways such as method, CAP coating method, dip-coating.Usually, because therefore the polymerizable liquid crystal compound that coating adopts solvent cut to cross will carry out drying after the coating.
(polymerization process)
About the converging operation of polymerizable liquid crystal compound of the present invention, remove solvent in the polymerizable liquid crystal compound by drying etc. after, light such as irradiation ultraviolet radiation or heating are carried out usually under the planar orientation state.When carrying out polymerization, particularly preferably shine the following UV-light of 390nm, most preferably shine the light of 250～370nm wavelength by rayed.Yet, when using the following UV-light of 390nm can cause polymerizable liquid crystal compound decomposition etc., also preferably use the above UV-light of 390nm to carry out aggregation processing sometimes.This light is preferably the diffusion light and the light of polarisation not.
On the other hand, about polymerization, preferably show the temperature of mesomorphic phase or carry out under the lower temperature, especially than it at polymerizable liquid crystal compound by heating, when using the thermal polymerization that passes through heating release free radical, preferably use the material of its Cracking Temperature in the said temperature scope.In addition, and during with this thermal polymerization and Photoepolymerizationinitiater initiater, except the restriction of said temperature scope, preferably do not have too the mode of big difference come selective polymerization temperature and each initiator according to optical alignment film and this two-layer polymerization velocity of polymerizable liquid crystal film.About Heating temperature, though also relevant to the tansition temperature of isotropic phase from mesomorphic phase with polymerizable liquid crystal compound preferably carried out than causing under the low temperature of heterogeneity polymeric temperature that heat causes.But, because when surpassing the second-order transition temperature of the base material that is formed by organic materials, the thermal distortion of base material becomes significantly, so the preferred second-order transition temperature of room temperature～base material.For example when polymerizable group is (methyl) acryl, preferably under than 90 ℃ of low temperature, carry out in addition.
For anti-solvent properties, the stable on heating stabilization of the cholesteric reflectance coating of gained, also can carry out heat treated to the cholesteric reflectance coating.At this moment, preferably more than the second-order transition temperature of aforementioned polymerizable liquid crystal film, heat.Usually preferred scope internal heating in the second-order transition temperature that is no more than the base material that forms by organic materials.In addition, for above-mentioned purpose, also can carry out photo-irradiation treatment.At this moment, the liquid crystalline cpd composition in the preferred cholesteric reflectance coating can be because of the degree of rayed photolysis.
(reflection-type Polarizer)
Reflection-type Polarizer of the present invention is the reflection-type Polarizer of base material, cholesteric reflectance coating, phase retardation film stacked above one another, or the reflection-type Polarizer of base material, cholesteric reflectance coating, phase retardation film, linear polarization film stacked above one another, this cholesteric reflectance coating uses aforementioned cholesteric reflectance coating of the present invention.
In addition, have 2 above phase retardation films in the reflection-type Polarizer, also preferred this phase retardation film uses the mode of the different phase retardation film of phase differential.
The method for making of the stacked reflectance coating of cholesteric as described above of base material and cholesteric reflectance coating is put down in writing.Phase retardation film stacked enumerated method shown below.
(direct stacked situation on the cholesteric reflectance coating)
Form alignment films on cholesteric reflectance coating of the present invention, coating thereon contains the solution and the drying of foregoing liquid crystal compound, can obtain by carry out polymerization under the state of foregoing liquid crystal compound uniaxial orientation.Not forming alignment films during foregoing liquid crystal compound uniaxial orientation, directly coating contains solution, the drying of foregoing liquid crystal compound on cholesteric films of the present invention, can obtain by polymerization.When using alignment films, put down in writing in alignment films such as the above-mentioned base material part, can use known habitual material.
(situation of on the cholesteric reflectance coating, fitting)
On above-mentioned base material, be coated with drying, use the method identical promptly to get phase retardation film with above-mentioned polymerization process according to above-mentioned coating process.Behind applying caking agent on the phase retardation film of gained or bonding film, can obtain by using fit cholesteric reflectance coating of the present invention and aforementioned phase retardation film of caking agent or bonding film.When using caking agent or bonding film, caking agent, bonding film can use the known habitual material of blooming purposes.
Further, above-mentioned phase retardation film also can be provided with 2 different phase retardation films.As the combination of 2 different phase retardation films, the orientation of liquid crystalline cpd can be enumerated horizontally (eurymeric A plate) (homogeneous (positive A-plate)) and horizontally (eurymeric A plate), horizontally (eurymeric A plate) and arranged vertical (eurymeric C plate), horizontally (eurymeric A plate) and mixing arrangement (O plate).In addition, when the linear polarization film is set on above-mentioned phase retardation film, stacked according to laminating type usually.
Laminating method is identical with the method for stacked phase retardation film on above-mentioned cholesteric reflectance coating.
By cholesteric reflectance coating of the present invention being carried out the adaptation that x-ray bombardment processing or electron rays radiation treatment improve the polymkeric substance of base material and polymerizable liquid crystal compound of the present invention.X ray is that wavelength is
Figure BSA00000466647700321
(dust), energy are the hertzian wave about 0.1～100keV, can use commercially available x-ray bombardment device usually.As for the energy of X ray, handle Undec degree as long as reach cholesteric reflectance coating of the present invention through x-ray bombardment, specifically be preferably 1～100kGy (gray(Gy)).On the other hand, electron rays (EB) be by accelerator give macro-energy, the flowing of the electronics that is accelerated, can use commercially available electron beam irradiation device usually.As for the output of electron rays,, specifically be preferably 10～200kGy as long as reach cholesteric reflectance coating of the present invention through the Undec degree of electron rays radiation treatment.
Embodiment
Below by synthesis example, embodiment and comparative example the present invention is described, certainly the present invention is not limited thereto.In addition, unless otherwise specified, " part " and " % " is quality criteria.
(modulation of polymerizable liquid crystal compound (1))
The liquid crystalline cpd of formula (A-1) expression, the liquid crystalline cpd of formula (B-1) expression, liquid crystalline cpd, the liquid crystalline cpd of formula (C-2) expression, the chipal compounds of formula (D-1) expression, the polymerization starter of formula (E-1) expression, the polymerization starter of formula (E-2) expression, 0.5 part of Liquid Paraffin (G-1) mixing that formula (C-1) is represented are promptly got polymerizable liquid crystal compound of the present invention (1).After in the polymerizable liquid crystal compound of gained, adding 0.07 part of 4-methoxyl group-1-naphthols (H-1), 60 parts of pimelinketone (F-1), make it, promptly get polymerizable liquid crystal compound of the present invention (2) 60 ℃ of dissolvings down.
Figure BSA00000466647700341
(modulation of polymerizable liquid crystal compound (3)～(25))
Obtain polymerizable liquid crystal compound (22)～(25) of polymerizable liquid crystal compound of the present invention (3)～(21) and comparative example in the same manner with the modulation of polymerizable liquid crystal compound of the present invention (2).The concrete composition of polymerizable liquid crystal compound (22)～(25) of table 1～table 6 expression polymerizable liquid crystal compound of the present invention (1)～(21) and comparative example.
Table 1
Table 2
Figure BSA00000466647700361
Table 3
Figure BSA00000466647700371
Table 4
Figure BSA00000466647700381
Table 5
Figure BSA00000466647700391
Table 6
Figure BSA00000466647700401
Compound shown in table 1～table 6 is expressed as follows.
Figure BSA00000466647700402
Figure BSA00000466647700411
Figure BSA00000466647700421
Cyclopentanone (F-2)
Toluene (F-3)
The matter average molecular weight is 2200 polypropylene (G-2)
4-methoxyphenol (H-2)
Figure BSA00000466647700422
(embodiment 1)
On the glass baseplate of thick 0.7mm, use spin-coating method coating alignment films polyimide solution, by 100 ℃ down drying after 10 minutes, under 200 ℃, burn till promptly to get in 60 minutes and film.Filming of gained carried out friction treatment promptly as cholesteric reflectance coating base material of the present invention.Friction treatment uses commercially available friction gear to carry out.
Be coated with polymerizable liquid crystal compound of the present invention (2) by spin-coating method on the base material after the friction, drying is 2 minutes under 80 ℃.Filming of gained placed on 60 ℃ the hot plate, use through bandpass filter and be adjusted to the high pressure mercury vapour lamp that can only obtain near the UV-light (UV light) the 365nm, with 15mW/cm 2Intensity shine 10 second UV light.Then take out bandpass filter, by with 70mW/cm 2Intensity shine 20 second UV light promptly get cholesteric reflectance coating of the present invention.
Use spectrophotometer (U-4100 " Hitachi Co., Ltd's manufacturing ") to measure the selection reflection wavelength of the cholesteric reflectance coating of gained, as shown in Figure 1, the polarisation reflected waveband is approximately 350nm.
(embodiment 2～16)
Obtain the cholesteric reflectance coating of embodiment 2～16 with embodiment 1 the samely.The polarisation reflected waveband of the cholesteric reflectance coating of gained is as shown in table 7, all is more than the 300nm.Therefore, can think that the cholesteric reflectance coating that uses polymerizable liquid crystal compound of the present invention to make is the cholesteric reflectance coating that can reflect the excellence of whole visible lights.In addition, the short in the past time of all available ratio of the arbitrary operation of coating, drying, irradiation when making the cholesteric reflectance coating carries out, and can think the productivity excellence.
Table 7
Polymerizable liquid crystal compound The polarisation reflected waveband
Embodiment 1 (2) 350nm
Embodiment 2 (4) 360nm
Embodiment 3 (6) 310nm
Embodiment 4 (8) 305nm
Embodiment 5 (9) 350nm
Embodiment 6 (10) 355nm
Embodiment 7 (11) 355nm
Embodiment 8 (12) 320nm
Embodiment 9 (13) 340nm
Embodiment 10 (14) 365nm
Embodiment 11 (15) 370nm
Embodiment 12 (16) 365nm
Embodiment 13 (17) 370nm
Embodiment 14 (18) 315nm
Embodiment 15 (19) 310nm
Embodiment 16 (20) 400nm
(comparative example 1～3)
Polymerizable liquid crystal compound (21)～(23) have been used in addition, with the embodiment 1 the same cholesteric reflectance coating that obtains comparative example 1～3.The polarisation reflected waveband of the reflectance coating of gained is as shown in table 8, wherein arbitrary being below the 150nm.
Table 8
Polymerizable liquid crystal compound The polarisation reflected waveband
Comparative example 1 (21) 140nm
Comparative example 2 (22) 150nm
Comparative example 3 (23) 145nm
(comparative example 4～5)
With embodiment 1 the same ground, attempt using polymerizable liquid crystal compound (24) and (25) to obtain the cholesteric reflectance coating of comparative example 4 and 5, the apparent unfavorable condition of result repeatedly takes place, and can't obtain desired cholesteric reflectance coating.
(embodiment 17)
Be coated with polymerizable liquid crystal compound of the present invention (4) on the PET of friction treatment film, being coated with method by rod, 90 ℃ dry 2 minutes down.Filming of gained remained on 60 ℃, use through bandpass filter and be adjusted to the high pressure mercury vapour lamp that can only obtain near the UV light of 365nm, with 15mW/cm 2Intensity shine 10 second UV light.Then take out bandpass filter, by with 70mW/cm 2Intensity shine 20 second UV light promptly get the cholesteric reflectance coating of embodiment 17.
Measure the selection reflection wavelength of the cholesteric reflectance coating of gained, the result is the same with embodiment 2, and as shown in Figure 2, the polarisation reflected waveband is approximately 360nm.
(embodiment 18～32)
Obtain the cholesteric reflectance coating of embodiment 18～32 with embodiment 17 the samely.The polarisation reflected waveband of the cholesteric reflectance coating of gained is as shown in table 9, arbitrary to be more than the 300nm.
Table 9
Polymerizable liquid crystal compound The polarisation reflected waveband
Embodiment 17 (2) 350nm
Embodiment 18 (4) 370nm
Embodiment 19 (6) 310nm
Embodiment 20 (8) 305nm
Embodiment 21 (9) 350nm
Embodiment 22 (10) 355nm
Embodiment 23 (11) 355nm
Embodiment 24 (12) 320nm
Embodiment 25 (13) 340nm
Embodiment 26 (14) 365nm
Embodiment 27 (15) 370nm
Embodiment 28 (16) 365nm
Embodiment 29 (17) 370nm
Embodiment 30 (18) 315nm
Embodiment 31 (19) 310nm
Embodiment 32 (20) 400nm
(embodiment 33)
2 parts of polyvinyl butyral acetals (production of ProductName " S-lec BM-2 " Sekisui Chemical Co., Ltd) are dissolved in 49 parts of ethanol, the 49 parts of butoxy ethanols.The polyvinyl butyral acetal solution of gained is coated on by spin-coating method on the cholesteric reflectance coating of gained among the embodiment 1, and drying is 2 minutes under 80 ℃.Filming of gained carried out friction treatment.Friction treatment uses commercially available friction gear to carry out.
Then (ProductName: the toluene solution production of UV curable liquid crystal " UCL-017 " Dainippon Ink Chemicals) is coated on above-mentioned on the base material that friction treatment is crossed the polymerizable liquid crystal compound that phase retardation film is used by spin-coating method, and drying is 2 minutes under 80 ℃.Use high pressure mercury vapour lamp on the filming of gained with 30mW/cm 2Intensity shine 15 second UV light, promptly get the reflection-type Polarizer of embodiment 33.
Use spectrophotometer (U-4100 " Hitachi Co., Ltd's manufacturing ") to measure the dichroism of the reflection-type Polarizer of gained.Be determined as: between the reflection-type Polarizer of embodiment 33 and detector, place commercially available linear polarization plate, in the reflection-type Polarizer of embodiment 33 situation parallel (parallel-nicol prism) and vertical situation (Nicol crossed) mensuration transmissivity down with commercially available linear polarization plate polarization direction separately.The prismatical occasion of parallel-nicol is more than 90% in the transmissivity of visible-range.The occasion of Nicol crossed is almost 0% in the transmissivity of visible-range.
(embodiment 34)
The toluene solution of the UCL-017 that uses in coating embodiment 33 on the poly-cellulose acetate film of handling through surface friction, drying is 3 minutes under 60 ℃.Use high pressure mercury vapour lamp on the filming of gained with 30mW/cm 2Intensity shine 15 second UV light, can obtain the phase retardation film that forms by polymerizable liquid crystal compound.After peeling the peel ply of one side of commercially available transparent double sticky tape off, be attached on the phase retardation film of gained, be fitted on the cholesteric reflectance coating of embodiment 17 after peeling the peel ply of another side again off, promptly get the reflection-type Polarizer of embodiment 34.By with embodiment 33 identical methods the dichroism of the reflection-type Polarizer of gained being measured, the result can obtain the 33 same good polarized light properties with embodiment.
(embodiment 35)
On the reflection-type Polarizer of embodiment 33, be coated with the polyvinyl butyral acetal solution of embodiment 33 by spin-coating method, 80 ℃ dry 2 minutes down.
Then (the solids component ratio: 25%) be coated on the above-mentioned reflection-type Polarizer by spin-coating method, drying is 2 minutes under 80 ℃ for the xylene solution of the polymerizable liquid crystal compound that phase retardation film is used (ProductName: UV curable liquid crystal " UCL-018 " Dainippon Ink Chemicals produces).Use high pressure mercury vapour lamp on the filming of gained with 30mW/cm 2Intensity shine 20 second UV light, promptly get the reflection-type Polarizer of embodiment 35.
(embodiment 36)
The xylene solution of the UCL-018 that uses among the coating embodiment 35 on surface treated poly-cellulose acetate film, drying is 3 minutes under 60 ℃.Use high pressure mercury vapour lamp on the filming of gained with 30mW/cm 2Intensity shine 20 second UV light, can obtain the phase retardation film that forms by polymerizable liquid crystal compound.After peeling the peel ply of one side of commercially available transparent double sticky tape off, be attached on the phase retardation film of gained, be fitted on the reflection-type Polarizer of embodiment 34 after peeling the peel ply of another side again off, promptly get the reflection-type Polarizer of embodiment 36.
(embodiment 37)
Be attached on the cholesteric reflectance coating of embodiment 17 after peeling the peel ply of one side of commercially available transparent double sticky tape off, be fitted on the cholesteric reflectance coating of embodiment 17 after peeling the peel ply of another side again off, promptly get the cholesteric reflectance coating of embodiment 37.
Measure the selection reflection wavelength of the cholesteric reflectance coating of embodiment 37, result and embodiment 2 are same, and the polarisation reflected waveband is approximately 400nm.In addition, the transmissivity at whole visible-range is approximately below 50%.
(embodiment 38)
The commercially available x-ray bombardment device of use at room temperature shines the X ray of 5kGy on the cholesteric reflectance coating of embodiment 17, promptly gets the cholesteric reflectance coating of embodiment 38.
The evaluation of the adaptation of the cholesteric reflectance coating of gained is undertaken by the hundred lattice test of being put down in writing among the JIS-K5400.It is to cut out cut channel in length and breadth at interval with 2mm that the test of hundred lattice is to use cutter, makes 25 grid.On these grid, attach the cellulose film band, the number of grid when counting is peeled off, remaining 24 of result.
(embodiment 39)
The commercially available electron beam irradiation device of use at room temperature shines the electron rays of 10kGy on the cholesteric reflectance coating of embodiment 17, promptly gets the cholesteric reflectance coating of embodiment 39.
Similarly carry out the evaluation of adaptation with embodiment 38, remaining 20 of result.

Claims (19)

1. polymerizable liquid crystal compound, it is characterized in that: contain more than a kind or 2 kinds the represented liquid crystalline cpd of a) general formula (1), contain b more than a kind or 2 kinds) have only 1 polymerizability functional group liquid crystalline cpd, contain c more than a kind or 2 kinds) have 2 above polymerizability functional groups liquid crystalline cpd, contain d more than a kind or 2 kinds) have 1 above polymerizability functional group chipal compounds, contain e more than a kind or 2 kinds) polymerization starter
R 1-Z 1-B-A-B-Z 2-R 2 (1)
In the formula, R 1And R 2Represent independently that respectively fluorine atom, chlorine atom, cyano group, carbonatoms are that 1～12 alkyl or carbonatoms are 2～12 alkenyl, 1 of the hydrogen atom that contains in these groups or can be replaced by fluorine atom more than it; Z 1The expression singly-bound ,-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; Z 2The expression singly-bound ,-O-,-S-,-COO-,-OCO-,-CH 2O-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; A represents-C ≡ C-,-C=N-,-N=N-or-C=N-N=C-or following arbitrary ring structure:
Figure FSA00000466647600011
R 3Expression fluorine atom, chlorine atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group or cyano group; B represents following ring structure:
Figure FSA00000466647600012
R 4Expression fluorine atom, chlorine atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group or cyano group.
2. polymerizable liquid crystal compound as claimed in claim 1, wherein, the containing ratio of the compound that general formula (1) is represented is 0.1～20 quality %.
3. polymerizable liquid crystal compound as claimed in claim 1 or 2 wherein, contains the liquid crystalline cpd that has only 1 polymerizability functional group more than 2 kinds.
4. as claim 1,2 or 3 described polymerizable liquid crystal compounds, wherein, contain the liquid crystalline cpd that has 2 polymerizability functional groups more than 2 kinds.
5. as each described polymerizable liquid crystal compound of claim 1～4, wherein, have only the liquid crystalline cpd of 1 polymerizability functional group to represent with general formula (2),
Figure FSA00000466647600021
In the formula, L represents hydrogen atom or methyl; Sp represents that singly-bound or carbonatoms are 1～10 alkyl; X represent singly-bound ,-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; G 1Expression singly-bound, 1,4-phenylene, naphthalene-2,6-two base or 1, the 4-cyclohexylidene, the hydrogen atom more than 1 or 2 that exists in these groups can be that 1～6 alkyl, carbonatoms are that 1～6 alkoxyl group or cyano group replace by fluorine atom, chlorine atom, carbonatoms; M represent singly-bound ,-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-, G 1During the expression singly-bound, M represents singly-bound, G 1Expression 1,4-phenylene, naphthalene-2,6-two base or 1, during the 4-cyclohexylidene, M represents-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; G 2Expression hydrogen atom, phenyl, cyclohexyl, naphthyl, carbonatoms are that 1～10 alkyl, carbonatoms are 1～10 alkoxyl group, carboxyl, formamyl, cyano group, nitro or halogen atom, hydrogen atom in this phenyl, cyclohexyl or the naphthyl can not be substituted or is that 1～6 alkyl, carbonatoms are that 1～6 alkoxyl group or cyano group replace by the halogen atom more than 1 or 2, carbonatoms, hydrogen atom in this carboxyl or the formamyl can not be substituted, and can is 1～10 alkyl replacement by carbonatoms yet; Y 1And Y 2Represent independently that respectively hydrogen atom, halogen atom, cyano group, nitro, carbonatoms are that 1～6 alkyl or carbonatoms are 1～6 alkoxyl group.
6. as each described polymerizable liquid crystal compound of claim 1～5, wherein, the containing ratio of the compound that general formula (2) is represented is 5～80 quality %.
7. as each described polymerizable liquid crystal compound of claim 1～6, wherein, have only the liquid crystalline cpd of 1 polymerizability functional group to represent with general formula (3),
Figure FSA00000466647600031
In the formula, L 1Expression hydrogen atom or methyl; Sp 1Expression singly-bound or carbonatoms are 1～10 alkyl; X 1And X 2Represent independently respectively singly-bound ,-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; Y 3, Y 4, Y 5And Y 6Represent independently that respectively hydrogen atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group, carboxyl, formamyl, cyano group, nitro or halogen atom; hydrogen atom in this alkyl or the alkoxyl group can be replaced by the halogen atom more than 1 or 2; hydrogen atom in this carboxyl or the formamyl can not be substituted, and can is 1～10 alkyl replacement by carbonatoms yet.
8. as each described polymerizable liquid crystal compound of claim 1～7, wherein, the containing ratio of polymerization starter is 1～10 quality %.
9. as each described polymerizable liquid crystal compound of claim 1～8, wherein, contain the tensio-active agent or the polymer of the promotion planar orientation more than a kind or 2 kinds.
10. polymerizable liquid crystal compound as claimed in claim 9 wherein, promotes that the tensio-active agent or the high molecular containing ratio of planar orientation are 0.01～3 quality %.
11. a composition wherein, contains each the described polymerizable liquid crystal compound of claim 1～10 and solvent more than a kind or 2 kinds.
12. cholesteric reflectance coating, it is characterized in that: the cholesteric reflectance coating that it constitutes for the cured article by the polymerizable liquid crystal compound of planar orientation, this polymerizable liquid crystal compound contains more than a kind or 2 kinds a) the represented liquid crystalline cpd of general formula (1), contain b more than a kind or 2 kinds) have only the liquid crystalline cpd of 1 polymerizability functional group, contain c more than a kind or 2 kinds) have a liquid crystalline cpd of 2 above polymerizability functional groups, contain d more than a kind or 2 kinds) have a chipal compounds of 1 above polymerizability functional group, contain e more than a kind or 2 kinds) polymerization starter
R 1-Z 1-B-A-B-Z 2-R 2 (1)
In the formula, R 1And R 2Represent independently that respectively fluorine atom, chlorine atom, cyano group, carbonatoms are that 1～12 alkyl or carbonatoms are 2～12 alkenyl, 1 of the hydrogen atom that contains in these groups or can be replaced by fluorine atom more than it; Z 1The expression singly-bound ,-O-,-S-,-COO-,-OCO-,-OCH 2-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; Z 2The expression singly-bound ,-O-,-S-,-COO-,-OCO-,-CH 2O-,-CH=CH-,-CH=CH-COO-or-OCO-CH=CH-; A represents-C ≡ C-,-C=N-,-N=N-or-C=N-N=C-or following arbitrary ring structure:
Figure FSA00000466647600041
R 3Expression fluorine atom, chlorine atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group or cyano group; B represents following ring structure:
Figure FSA00000466647600042
R 4Expression fluorine atom, chlorine atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group or cyano group.
13. cholesteric reflectance coating as claimed in claim 12, wherein, the polarisation reflected waveband is more than the 300nm.
14. as claim 12 or 13 described cholesteric reflectance coatings, it is the cholesteric reflectance coating with base material, this base material is a plastic film.
15. a reflection-type Polarizer is characterized in that: it is the reflection-type Polarizer of base material, cholesteric reflectance coating and phase retardation film stacked above one another, each described cholesteric reflectance coating that this cholesteric reflectance coating is a claim 12～14.
16. a reflection-type Polarizer is characterized in that: it is the reflection-type Polarizer of base material, cholesteric reflectance coating, phase retardation film and linear polarization film stacked above one another, each described cholesteric reflectance coating that this cholesteric reflectance coating is a claim 12～14.
17. as claim 15 or 16 described reflection-type Polarizers, wherein, have the phase retardation film more than 2 in the reflection-type Polarizer, this phase retardation film has the different phase retardation film of phase differential.
18. each the described cholesteric reflectance coating as claim 12～14 is characterized in that: it was carried out x-ray bombardment processing or electron rays radiation treatment.
19. as each described reflection-type Polarizer of claim 14～18, it is characterized in that: base material is an optical diffusion film.
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