CN101622219A - Polymerizable liquid crystal compound, polymerizable liquid crystal composition, liquid crystal polymer and optically anisotropic substance - Google Patents

Polymerizable liquid crystal compound, polymerizable liquid crystal composition, liquid crystal polymer and optically anisotropic substance Download PDF

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CN101622219A
CN101622219A CN200880006725A CN200880006725A CN101622219A CN 101622219 A CN101622219 A CN 101622219A CN 200880006725 A CN200880006725 A CN 200880006725A CN 200880006725 A CN200880006725 A CN 200880006725A CN 101622219 A CN101622219 A CN 101622219A
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liquid crystal
compound
expression
crystal compound
polymerizable
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坂本圭
谷地义秀
小越直人
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Zeon Corp
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Nippon Zeon Co Ltd
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Abstract

Polymerizable liquid crystal compounds of the following formula (I); a polymerizable liquid crystal composition containing any of the compounds and a polymerizable chiral compound; and a liquid crystal polymer, etc. obtained by polymerization of the compound or composition. There are provided a polymerizable liquid crystal compound and polymerizable liquid crystal composition from which a liquid crystal polymer exhibiting an extremely high optical anisotropy and an excellent solubility in organic solvents and excelling in compatibility with various additives, such as alignment agents, can be formed; and provided a liquid crystal polymer, etc. obtained by polymerization of the compound or composition. In the formula (I), M1 is a C6-C24 aromatic hydrocarbon having three or four bonds; each of Y1 to Y8 is -C(=O)-O-CH2CH2-O-, -C(=O)-O-CH2CH2-, etc.; each of G1 to G3 is a C1-C20 bivalent aliphatic group, etc.; each of Z1 to Z3 is a C2-C10 alkenyl group, etc.; each of A1 and A2 is a C4-C24 bivalent or trivalent aromatic-ring containing group, etc.; and each of a and b is 0, 1 or 2, c 1 or 2, and each of p, q and r 0 or 1.

Description

Polymeric liquid crystal compound, polymerizable liquid-crvstalline composition, liquid crystalline polymers, and optically anisotropic substance
Technical field
[0001]
The present invention relates to polymeric liquid crystal compound, the polymerizable liquid-crvstalline composition that contains polymeric liquid crystal compound and polymerizable chiral compound, the liquid crystalline polymers that is obtained by this liquid crystalline cpd or liquid-crystal composition of polymerization, and contain the optically anisotropic substance of liquid crystalline polymers as component.
Background technology
[0002]
Liquid crystal material has utilized their reciprocal movement and has been widely used as various display mediums.Recently, except being applied to display medium, utilized their physicals such as orientation characteristic, specific refractory power, specific inductivity and susceptibility, studied application for optically anisotropic substance such as phase shift films, polaroid, optics polarizing prism and various spectral filters.
[0003]
In order to obtain stable and optically anisotropic substance uniformly, can under the liquid crystal condition, keep the even state of orientation of liquid crystal molecule, the use that has stable machinery and thermal characteristics, has high second-order transition temperature and have a liquid crystalline polymers of excellent orientation characteristic is preferred.
[0004]
As the material that forms this type of liquid crystalline polymers, has the simple function polymerisable liquid crystal compound of a polymerizable groups, the trifunctional polymerisable liquid crystal compound that has the difunctionality polymerisable liquid crystal compound of two polymerizable groups and have three polymerizable groups is known.This type of polymeric liquid crystal compound has chain-like structure usually and has the linear atomic radical of the conjugation that the liquid crystal aligning performance is provided at the center of chain, and the latter is known as mesogenic group group.
Liquid crystalline polymers can be for example by causing polymeric liquid crystal compound or polymerizable liquid-crvstalline composition even orientation under mesomorphic state, and randomly when keeping mesomorphic state, carry out polymerization and obtain by active energy beam such as ultraviolet radiation.
[0005]
As the example of simple function liquid crystalline cpd, can be set forth in the compound of describing in patent document 1 and 2.This type of polymeric liquid crystal compound is described has high optical anisotropy performance (Δ n).
On the other hand, known film hardness, thermotolerance and the solvent resistance that can improve the polymkeric substance that is obtained effectively of the polymerisable liquid crystal compound of difunctionality and trifunctional.As the example of difunctionality liquid crystalline cpd, can be set forth in the compound described among the patent document 3-5 and, can be set forth in the compound of describing in patent document 6 and 7 as the example of trifunctional liquid crystalline cpd.
[0006]
Patent document 1:JP-A-2002-265421
Patent document 2:JP-A-2002-308832
Patent document 3:JP-T-2002-533742
Patent document 4:JP-A-2005-263789
Patent document 5:JP-A-2005-309255
Patent document 6:JP-A-8-104870
Patent document 7:JP-A-11-130729
Of the present invention open
Problem to be solved by this invention
[0007]
As the result of the above general known polymerisable liquid crystal compound of research, the single functionality that the compound of describing in patent document 1 and 2 is found owing to them has lower crosslink density, causes producing the liquid crystalline polymers with low film hardness.Also find since the high rigidity of molecule caused in organic solvent low solubility and and various additive as the problem of the low mutual solubility between the orientation reagent.The polymerisable liquid crystal compound of describing in patent document 3-5 has polymerizable groups at the two ends of molecule.Polyreaction (comprising crosslinking reaction) is only carried out in molecular end.Be improved though compare with the polymerisable liquid crystal compound of producing from monofunctional compound, the film hardness of gained liquid crystalline polymers remains not enough.Be described in polymerisable liquid crystal compound in patent document 6 and 7 in organic solvent, have low solubility and and various additive between have low mutual solubility.In addition, liquid crystal that can obtain and liquid crystalline polymers only have extremely low optical anisotropy (Δ n).
[0008]
The present invention has considered that the problems referred to above realize and the object of the present invention is to provide: liquid crystalline cpd in general technology, this compound have excellent solubility in organic solvent, with the excellent mutual solubility of various additives, high optical anisotropy (Δ n), excellent orientation characteristic and high film hardness, and this compound can be produced the have high optical anisotropy liquid crystalline polymers of (Δ n); The polymerizable liquid-crvstalline composition that comprises this type of polymeric liquid crystal compound and polymerizable chiral compound; The liquid crystalline polymers that is obtained by polymerisable liquid crystal compound or liquid-crystal composition; With the optically anisotropic substance that contains this type of liquid crystalline polymers.
The means of dealing with problems
[0009]
As the result of broad research, the present inventor has been found that above purpose can realize by the polymerisable liquid crystal compound with the special construction that has three or more aliphatic polymerizable groups.This discovery causes of the present invention finishing.
[0010]
According to a first aspect of the invention, provide a description polymeric liquid crystal compound in following (1)-(4).
(1) polymeric liquid crystal compound of representing by following formula (1),
[0011]
[0012]
M wherein 1Expression has replacement or the unsubstituted trivalent or the tetravalence aromatic hydrocarbon radical of 6-24 carbon atom; Y 1-Y 8Represent chemical single bond separately ,-O-,-S-,-O-C (=O)-,-C (=O)-O-,-O-C (=O)-and O-,-NR 1-C (=O)-,-C (=O)-NR 1-,-O-C (=O)-NR 1-,-NR 1-C (=O)-and O-,-NR 1-C (=O)-NR 1-,-O-NR 1-or-NR 1-O-, wherein R 1Expression hydrogen atom or have the alkyl of 1-6 carbon atom; G 1-G 3Expression has the replacement or the unsubstituted aliphatic divalent group of 1-20 carbon atom separately, and it can comprise-O-,-S-,-O-C (=O)-,-C (=O)-O-,-O-C (=O)-and O ,-NR 2-C (=O)-,-C (=O)-NR 2-,-NR 2-or-C (=O)-(getting rid of the situation that wherein two or more-O-and two or more-S-exist side by side), wherein R 2Expression hydrogen atom or have the alkyl of 1-6 carbon atom; Z 1-Z 3Expression has the thiazolinyl of 2-10 carbon atom separately, and it can be replaced by halogen atom; A 1And A 2Expression has the group that the replacement of 4-24 carbon atom or unsubstituted divalence or trivalent contain aromatic ring separately; A, b and c each naturally 1 or 2; And p, q and r each naturally 0 or 1.
[0013]
(2) polymeric liquid crystal compound of basis (1) is wherein by M 1The aromatic hydrocarbon radical of expression is a phenyl ring, cyclohexyl biphenyl, naphthalene nucleus, terphenyl ring, or anthracene nucleus.
(3) polymeric liquid crystal compound of basis (1) or (2), wherein A 1And A 2Represent phenyl ring separately, cyclohexyl biphenyl, naphthalene nucleus, or anthracene nucleus.
(4) polymeric liquid crystal compound of any one in basis (1)-(3) is wherein by Z 1-Z 3Each CH naturally of the thiazolinyl of expression 2=CH-, CH 2=C (CH 3)-, CH 2=C (Cl)-, CH 2=CH-CH 2-, CH 2=C (CH 3)-CH 2-, CH 2=C (CH 3)-CH 2CH 2-, (CH 3) 2C=CH-CH 2-, CH 3-CH=CH-or CH 3-CH=CH-CH 2-.
[0014]
According to a second aspect of the invention, provide a description polymerizable liquid-crvstalline composition in following (5).
(5) be included in above (1)-(4) polymerizable liquid crystal composition of defined polymeric liquid crystal compound and polymerizable chiral compound in any one.
[0015]
According to a third aspect of the invention we, provide a description the liquid crystalline polymers of in following (6)-(7), describing.
(6) by making in above (1)-(4) polymeric liquid crystal compound described in any one or carrying out the liquid crystalline polymers that polymerization obtained at the polymerizable liquid-crvstalline composition described in above (5).
(7) in the liquid crystalline polymers described in (6), it has 2H or higher pencil hardness.
[0016]
According to a fourth aspect of the present invention, provide a description optically anisotropic substance in following (8).
(8) optically anisotropic substance, it comprises the liquid crystalline polymers that is described in above (6) or (7).
Beneficial effect of the present invention
[0017]
Having the polymeric liquid crystal compound that the liquid crystalline polymers of excellent orientation characteristic, high film hardness and high optical anisotropy (Δ n) can the application of the invention obtains.
Liquid crystalline polymers with above performance can easily be produced and the high quality cholesteric liquid crystal can carry out polymerization by composition of the present invention mutually and forms.
[0018]
Because excellent orientation characteristic, high film hardness and high optical anisotropy (Δ n), liquid crystalline polymers of the present invention can be used as raw material and produces optically anisotropic substance, as phase shift films, the alignment films of liquid crystal display device, polaroid, viewing angle expansion board, colour filter, low pass colour filter, optics polarizing prism and various light-filter.
Because optically anisotropic substance of the present invention is to use polymeric liquid crystal compound preparation of the present invention, optically anisotropic substance has all even high-quality liquid crystal aligning performance.
Implement optimal mode of the present invention
[0019]
The present invention is for 1) polymeric liquid crystal compound, 2) the polymerizable liquid-crvstalline composition, 3) liquid crystalline polymers and 4) each detailed description in the optically anisotropic substance.
[0020]
1) polymeric liquid crystal compound
Polymerisable liquid crystal compound of the present invention is by the compound with following formula (I) expression.
In formula (I), M 1Expression has replacement or the unsubstituted trivalent or the tetravalence aromatic hydrocarbon radical of 6-24 carbon atom.From the consideration of being easy to get property of starting material, the trivalent aromatic hydrocarbon radical is preferably as by M 1The aromatic hydrocarbon radical of expression.The preferred 6-18 of the quantity of the carbon atom in aromatic hydrocarbon radical.
[0021]
Though for by M 1The aromatic hydrocarbon radical of expression is not specifically limited, but from raw-material being easy to get property consideration, phenyl ring, cyclohexyl biphenyl, naphthalene nucleus, terphenyl ring or anthracene nucleus are preferred, and wherein phenyl ring, cyclohexyl biphenyl or naphthalene nucleus are preferred.
[0022]
As the substituent example of aromatic hydrocarbon radical, can enumerate halogen atom such as fluorine atom, chlorine atom and bromine atoms; Cyano group; Hydroxyl; Alkyl such as methyl and ethyl with 1-6 carbon atom; Alkoxyl group such as methoxyl group and oxyethyl group with 1-6 carbon atom; And nitro.
[0023]
Y 1-Y 8Represent chemical single bond separately ,-O-,-S-,-O-C (=O)-,-C (=O)-O-,-O-C (=O)-and O-,-NR 1-C (=O)-,-C (=O)-NR 1-,-O-C (=O)-NR 1-,-NR 1-C (=O)-and O-,-NR 1-C (=O)-NR 1-,-O-NR 1-or-NR 1-O-.
[0024]
R 1Expression hydrogen atom or have the alkyl of 1-6 carbon atom.As by R 1The example of the alkyl with 1-6 carbon atom of expression can be enumerated methyl, ethyl, propyl group and sec.-propyl.As R 1, hydrogen atom or methyl are preferred.
[0025]
G 1-G 3Expression has the replacement or the unsubstituted aliphatic divalent group of 1-20 carbon atom separately.The quantity of the carbon atom in aliphatic group is 1-12 preferably.
[0026]
As by G 1-G 3The aliphatic divalent group with 1-20 carbon atom of expression, the chain aliphatic group is as alkylidene group with 1-20 carbon atom such as ethylidene, propylidene, butylidene, hexylidene and octylene, alkenylene such as vinylidene, crotonylidene, inferior hexenyl and inferior octenyl or the like with 2-20 carbon atom are preferred, so that make composition of the present invention bring into play desired result of the present invention.
[0027]
As by G 1-G 3The substituent example of the aliphatic group of expression can be enumerated halogen atom such as fluorine atom or chlorine atom; Alkoxyl group such as methoxy or ethoxy with 1-6 carbon atom; Alkyl such as methyl or ethyl with 1-6 carbon atom; Or the like.
[0028]
Aliphatic group can comprise-O-,-S-,-O-C (=O)-,-C (=O)-O-,-O-C (=O)-and O ,-NR 2-C (=O)-,-C (=O)-NR 2-,-NR 2-, or-C (=O)-(getting rid of the situation that wherein two or more-O-and two or more-S-exist side by side), R 2Expression hydrogen atom or have the alkyl of 1-6 carbon atom.As by R 2The example of the alkyl with 1-6 carbon atom of expression can be enumerated methyl, ethyl, propyl group, sec.-propyl, and butyl.As R 2, hydrogen atom or methyl are preferred.
[0029]
Z 1-Z 3Expression has the thiazolinyl of 2-10 carbon atom separately, and it can be replaced by halogen atom.The quantity of carbon atom 2-6 preferably in thiazolinyl.
[0030]
As by Z 1-Z 3The object lesson of the thiazolinyl with 2-10 carbon atom of expression can be enumerated CH 2=CH-, CH 2=C (CH 3)-, CH 2=CH-CH 2-, CH 3CH=CH-, CH 2=CH-CH 2-CH 2-, CH 2=C (CH 3) CH 2-, CH 3CH=CH-CH 2-, CH 2=C (CH 3) CH 2CH 2-, (CH 3) 2C=CHCH 2-and (CH 3) 2C=CHCH 2CH 2-.
[0031]
As can be used as by Z 1-Z 3The example of the substituent halogen atom of the thiazolinyl of expression can be enumerated fluorine atom, chlorine atom and bromine atoms.
[0032]
In order to make compound exhibits desired result of the present invention, Z 1-Z 3CH preferably 2=CH-, CH 2=C (CH 3)-, CH 2=C (Cl)-, CH 2=CHCH 2-, CH 2=C (CH 3) CH 2-, CH 2=C (CH 3) CH 2CH 2-, (CH 3) 2C=CHCH 2-, CH 3CH=CH-, or CH 3-CH=CH-CH 2-and more preferably CH 2=CH-, CH 2=C (CH 3)-, CH 2=C (Cl)-, CH 2=CHCH 2-, CH 2=C (CH 3) CH 2-or CH 2=C (CH 3) CH 2CH 2-.
[0033]
A, b and c separately 1 or 2; With p, q and r each naturally 0 or 1.
[0034]
As in following formula (I), being bonded in M 1On by formula-Y 7-(G 3-Y 8) r-Z 3The object lesson of the group of expression can be enumerated following group.In with following formula (I), c is bonded in M 1On by formula-Y 7-(G 3-Y 8) r-Z 3The quantity and the r of the group of expression represent by (G 3-Y 8) quantity of repeating unit of expression.
[0035]
(wherein r=1-Y 7-(G 3-Y 8) r-Z 3Example)
Following general formula is applicable at formula-Y 7-G 3-Y 8-Z 3And the structural relation between the following special groups.Below in the general formula, Y 7=-C (=O)-and O-, G 3=ethylidene, Y 8=-O-C (=O)-, and Z 3=vinyl.
[0036]
Figure A20088000672500091
[0037]
Figure A20088000672500101
[0038]
[0039]
Figure A20088000672500103
[0040]
Figure A20088000672500111
[0041]
(wherein r=0-Y 7-(G 3-Y 8) r-Z 3Example)
Following general formula is applicable at formula-Y 7-Z 3And the structural relation between the following special groups.Below in the general formula, Y 7=-C (=O)-O-and Z 3=vinyl.
[0042]
Figure A20088000672500112
[0043]
Figure A20088000672500113
[0044]
As by formula M 1-Y 7-(G 3-Y 8) r-Z 3The group that shows, following group (M 11)-(M 13) in any be preferred.
[0045]
[0046]
Y wherein 7, G 3, Y 8, r, Z 3Has same meaning with above definition with c.With following formula (M 11), (M 12) and (M 13) in, formula-Y 7-(G 3-Y 8) r-Z 3But can be bonded on any optional the position of substitution on the aromatic ring.
[0047]
As being bonded in respectively with the A in the following formula (I) 1And A 2On by formula-Y 2-(G 1-Y 1) p-Z 1And formula-Y 5-(G 2-Y 6) q-Z 2The object lesson of the group of expression can be enumerated following groups.A and b represent to be bonded in respectively A in following formula (I) 1And A 2On formula-Y 2-(G 1-Y 1) p-Z 1Group and structural formula-Y 5-(G 2-Y 6) q-Z 2The quantity of group.On the other hand, representing unit (G with p in the following formula (I) and q 1-Y 1) and unit (G 2-Y 6) repeat number.
[0048]
(wherein p or q are 1-Y 2-(G 1-Y 1) p-Z 1With-Y 5-(G 2-Y 6) q-Z 2Example)
Following general formula is applicable at formula-Y 2-G 1-Y 1-Z 1And formula-Y 5-G 2-Y 6-Z 2And the structural relation between the following special groups.Below in the general formula, Y 2Or Y 5=-C (=O)-O-, and G 1Or G 2=hexylidene, Y 1Or Y 6=-O-C (=O)-, and Z 1Or Z 2=vinyl.
[0049]
Figure A20088000672500131
[0050]
Figure A20088000672500132
[0051]
Figure A20088000672500133
[0052]
Figure A20088000672500134
[0053]
Figure A20088000672500135
[0054]
Figure A20088000672500141
[0055]
Figure A20088000672500142
[0056]
[0057]
Figure A20088000672500144
[0058]
[0059]
Figure A20088000672500152
[0060]
Figure A20088000672500153
[0061]
(wherein p or q are 0-Y 2-(G 1-Y 1) p-Z 1With-Y 5-(G 2-Y 6) q-Z 2Example)
Following general formula is applicable at formula-Y 2-Z 1Or formula-Y 5-Z 2And the structural relation between the following special groups.Below in the general formula, Y 2Or Y 5=-C (=O)-O-and Z 1Or Z 2=vinyl.
[0062]
Figure A20088000672500161
[0063]
Figure A20088000672500162
[0064]
A 1And A 2Expression replacement or unsubstituted divalence or trivalent contain the group of aromatic ring separately.The group that contains aromatic ring is to have the organic group of aromatic ring and preferably come keyed jointing group Y via this aromatic ring 2And Y 3And group Y 4And Y 5The quantity of carbon atom is 4-24 and preferred 6-20 in containing the group of aromatic ring.
Though the aromatic ring for the group that contains aromatic ring is not particularly limited, phenyl ring, cyclohexyl biphenyl, naphthalene nucleus, the terphenyl ring, anthracene nucleus, pyridine ring, pyrimidine ring, the pyridazine ring, thiphene ring etc. can be enumerated as an example.
Among these groups, from raw-material being easy to get property consideration, the group that contains aromatic ring of divalence is preferably as A 1And A 2The group that contains aromatic ring.
By A 1And A 2The object lesson of the group of expression is listed below.
[0065]
Figure A20088000672500171
[0066]
Figure A20088000672500181
As by A 1And A 2The substituent example of the group that contains aromatic ring of expression can be enumerated halogen atom such as fluorine atom, chlorine atom and bromine atoms; Cyano group; Hydroxyl; Alkyl such as methyl and ethyl with 1-6 carbon atom; Alkoxyl group such as methoxyl group and oxyethyl group with 1-6 carbon atom; And nitro.
[0067]
[0068]
In order to demonstrate desired result of the present invention, phenyl ring, cyclohexyl biphenyl, naphthalene nucleus or anthracene nucleus are preferably as A 1And A 2, following groups (A wherein 11), (A 21) and (A 31) be preferred.Following groups (A 11), (A 21) and (A 31) have substituting group in can be at an arbitrary position.
[0069]
Figure A20088000672500191
[0070]
Object lesson by the polymerisable liquid crystal compound of the present invention of formula (I) expression includes but not limited to compound shown below.In polymerisable liquid crystal compound, by the M that is bonded in shown in the following formula with following formula (I) expression 1On two kinds of groups:
[0071]
Figure A20088000672500192
[0072]
Figure A20088000672500193
[0073]
Can be identical or different.
In each following formula, formula:
[0074]
Figure A20088000672500194
[0075]
Expression, by formula-C (=O)-O-CH 2CH 2O-C (=O)-CH=CH 2But shown group is bonded in any optional the position of substitution (the same applies to phenyl ring, cyclohexyl biphenyl and terphenyl ring) on naphthalene nucleus.
[0076]
Figure A20088000672500201
[0077]
Figure A20088000672500211
[0078]
Figure A20088000672500221
[0079]
Figure A20088000672500231
[0080]
[0081]
Figure A20088000672500251
[0082]
Figure A20088000672500261
[0083]
Figure A20088000672500271
[0084]
Figure A20088000672500281
[0085]
Figure A20088000672500291
[0086]
Figure A20088000672500301
[0087]
Figure A20088000672500311
[0088]
Figure A20088000672500321
[0089]
Figure A20088000672500331
[0090]
Figure A20088000672500341
[0091]
Figure A20088000672500351
[0092]
Figure A20088000672500361
[0093]
[0094]
Figure A20088000672500381
[0095]
Figure A20088000672500391
[0096]
Figure A20088000672500401
[0097]
Figure A20088000672500411
[0098]
Figure A20088000672500421
[0099]
[0100]
Figure A20088000672500441
[0101]
Figure A20088000672500451
[0102]
Figure A20088000672500461
[0103]
Figure A20088000672500471
[0104]
Figure A20088000672500481
[0105]
Figure A20088000672500491
[0106]
[0107]
Figure A20088000672500511
[0108]
[0109]
Figure A20088000672500531
[0110]
Figure A20088000672500541
[0111]
[0112]
Figure A20088000672500561
[0113]
[0114]
Figure A20088000672500581
[0115]
[0116]
[0117]
Figure A20088000672500611
[0118]
Figure A20088000672500621
[0119]
Figure A20088000672500631
[0120]
Whole polymerisable liquid crystal compound of the present invention can prepare by the currently known methods that forms various chemical bonds in conjunction with those, chemical bond is as-O-,-S-,-ONH-,-C (=O) NH-,-NHC (=O) NH-,-C (=O)-O-, or the like (referring to, Sandler Callot OrganicCompound Synthetic Method[I for example], [II] categorized by functional groups, Hirokawa Publishing, 1976).Typically, polymerisable liquid crystal compound of the present invention can be by being used to form ehter bond (O-) in conjunction with those arbitrarily, ester bond (C (=O)-O-), (reaction COCl) is prepared by the suitable keyed jointing or the modification of two or more generalization compounds with desired structure for amido linkage (C (=O) NH-) and acyl chlorides.
[0121]
Ehter bond can form by for example the following stated.
I) compound and the condensation of the compound of formula Q1-X (X is a halogen atom, below identical) and formula Q2-OM (M represents basic metal, mainly is sodium, below identical).In formula, Q1 is any optional organic group B (following identical) with Q2.This reaction common name Williamson (Williamson) synthesis method.
Ii) the compound of formula Q1-X mixes and condensation in the presence of alkali such as sodium hydroxide or potassium hydroxide with the compound of formula Q2-OH.
Iii) the compound of formula Q1-E (E represents epoxy group(ing)) mixes and condensation in the presence of alkali such as sodium hydroxide or potassium hydroxide with the compound of formula Q2-OH.
Iv) the compound of formula Q1-OFN (OFN represents unsaturated link(age)) mixes in the presence of alkali such as sodium hydroxide or potassium hydroxide with the compound of formula Q2-OM and carries out addition reaction.
V) the compound of formula Q1-X mixes and condensation in the presence of cupric chloride or cuprous chloride with the compound of formula Q2-OM.This reaction common name Liv Ullmann (Ullmann) condensation reaction.
[0122]
Ester bond and amido linkage can form by for example the following stated.
I) compound of formula Q1-COOH and formula Q2-OH or Q2-NH 2The compound condensation that under dehydrating condensation agent (N, N-dicyclohexyl carbodiimide, or the like) exists, is hydrolyzed.
Ii) the compound of formula Q1-COOH and halogenating agent react the compound of acquisition formula Q1-COX, the latter and formula Q2-OH or Q2-NH 2Compound in the presence of alkali, react.
Iii) the compound of formula Q1-COOH and anhydride reaction obtain mixed acid anhydride, the latter and formula Q2-OH or Q2-NH 2Compound react.
The iv) compound of formula Q1-COOH and formula Q2-OH or Q2-NH 2The compound condensation that in the presence of acid catalyst or alkaline catalysts, is hydrolyzed.
[0123]
Acyl chlorides can form by for example the following stated.
I) compound of formula Q1-COOH and phosphorus trichloride or phosphorus pentachloride react.
Ii) the compound of formula Q1-COOH and thionyl chloride are reacted.
Iii) the compound of formula Q1-COOH and oxalyl chloride react.
Iv) compound and the chlorine or bromine of formula Q1-COOAg (Ag is a silver) react.
V) the carbon tetrachloride solution (redness) of the compound of formula Q1-COOH and red precipitate (II) reacts.
[0124]
In any reaction, reaction product can randomly be handled by the post-treating method commonly used in Synthetic Organic Chemistry after reaction is finished, and target compound can wait and separate by general purification and separate mode such as column chromatography, recrystallization, distillation.
The structure of target compound can be by adopting the NMR spectrum, and IR composes, and the measurement of mass spectrum etc., ultimate analysis and similar approach are identified.
[0125]
2) polymerizable liquid-crvstalline composition
In a second aspect of the present invention, the polymerizable liquid-crvstalline composition is provided, it comprises polymerisable liquid crystal compound of the present invention and can carry out polymeric chipal compounds (hereinafter to be referred as " polymerizable chiral compound ") with this polymerisable liquid crystal compound.This type of polymerizable liquid-crvstalline composition is called " composition of the present invention " below sometimes.
[0126]
As the polymeric liquid crystal compound that is used for composition of the present invention, can enumerate aforesaid one or more polymerisable liquid crystal compounds of the present invention.Except that polymerisable liquid crystal compound of the present invention, can use other common known polymerisable liquid crystal compound those as in above-mentioned patent document, mentioning.
When using this type of other polymerisable liquid crystal compound, the 5wt% of the total amount of the polymerisable liquid crystal compound that the amount of polymerisable liquid crystal compound of the present invention is normally used in composition or more and 10wt% or more preferably.
[0127]
The polymerizable chiral compound that is used for composition of the present invention must have chiral carbon atom in molecule, must with polymerisable liquid crystal compound polymerizable of the present invention, and must not disturb the orientation of polymerisable liquid crystal compound.Any compound that satisfies these conditions can be used with being not particularly limited.
Term " polymerisable " refers to participate in the ability in the generalized chemical reaction, not only comprises general polyreaction, and comprises crosslinking reaction.
The mixture of the polymerizable chipal compounds of any type or the polymerizable chipal compounds of two or more types can be used in the composition of the present invention.Except that the polymerizable chipal compounds, not polymerisable common chipal compounds can add in the composition of the present invention, as long as desired result of the present invention is without prejudice.
If mix, form the polymerisable liquid crystal compound exhibits cholesteric phase of composition of the present invention with the polymerizable chipal compounds.
[0128]
As the polymerizable chipal compounds, the compound that compound known is for example used in the embodiment of JP-A-11-193287 can both use.As the example of this type of chipal compounds, can enumerate the compound of representing by following three formulas.
[0129]
Figure A20088000672500661
[0130]
Figure A20088000672500662
[0131]
Figure A20088000672500663
[0132]
In above structural formula, R 3And R 4The expression hydrogen atom, methyl or methoxy.As Y 9And Y 10, can enumerate-O-,-O-C (=O)-,-O-C (=O)-O-etc.m 1And m 2Each is naturally 2,4 or 6 years old.The compound that is expressed from the next can be listed as the object lesson of the compound of being represented by these formulas.
[0133]
Figure A20088000672500671
[0134]
Except the compound of representing by above three formulas, can also use the compound that is expressed from the next.
[0135]
[0136]
The polymerizable chipal compounds uses with the amount of common 0.1-100 weight part and preferred 0.5-10 weight part in composition of the present invention, for the polymerisable liquid crystal compound of 100 weight parts.
[0137]
In order to ensure polyreaction efficiently, preferably polymerization starter (particularly Photoepolymerizationinitiater initiater) is added in the composition of the present invention.Can enumerate as the example of initiators for polymerization by the compound shown in following " 3) liquid crystalline polymers " part.Initiators for polymerization uses with the amount of common 0.1-30 weight part and preferred 0.5-5 weight part in composition of the present invention, for the polymerisable liquid crystal compound of 100 weight parts.
[0138]
Preferably tensio-active agent is added in the composition of the present invention, so that the reconciliation statement surface tension.Though be not particularly limited,, preferably use nonionogenic tenside.Can use the nonionogenic tenside that is purchased, for example, have approximately the nonionogenic tenside oligopolymer of several thousand molecular weight, as by AGC Seimi Chemical Co., " KH-40 " that Ltd makes.Tensio-active agent uses with the amount of common 0.01-10 weight part and preferred 0.1-2 weight part in composition of the present invention, for the polymerisable liquid crystal compound of 100 weight parts.
[0139]
When composition of the present invention as the starting material of polarization film and alignment films or as printing-ink, when coating or protective membrane, except that said components, other various additives such as other copolymerisable monomer of mentioning later; metal, metal complex, dyestuff; pigment, fluorescent substance, phosphor material; flow agent, thixotropic agent, gelifying agent; polysaccharide, UV absorption agent, infrared absorbing agents; antioxidant, ion exchange resin and metal oxides such as titanium dioxide also can add.These other additives amount with common 0.01-20 weight part in composition of the present invention is used, for the polymerisable liquid crystal compound of 100 weight parts.
[0140]
Typically, composition of the present invention can be by the polymerisable liquid crystal compound of the present invention with specified quantitative, the polymerizable chipal compounds, and Photoepolymerizationinitiater initiater, nonionogenic tenside and other optional additive are dissolved in the appropriate organic solvent and prepare.
[0141]
As employed representative examples of organic, can enumerate ketone such as cyclopentanone, pimelinketone and methyl ethyl ketone, ester such as butylacetate and pentyl acetate, halohydrocarbon such as chloroform, methylene dichloride and ethylene dichloride, with ether as 1,4-diox, cyclopentyl-methyl ether, tetrahydrofuran (THF) and tetrahydropyrans.
[0142]
So the polymerizable liquid-crvstalline composition that obtains can be used as starting material and the cholesteric liquid crystal polymer (back will be described) that forms the cholesteric liquid crystal phase.
[0143]
3) liquid crystalline polymers
As the third aspect, the invention provides the liquid crystalline polymers that is obtained by polymerization polymerisable liquid crystal compound of the present invention or polymerizable liquid-crvstalline composition.
Term " polymerisable " refers to participate in the ability in the generalized chemical reaction, not only comprises general polyreaction, and comprises crosslinking reaction.
[0144]
Liquid crystalline polymers of the present invention is the polymkeric substance that obtained by polymerization polymerizable liquid crystal composition of the present invention of (1) polymkeric substance of being obtained by polymerization polymerisable liquid crystal compound of the present invention or (2) specifically.
[0145]
(1) polymkeric substance that is obtained by polymerization polymerisable liquid crystal compound of the present invention
The polymkeric substance that is obtained by polymerization polymerisable liquid crystal compound of the present invention comprises the homopolymer of polymerisable liquid crystal compound of the present invention, the multipolymer of two or more polymerisable liquid crystal compound of the present invention, the multipolymer of polymerisable liquid crystal compound of the present invention and another kind of general known polymeric liquid crystal compound, and the multipolymer of polymerisable liquid crystal compound of the present invention and another kind of general known copolymerisable monomer.
[0146]
As the example of the general known polymerisable liquid crystal compound of another kind, can be set forth in any polymeric liquid crystal compound of describing in the above-mentioned patent document.
Another kind of general known copolymerisable monomer is not particularly limited.The example that can enumerate comprises 4-(2-methacryloxy oxyethyl group) phenylformic acid 4 '-p-methoxy-phenyl ester; 4-(6-methacryloxy hexyloxy) phenylformic acid biphenyl ester; 4-(2-methacryloxy oxyethyl group) phenylformic acid 4 '-cyanobiphenyl base ester; 4-(2-methacryloxy oxyethyl group) phenylformic acid 3 '; 4 '-difluorophenyl ester; 4-(2-methacryloxy oxyethyl group) phenylformic acid naphthyl ester; 4-acryloxy-4 '-decyl biphenyl; 4-acryloxy-4 '-cyanobiphenyl; 4-(2-methacryloxy oxyethyl group)-4 '-methoxyl biphenyl; 4-(2-methacryloxy oxyethyl group)-4 '-(4 "-the fluorine benzyloxy) biphenyl; 4-acryloxy-4 '-propyl cyclohexyl base; 4-methacryloyl-4 '-butyl dicyclohexyl; 4-acryl-4 '-amyl group tolane; 4-acryl-4 '-(3; the 4-difluorophenyl) dicyclohexyl; 4-(2-acryloxy ethyl) phenylformic acid (4-amyl group phenyl) ester, and 4-(2-acryloxy ethyl) phenylformic acid (4-(4 '-propyl group cyclohexyl) phenyl) ester.
[0147]
When liquid crystalline polymers of the present invention is the multipolymer of polymerisable liquid crystal compound of the present invention and another kind of copolymerisable monomer and/or another kind of general known polymerisable liquid crystal compound, the amount of polymerisable liquid crystal compound of the present invention is the 5wt% of monomer total amount or more and be more preferably 10wt% or more preferably.The amount of polymerisable liquid crystal compound of the present invention in this scope guaranteed to produce the liquid crystalline polymers with high glass-transition temperature (Tg) and produced the film with high rigidity.
[0148]
(being total to) polyreaction of polymerisable liquid crystal compound of the present invention and optional other copolymerisable monomer that uses can be carried out in the presence of polymerization starter.More than be applicable to the amount of initiators for polymerization for the narration of the amount of polymerisable liquid crystal compound in polymerizable liquid crystal composition.
[0149]
Suitable polymerization starter is selected according to the type of polymerizable groups in the polymerisable liquid crystal compound.For example, when polymerisable group is the polymerisable group of free radical, use radical polymerization initiator; When polymerisable group is the group of anion polymerisable, use anionic polymerization initiator; With when polymerisable group is the group of cationic polymerizable, use cationic polymerization initiators.Though can use thermic free-radical generating agent or photic free-radical generating agent, photic free-radical generating agent is preferred.
[0150]
The example of photic free-radical generating agent comprises bitter almond oil camphor class such as bitter almond oil camphor, benzoin methyl ether and bitter almond oil camphor propyl ether; Phenyl methyl ketone class such as phenyl methyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-Er Lvyixianben, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino-third-1-ketone, and N, N-dimethylamino acetyl benzene; Anthraquinone class such as 2-methylanthraquinone, 1-chloroanthraquinone and 2-amyl anthraquinone; The thioxanthene ketone is as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone and 2,4-di-isopropyl thioxanthone; Ketal class such as phenyl methyl ketone dimethyl ketal and benzyl dimethyl ketal; Benzophenone such as benzophenone, methyldiphenyl ketone, 4,4-dichloro benzophenone, 4, the two diethylamino benzophenone of 4-, Michiler ketone and 4-benzoyl-4-dimethyl diphenyl sulfide; With 2,4,6-trimethylbenzoyl diphenyl phosphine oxide.
[0151]
As the object lesson of photic free-radical generating agent, can enumerate SpecialtyChemicals by Ciba, the Irgacure 907 that Co. makes, Irgacure 184, and Irgacure 369, Irgacure651 or the like.
[0152]
The example of anionic polymerization initiator comprises alkyl lithium compounds; Lithium salts of biphenyl, naphthalene, pyrene or the like or sodium salt; Polyfunctional initiator; Two lithium compounds; With three lithium compounds.
[0153]
As the example of cationic polymerization initiators, can enumerate protonic acid such as sulfuric acid, phosphoric acid, perchloric acid and trifluoromethanesulfonic acid; Lewis acid such as boron trifluoride, aluminum chloride, titanium tetrachloride and tin tetrachloride; And the combination of aromatics salt or aromatics salt and reductive agent.
These polymerization starters can use separately or being used in combination with two or more.
[0154]
(being total to) polyreaction of polymerisable liquid crystal compound and optional other copolymerisable monomer that uses can be carried out in the presence of functional compound such as UV absorption agent, infrared absorbing agents and antioxidant.
[0155]
More particularly, liquid crystalline polymers of the present invention can be produced by the following method: the method that (A) (is total to) polymerization polymerisable liquid crystal compound and optional other copolymerisable monomer that uses in appropriate organic solvent in the presence of suitable polymerization starter, or (B) preparation polymerisable liquid crystal compound, optional other copolymerisable monomer and the solution of polymerization starter in organic solvent that uses, by general method of application with on this solution paint carrier, desolvate with under the state of monomer orientation, removing, and heat or apply the method for active energy beam.
[0156]
Any inert organic solvents can be used for method (A) with being not particularly limited.Example comprises aromatic hydrocarbon such as toluene, dimethylbenzene and sym-trimethylbenzene; Ketone such as pimelinketone, cyclopentanone, and methyl ethyl ketone, acetic ester such as butylacetate and pentyl acetate; Halohydrocarbon such as chloroform, methylene dichloride, and ethylene dichloride; With ether such as cyclopentyl-methyl ether, tetrahydrofuran (THF), and tetrahydropyrans.Among these, the solvent with boiling point of 60-250 ℃ is preferred, considers that from easy disposal 60 to 150 ℃ is preferred especially.
[0157]
When using method (A), after the polyreaction under following mentioned condition from polymers soln isolated liquid crystalline polymers be dissolved in and prepare solution in the appropriate organic solvent, this solution is applied to then and obtains coating on the suitable carriers, this coating is dried and heats till polymkeric substance becomes anisotropy, and little by little liquid crystal state is kept in cooling.
[0158]
As the organic solvent that is used for the lysate crystalline polymer, can enumerate ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, and pimelinketone; Ester such as butylacetate and pentyl acetate; Halohydrocarbon such as methylene dichloride, chloroform and ethylene dichloride; With ether such as tetrahydrofuran (THF), tetrahydropyrans, 1,2-glycol dimethyl ether, 1,4-diox and cyclopentyl-methyl ether.
[0159]
As carrier, can use the base material of making by the organic or inorganic material of general use.As the examples of material that is used for base material, (registered trademark is by Nippon Zeon Co. can to enumerate poly-cycloolefin such as Zeonex and Zeonor, Ltd makes), Arton (registered trademark is made by JSR Corp.), and Apel (registered trademark, by Mitsui Chemicals, Inc. makes), polyethylene terephthalate, polycarbonate, polyimide, polymeric amide, polymethylmethacrylate, polystyrene, polyvinyl chloride, tetrafluoroethylene, Mierocrystalline cellulose, cellulose triacetate, polyethersulfone, silicon, glass, and calcite.Flat board or curved slab can be used as base material.Base material can have electrode layer, anti-reflective function, or reflection function, and it is fixed to come as required.
[0160]
General method can be used in solution coat with liquid crystalline polymers to carrier.As an example, can enumerate coating method, eject (knockout) coating method, rolling method, spin coating method, dip coating, rod is coated with method, spraying method, slippage coating method and printing coating method.
[0161]
As the organic solvent that in above method (B), uses, can enumerate ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, and pimelinketone; Ester such as butylacetate and pentyl acetate; Halohydrocarbon such as methylene dichloride, chloroform and ethylene dichloride; With ether such as tetrahydrofuran (THF), tetrahydropyrans, 1,2-glycol dimethyl ether, 1,4-diox and cyclopentyl-methyl ether.
[0162]
Carrier is not particularly limited.Example comprises above-mentioned as the material on the liquid crystalline polymers solution paint carrier those.
[0163]
In above method (B), the solution that general method can be used in polyreaction is applied on the carrier.Example comprises that above-mentioned conduct applies those of material of liquid crystalline polymers solution.
[0164]
In the aforesaid method (B), preferably make the polymerisable liquid crystal compound be coated with portion to carrier to be orientated.As the method that makes polymerisable liquid crystal compound orientation, can for example enumerate making carrier carry out the method for orientation process in advance.As the preferred method of orientation process, can enumerate general known method, as on substrate surface, forming the method for liquid crystal aligning layer or alignment film of polyimide, polyvinyl alcohol alignment films or similar film and this alignment films that rubs, by SiO 2Oblique evaporation forms the method for alignment films to the base material, in molecule, have the organic film of functional group's (reacting) or in molecule, have the method for organic film of the functional group of optical isomerization with radiation such as polarized light or non-polarized lights by photo-induced dimerization, or the like.The polyreaction of polymerisable liquid crystal compound can be carried out under the described below polymeric reaction condition.
[0165]
(2) liquid crystalline polymers that is obtained by polymerization polymerizable liquid crystal composition of the present invention
Liquid crystalline polymers of the present invention can easily obtain by polymerization polymerizable liquid crystal composition of the present invention in the presence of polymerization starter.The liquid crystalline polymers that is obtained is a cholesteric liquid crystal polymer.In order to ensure polyreaction more efficiently, preferably use the polymerizable liquid crystal composition that comprises polymerization starter (particularly Photoepolymerizationinitiater initiater) and polymerizable chiral compound.Use this type of polymerizable liquid-crvstalline method for compositions to be described below.
[0166]
Specifically, on the carrier (it by above-mentioned base material is applied orientation process obtain) that liquid crystalline polymers can be by having polymerizable liquid crystal composition paint of the present invention the orientation function, and polymerisable liquid crystal compound in the composition is orientated equably obtain keeping cholesteric.As carrier, can use above-mentioned those.
[0167]
In order to form even state of orientation, can use Kapton, it can cause employed pre-tilt angle in general stable twisted nematic (TN) element or STN Super TN (STN) element, and described element can easily be controlled the state of orientation of polymerisable liquid crystal compound.
[0168]
Generally, when liquid-crystal composition contacted with the carrier with orientation function, liquid crystalline cpd is orientated on carrier surface in one direction, and was processed to be orientated along this direction carrier.The direction of liquid crystalline cpd orientation (horizontal plane tilts, or perpendicular to the surface of carrier) mainly is subjected to the method for the orientation process of carrier surface is influenced.
For example, when the very little alignment films of the pre-tilt angle in the liquid crystal display device that on carrier, is provided for plane internal switch (IPS) system, obtained the almost polymerizable liquid-crvstalline layer of horizontal alignment.
[0169]
During alignment films on carrier, being provided for TN type liquid crystal display device, obtained to have the polymerizable liquid crystal layer of the orientation that tilts a little, and during the alignment films on base material, being provided for STN type liquid crystal display device, obtained to have the polymerizable liquid crystal layer of remarkable tilted alignment.
[0170]
When composition of the present invention contacts with the pre-tilt angle with the carrier with horizontal alignment function, can obtain optically anisotropic substance, the latter is a tilted alignment, change equably or continuously simultaneously near carrier surface to angle near air interface.
[0171]
If use wherein in molecule, to have to have the organic film of reactive functional group by the photo-induced dimerization reaction or have the organic film (below abbreviation " optical orientation film ") that isomerized functional group takes place by radiation and carry out radiating method (optical orientation method) with polarized light or non-polarized light, then can obtain to have the base material in many zones, each in these zones has and the different differently-oriented directivity in other zone that distributes according to the pattern mode.
[0172]
At first, provide carrier to carry out radiation with the preparation carrier thereon, on this carrier, can obtain uniform orientation with the light of wavelength within the absorption band of optical orientation film with optical orientation film.After this, carrier covers with mask and uses the light different with first kind of radiant light of the absorbing wavelength with optical orientation film to carry out radiation, the light that for example has the light of different polarization state or have different angle of radiation and direction, so that the film with orientation function to be provided, this function be different from by selectively on radiation areas the first time zone that radiation is obtained function.
[0173]
If polymerizable liquid crystal composition of the present invention contacts with carrier, each zone on carrier (wherein being orientated the function difference) distributes according to the pattern form that is obtained in the above described manner, and then each zone that differently-oriented directivity is different in pattern form distributes according to the orientation function of carrier.If under this state, carry out radio polymerization, then can obtain to have the liquid crystalline polymer film of orientation pattern.
[0174]
When the carrier with approximate horizontal orientation function (zone that wherein has the different orientation direction distributes according to pattern form) is used as above carrier, can obtain to can be used as especially the liquid crystalline polymer film of phase retardation film.
[0175]
Can also enumerate the method for not using the optical orientation film as method with AFM (atomic force microscope) perception pin friction orientation film, the method for etching optically anisotropic substance, or the like.Yet the method for using the optical orientation film is simple and preferred.
[0176]
As the method that composition of the present invention is applied on the carrier, can enumerate general method, be coated with spin coating, roller coat, intaglio plate coating, spraying, mouthful mould coating, veneer (cap) coating, dip-coating or the like as rod.But in order to improve coating, common known organic solvent can be added in the composition of the present invention.In this case, preferably after being applied to composition on the carrier by dry air, heat drying, decompression is dry down, heat drying under reduced pressure, or the like remove organic solvent.
[0177]
After coating, preferably the liquid crystalline cpd in composition is orientated under the state of keeping the cholesteric phase equably.Specifically, orientation can promote that thermal treatment can promote liquid crystal aligning by thermal treatment.
[0178]
For example, after being applied to composition of the present invention on the carrier, coating is heated above the transformation temperature from solid phase (C) to nematic phase (N) of liquid crystalline cpd or the temperature of the transformation temperature from solid phase (C) to smectic phase (S) (hereinafter to be referred as " C-N or C-S transition temperature "), and as required, little by little be cooled and cause that cholesteric shows mutually.In this case, preferably composition is maintained certain temperature, under this temperature, demonstrate mesomorphic phase, thereby cause that the mesomorphic phase farmland fully grows into single domain.
[0179]
After being applied to composition of the present invention on the carrier, might heat the composition for some time that is coated with down in a kind of temperature (cholesteric of liquid-crystal composition shows mutually under this temperature).
[0180]
If temperature is too high, then owing to undesirable polyreaction, the polymerisable liquid crystal compound may deterioration.If cooling excessively, then polymerizable liquid crystal composition may be separated and deposited crystal, thereby produces the mesomorphic phase such as the smectic phase of high-sequential, makes and can not carry out orientation process.
This type of thermal treatment can be prepared the even liquid crystalline polymer film of the orientation defective with lesser amt, compares with the method for simple coating composition.
[0181]
After this type of even orientation process, this is filmed and is cooled to minimum temperature (mesomorphic phase does not cause and is separated under this temperature, promptly be cooled to undue refrigerative state), and keep mesomorphic phase under state of orientation in polymerization under this temperature, can obtain to have the high ordered orientation and the liquid crystalline polymer film of excellent transparency in view of the above.
[0182]
As the method for polymerization polymerisable liquid crystal compound of the present invention or polymerizable liquid crystal composition, can enumerate the method for radiation high reactivity energy-ray, the method for heating, or the like.It is preferred can need not to heat the induce reaction method of the radiation active energy beam that at room temperature carries out.As method of radiating, it is preferred only to need making of simple program to use up as the method for UV ray.
[0183]
Carry out radiation making polymerisable liquid crystal compound or polymerizable liquid crystal composition can keep under the temperature of mesomorphic phase.For fear of the thermopolymerization of polymerisable liquid crystal compound or polymerizable liquid crystal composition, the temperature that is no more than 30 ℃ as far as possible is preferred.In heat-processed, polymerisable liquid crystal compound or polymerizable liquid crystal composition demonstrate mesomorphic phase usually in the scope of (isotropic liquid phase) transition temperature from the C-N transition temperature to N-I.On the other hand, because polymerisable liquid crystal compound and polymerizable liquid crystal composition enter into thermodynamics non-equilibrium in the refrigerative process, so there is such situation: compound and composition are kept liquid crystal state, not cohesion under the temperature that is lower than the C-N transition temperature.This state is known as but state of supercool.In the present invention, but the polymerisable liquid crystal compound and the polymerizable liquid crystal composition of state are considered to maintain liquid crystal state to be in supercool.The yield of radiation of UV ray is 1W/m normally 2-10kW/m 2And preferred 5W/m 2-2kW/m 2
[0184]
Having two or more liquid crystalline polymer film with zone of different orientation direction can be by the UV radio polymerization specific region via mask, change the not state of orientation of the zone of convergency by applying electric field, magnetic field or heating, and this unpolymerized zone of polymerization obtains.
[0185]
Liquid crystalline polymer film with two or more zones with different orientation direction also can be regulated orientation in advance by before polymerization polymerisable liquid crystal compound or polymerizable liquid crystal composition being applied electric field, magnetic field or heat, and only comes by the UV radiation radius on mask via mask when keeping this state that the polymerization specific region obtains.
[0186]
The liquid crystalline polymers that is obtained by polymerization polymerisable liquid crystal compound or polymerizable liquid crystal composition of the present invention can be separated with employed carrier former state and maybe can be kept being attached on the carrier, with carrier as optically anisotropic substance.Only stain (stain) other material because adhered to the carrier of liquid crystalline polymers on it, this material can be as using by laminated main body or by being attached on another carrier quite difficultly.
[0187]
The liquid crystalline polymer film that is obtained by polymerization composition of the present invention is a cholesteric liquid crystal film.Because cholesteric liquid crystal film has high reflectivity, film is suitable as the polarizer in liquid crystal display device.
[0188]
In addition, might be by laminating method with two-layer or this type of liquid crystalline polymers film lamination of multiwalled and obtain multilayer polarizer, the latter covers whole light (referring to EP 0720041) of visible spectrum by the wavelength of suitably selecting selected liquid crystalline polymers.
[0189]
Substitute and produce this type of multilayer polarizer, liquid crystalline polymer film can be used for by making the more polarizer of broad band in conjunction with suitable compound and suitable process conditions.Can use at for example WO 98/08135, EP 0606940, the method for describing among GB 2312529 and the WO 96/02016.
[0190]
Colour filter can use polymerisable liquid crystal compound of the present invention and polymerizable liquid crystal composition to produce.In order to produce colour filter, the method that can use always according to those skilled in the art suitably applies required wavelength.
[0191]
In addition, also can use the thermochromism of cholesteric liquid crystal.By attemperation, the color of cholesteric phase changes to blueness from redness via green.Specific zone can be by using mask polymerization under the temperature of regulation.
[0192]
The number-average molecular weight of the liquid crystalline polymers of the present invention of Huo Deing 500-500 preferably in a manner described, 000 and more preferably 5,000-300,000.Number-average molecular weight in this scope is not only for obtaining high film hardness, and is preferred for easily handling this polymkeric substance.The number-average molecular weight of liquid crystalline polymers can use monodisperse polystyrene as standard model and tetrahydrofuran (THF) (THF) as eluent, measure by gel permeation chromatography (GPC).
[0193]
Liquid crystalline polymers of the present invention is considered to have equally distributed cross-linking set in molecule.Because polymkeric substance obtains by the polyreaction of the liquid crystalline cpd of the present invention of the high cross-linking efficiency of demonstration, so polymkeric substance has high hardness.
[0194]
Liquid crystalline polymers of the present invention has 2H or higher pencil hardness usually, according to JIS K5600-5-4.When as optically anisotropic substance, the liquid crystalline polymers of the present invention with high rigidity can be protected the surface of carrier such as glass with other functional materials lamination the time.
[0195]
By utilizing orientation characteristic and physicals such as specific refractory power, specific inductivity and susceptibility, liquid crystalline polymers of the present invention can be used as the starting material of producing optically anisotropic substance, this class material for example is a phase shift films, the alignment films of liquid crystal display device, polaroid, visual angle expansion board, colour filter, low-pass filter, optics polarizing prism and various spectral filter.
[0196]
4) optically anisotropic substance
The 4th aspect of the present invention provides the optically anisotropic substance of making from liquid crystalline polymers of the present invention.
As the example of optically anisotropic substance of the present invention, can enumerate phase shift films, the alignment films of liquid crystal display device, polaroid, visual angle expansion board, colour filter, low-pass filter, optics polarizing prism and various spectral filter.
[0197]
Because optically anisotropic substance of the present invention is to obtain by polymerization polymerisable liquid crystal compound of the present invention, optically anisotropic substance has uniform and high-quality liquid crystal aligning performance.
Embodiment
[0198]
The present invention utilizes embodiment to describe in detail now, but should not be considered as restriction the present invention.
[0199]
Synthesizing of (embodiment 1) compound 1
[0200]
Figure A20088000672500781
[0201]
(step 1) intermediate compound A's is synthetic
[0202]
[0203]
The 2-acryloxy ethyl succsinic acid (by Kyoeisha ChemicalCo., Ltd makes) that adds 50g (0.23mol) in the four neck reaction vessels of condenser, thermometer and dropping funnel is being housed under nitrogen gas stream.Use dropping funnel will be dissolved at room temperature that formed solution adds at leisure in the tetrahydrofuran (THF) (THF) of 300ml by the oxalyl chloride of 292g (2.3mol).After adding, mixture at room temperature stirred 24 hours.
After reaction is finished, from reaction soln, remove unreacted oxalyl chloride by using rotatory evaporator under reduced pressure to distill, obtain the 2-acryloxy Ethyl Succinyl Chloride of the yellow oil form of 54g.Acyl chlorides former state under the situation that does not have purification is used for next reaction.
[0204]
Then, formed solution among the THF that the 6-hydroxyl-2-naphthoic acid that adds in the four neck reaction vessels of condenser, thermometer and dropping funnel by 10g (53.1mmol) is dissolved in 200ml is being housed under nitrogen gas stream.With in ice-cooled, the triethylamine of 11.3g (111.5mmol) slowly is added drop-wise in this solution.Then, with in ice-cooled, through 30 minutes in advance the 2-acryloxy Ethyl Succinyl Chloride of synthetic 13.7g (58.4mmol) drip into.After adding, reaction mixture is with being stirred 30 minutes in ice-cooled and at room temperature stirring other 3 hours.After reaction, reaction mixture is poured onto in the 1N aqueous hydrochloric acid of 2l, uses the ethyl acetate extraction three times of 500ml subsequently.The ethyl acetate layer anhydrous magnesium sulfate drying, and by filtering to isolate sal epsom.The filtrate ethyl acetate layer uses rotatory evaporator condensation under reduced pressure, obtains the crude product of intermediate compound A, is light yellow oil.
Crude product is by silica gel column chromatography (chloroform: methyl alcohol=95: 5 (by volume)) purify, obtain the light yellow solid of 17g.Light yellow solid is from chloroform: recrystallization the mixed solvent of toluene=1: 4 ((by volume)) obtains 12.5g (productive rate: purification intermediate compound A 61%).
[0205]
Intermediate compound A's 1H-NMR spectrum data presentation is as follows:
1H-NMR(400MHz，CDCl 3，TMS，δppm)：8.76(s，1H)，8.21-7.69(m，4H)，7.37(dd，J＝8.8Hz，J＝2.4Hz，1H)，6.43(dd，J＝17.2Hz，J＝1.2Hz，1H)，6.12(dd，J＝17.2Hz，J＝10.6Hz，1H)，5.83(dd，J＝10.8Hz，J＝1.2Hz，1H)，4.40(s，4H)，2.98(t，J＝6.6Hz，2H)，2.83(t，J＝6.6Hz，2H)
[0206]
(step 2) intermediate compound B's is synthetic
[0207]
Figure A20088000672500801
[0208]
In being housed, four neck reaction vessels of condenser, thermometer and dropping funnel add formed solution among the THF that the intermediate compound of synthetic in advance A by 12g (31mmol) is dissolved in 300ml.At room temperature through 30 minutes, the oxalyl chloride of 20g (158mmol) is dissolved in formed solution drips at leisure among the THF of 25ml.After adding, reaction mixture is heated to 40 ℃ and stirred 24 hours by using water-bath under same temperature.After reaction is finished, from reaction soln, remove unreacted oxalyl chloride by under reduced pressure distilling, the acyl chlorides of the intermediate compound A of the yellow oil form of acquisition 13g.Acyl chlorides former state under the situation that does not have purification is used for next reaction.
[0209]
Then, be equipped with under nitrogen gas stream and adding in the four neck reaction vessels of condenser, thermometer and dropping funnel by 3 of 1.25g (6.1mmol), the triethylamine of 7-dihydroxyl-2-naphthoic acid and 1.85g (18mmol) is dissolved in formed solution among the THF of 200ml.Solution is cooled to 0-5 ℃ in ice-water bath, be dissolved in by the acyl chlorides of the intermediate compound of the synthetic in advance A of 7.5g (19mmol) that formed solution is dripped through 30 minutes by using dropping funnel among the THF of 100ml.After dripping, reaction mixture at room temperature stirred 12 hours.After reaction, reaction soln is poured onto in the 1N aqueous hydrochloric acid of 500ml, uses the ethyl acetate extraction three times of 500ml subsequently.The ethyl acetate layer anhydrous magnesium sulfate drying, and by filtering to isolate sal epsom.The filtrate ethyl acetate layer uses rotatory evaporator condensation under reduced pressure, obtains the yellow oil of 18g.Yellow oil is by silica gel column chromatography (chloroform: methyl alcohol=98: 2 (by volume)) purify, obtain the white crystal (productive rate: 34.8%) of the intermediate compound B of 2g.
[0210]
Intermediate compound B's 1H-NMR spectrum data presentation is as follows:
1H-NMR(400MHz，CDCl 3，TMS，δppm)：8.81-7.27(m，17H)，6.32-6.28(m，2H)，6.09-6.02(m，2H)，5.74-5.70(m，2H)，4.29-4.20(m，8H)，2.86-2.83(m，4H)，2.80-2.65(m，4H)
[2011]
(synthetic (esterification of intermediate compound B) of step 3) compound 1
[0212]
Figure A20088000672500811
[0213]
In being housed, four neck reaction vessels of condenser, thermometer and dropping funnel add formed solution among the THF that the intermediate compound of synthetic in advance B by 2g (2.1mmol) is dissolved in 50ml.At room temperature through 30 minutes, the oxalyl chloride of 1.35g (10.6mmol) is diluted resulting solution with the THF of 25ml drip at leisure.After adding, reaction mixture is heated to 40 ℃ and stirred 24 hours by using water-bath under same temperature.After reaction is finished, from reaction soln, remove unreacted oxalyl chloride by using rotatory evaporator under reduced pressure to distill, the acyl chlorides of the intermediate compound B of the yellow oil form of acquisition 2g.Acyl chlorides former state under the situation that does not have purification is used for next reaction.
[0214]
Then, formed solution among the THF that the triethylamine that adds in the four neck reaction vessels of condenser, thermometer and dropping funnel by the vinylformic acid 2-hydroxyethyl ester of 0.5g (4.5mmol) and 4.3g (42.6mmol) is dissolved in 50ml is being housed under nitrogen gas stream.Solution is heated to 40 ℃, is dissolved in by the acyl chlorides of the intermediate compound of the synthetic in advance B of 2g (2.1mmol) then that formed solution is dripped through 10 minutes by using dropping funnel among the THF of 50ml.After dripping, reaction mixture at room temperature stirred 2 hours.After reaction, reaction mixture is poured onto in 11 the 1N aqueous hydrochloric acid, uses the ethyl acetate extraction three times of 300ml subsequently.The ethyl acetate layer anhydrous magnesium sulfate drying, and by filtering to isolate sal epsom.The filtrate ethyl acetate layer uses rotatory evaporator condensation under reduced pressure, obtains the yellow oil of 2.4g.Yellow oil is by silica gel column chromatography (chloroform: methyl alcohol=98: 2 (by volume)) purify, obtain the white crystal (productive rate: 17.4%) of the compound 1 of 0.38g.
[0215]
Compound 1 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：8.85-7.38(m，17H)，6.45-5.82(m，9H)，4.48-4.29(m，12H)，3.00-2.97(m，4H)，2.86-2.82(m，4H)
[0216]
Synthesizing of (embodiment 2) compound 2
[0217]
Figure A20088000672500831
[0218]
(step 1) intermediate compound C's is synthetic
[0219]
Figure A20088000672500832
[0220]
Intermediate compound C according to embodiment 1 in identical mode prepare, just in the step 1 of synthetic compound 1, use 4-(4-hydroxyphenyl) phenylformic acid to replace 6-hydroxyl-2-naphthoic acid (productive rate: 65%).
[0221]
Intermediate compound C's 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：8.18(d，J＝8Hz，2H)，7.67(d，J＝8Hz，2H)，7.63(d，J＝8.8Hz，2H)，7.21(d，J＝8.8Hz，2H)，6.44(dd，J＝17.2Hz，J＝1.2Hz，1H)，6.13(dd，J＝17.2Hz，J＝10.6Hz，1H)，5.85(dd，J＝10.8Hz，J＝1.2Hz，1H)，4.39(s，4H)，2.93(t，J＝6.6Hz，2H)，2.81(t，J＝6.6Hz，2H)
[0222]
(step 2) intermediate compound D's is synthetic
[0223]
Figure A20088000672500841
[0224]
Add in the three-necked flask that thermometer and dropping funnel are housed by 3 of 3.0g (14.7mmol), the vinylformic acid 2-hydroxyethyl ester of 7-dihydroxyl-2-naphthoic acid and 34.2g (294mmol) is dissolved in formed solution in the pyridine of 100ml.With in ice-cooled, be dissolved in by the dimethyl aminopyridine (hereinafter to be referred as " DMAP ") of 9.0g (73.5mmol) that formed solution adds at leisure by using dropping funnel in the pyridine of 100ml.After further adding 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (WSC) of 14.1g (73.5mmol), mixture at room temperature reacted 18 hours.After reaction, add the ethyl acetate of 500ml and the distilled water of 100ml, organic layer is separated with water layer.Organic layer is used anhydrous magnesium sulfate drying then with the water washing of 100ml.Filter to isolate sal epsom.Filtrate is condensed, and (the acetate ethyl ester: toluene=2: 8 (by volume)) purification obtains the intermediate compound D (productive rate: 22.5%) of 1.0g to condensation product by silica gel column chromatography.
[0225]
Intermediate compound D's 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：10.01(s，1H)，8.32(s，1H)，7.62，7.60(d，J＝8.0，1H)，7.28-7.13(m，3H)，6.47(dd，J＝0.8，16，1H)，6.18(dd，J＝10.2，17.6，1H)，5.89(dd，J＝1.8，10.8，1H)，4.57-4.67(m，4H)
[0226]
(synthetic (esterification of intermediate compound C and intermediate compound D) of step 3) compound 2
[0227]
[0228]
In three neck reaction vessels, add formed solution in the pyridine that intermediate compound C by the intermediate compound D of 0.5g (1.7mmol) and 2.7g (6.6mmol) is dissolved in 30ml.With in ice-cooled, the DMAP of 1g (8.2mmol) is dissolved in formed solution adds in the pyridine of 10ml.After further adding 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (WSC) of 1.5g (7.8mmol), mixture at room temperature reacted 2 hours.After reaction, add the ethyl acetate of 300ml and the distilled water of 100ml, organic layer is separated with water layer.Organic layer is used anhydrous magnesium sulfate drying then with the water washing of 100ml.Filter to isolate sal epsom.Filtrate is condensed, and (the acetate ethyl ester: toluene=2: 8 (by volume)) purification obtains the compound 2 (productive rate: 28.3%) of 0.5g to condensation product by silica gel column chromatography.
[0229]
Compound 2 1H-NMR spectrum data presentation is as follows.
1H-NMR(500MHz，CDCl 3，TMS，δppm)：8.67(s，1H)，8.31(d，J＝8.6，4H)，7.92(d，2H)，7.87(d，J＝2.3，1H)，7.74-7.65(m，9H)，7.53(dd，J＝2.3，9.2，1H)，7.25-7.20(m，4H)，6.45-6.37(m，3H)，6.16-6.04(m，3H)，5.86-5.80(m，3H)，4.49(dd，2H)，4.39(s，8H)，4.32(dd，2H)，2.94(t，J＝7.5，4H)，2.82(t，J＝7.5，4H)
[0230]
Synthesizing of (embodiment 3) compound 3
[0231]
[0232]
(step 1) intermediate compound E's is synthetic
[0233]
Figure A20088000672500862
[0234]
Add in four neck reaction vessels of condenser, thermometer and dropping funnel are housed by 2 of the vinylformic acid 2-hydroxyethyl ester of 45.2g (0.39mol) and 6g (0.039mol), the 5-resorcylic acid is dissolved in formed solution among the THF of 100ml.At room temperature, the DMAP of 0.5g (4.1mmol) is dissolved in formed solution adds in this solution among the THF of 5ml.Then, will be by the N of 8.8g (0.04mol), N-dicyclohexylcarbodiimide (DCC) is dissolved in that formed solution at room temperature dripped through 15 minutes among the THF of 50ml.After adding, mixture is heated to 50 ℃ and reacted 12 hours by using water-bath.After reaction was finished, reaction mixture was filtered, and filtrate is by using rotatory evaporator condensation under reduced pressure.
[0235]
The gained condensation product is dissolved in the ethyl acetate of 200ml, uses the water washing three times of 1l then, to remove unreacted vinylformic acid 2-hydroxyethyl ester.The ethyl acetate layer anhydrous magnesium sulfate drying, and by filtering to isolate sal epsom.The ethyl acetate layer that obtains as filtrate uses rotatory evaporator condensation under reduced pressure, obtains the light yellow oil of 12g.The gained light yellow oil is by silica gel column chromatography (toluene: acetate ethyl ester=90: 10 (by volume)) purify, obtain the intermediate compound E (productive rate: 74%) of the yellow oil form of 7.3g.
[0236]
Intermediate compound E's 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：10.16(s，1H)，7.28(d，J＝2.8Hz，1H)，7.05-7.02(m，1H)，6.87(d，J＝8.8Hz，1H)，6.45(d，J＝16.4Hz，1H)，6.15(dd，J＝17.6Hz，J＝10.8Hz，1H)，5.88(d，J＝10.8Hz，1H)，4.54(d，J＝2.8Hz，4H)
[0237]
Synthesizing of (step 2) compound 3
[0238]
Figure A20088000672500871
[0239]
In being housed, four neck reaction vessels of condenser, thermometer and dropping funnel are added on the intermediate compound A of the 2g (5.2mmol) that makes in the synthetic step 1 of compound 1 and the toluene of 30ml.4.4g the formed solution in the toluene of 5ml of trifluoroacetic anhydride (0.021mol) at room temperature was added drop-wise in the gained slurry through 10 minutes.After adding, mixture at room temperature reacted 2 hours.Along with the carrying out of reaction, mixture becomes uniform solution.After reaction was finished, unreacted trifluoroacetic anhydride was removed by under reduced pressure distilling from reaction soln with the trifluoroacetic acid that belongs to byproduct of reaction, obtains the light yellow oil of 2.4g.Former state is used for next reaction but the gained acid anhydride mixture just need not to purify.
[0240]
In being housed, add by four neck reaction vessels of condenser, thermometer and dropping funnel synthetic intermediate compound E in step 1 by 0.44g (1.74mmol), 1.05g triethylamine (0.01mol), and the DMAP of 0.32g (2.62mmol) is dissolved in formed solution among the THF of 30ml.Be dissolved in by the acid anhydride mixture of synthetic in advance of 2.4g (5.3mmol) that resulting solution at room temperature dripped through 10 minutes among the THF of 10ml.After adding, mixture at room temperature reacted 12 hours.
[0241]
After reaction, reaction soln is poured onto in the 1N aqueous hydrochloric acid of 500ml, uses the ethyl acetate extraction three times of 300ml subsequently.The ethyl acetate layer anhydrous magnesium sulfate drying, and by filtering to isolate sal epsom.The gained ethyl acetate layer uses the rotatory evaporator condensation, obtains the light yellow oil of 2.7g.Light yellow oil is by silica gel column chromatography (chloroform: methyl alcohol=90: 10 (by volume)) purify, obtain the compound 3 (productive rate: 46.5%) of the water white oil form of 0.8g.
[0242]
Compound 3 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：8.84-8.78(m，2H)，8.25-8.17(m，2H)，8.07-7.87(m，5H)，7.70-7.55(m，3H)，7.42-7.30(m，3H)，6.43(d，J＝17.2Hz，2H)，6.30(d，J＝17.4Hz，1H)，6.13(dd，J＝17.2Hz，J＝10.4Hz，2H)，5.94(dd，J＝17.2Hz，J＝10.4Hz，1H)，5.83(d，J＝10.4Hz，2H)，5.71(d，J＝10.6Hz，1H)，4.46-4.36(m，10H)，4.27-4.21(m，2H)，2.98(t，J＝6.6Hz，4H)，2.83(t，J＝6.6Hz，4H)
[0243]
Synthesizing of (embodiment 4) compound 4
[0244]
Figure A20088000672500881
[0245]
By will synthetic intermediate compound C and synthetic intermediate compound E condensation in the synthetic step 1 of compound 3 in the synthetic step 1 of compound 2, come synthetic compound 4.
[0246]
In being housed, four neck reaction vessels of condenser, thermometer and dropping funnel add formed solution in the toluene that the intermediate compound C that makes in the synthetic step 1 at compound 2 by 2g (4.8mmol) is dissolved in 30ml.4.1g the formed solution in the toluene of 5ml of trifluoroacetic anhydride (0.019mol) at room temperature was added drop-wise in the gained slurry through 10 minutes.After adding, mixture at room temperature reacted 2 hours.Along with the carrying out of reaction, mixture becomes uniform solution.After reaction was finished, unreacted trifluoroacetic anhydride was removed by under reduced pressure distilling from reaction soln with the trifluoroacetic acid that belongs to byproduct of reaction, obtains the light yellow oil of 2.4g.Former state is used for next reaction but the gained acid anhydride mixture just need not to purify.
[0247]
In being housed, add by four neck reaction vessels of condenser, thermometer and dropping funnel by synthetic intermediate compound E in the synthetic step 1 of 0.4g (1.6mmol) at compound 3,0.97g triethylamine (9.6mol), and the DMAP of 0.29g (2.4mmol) is dissolved in formed solution among the THF of 30ml.Be dissolved in by the acid anhydride mixture of synthetic in advance of 2.4g (4.8mmol) that resulting solution at room temperature dripped through 10 minutes among the THF of 50ml.After adding, mixture at room temperature reacted 12 hours.After reaction, reaction soln is poured onto in the 1N aqueous hydrochloric acid of 800ml, uses the ethyl acetate extraction three times of 300ml subsequently.The ethyl acetate layer anhydrous magnesium sulfate drying, and by filtering to isolate sal epsom.The gained ethyl acetate layer uses the rotatory evaporator condensation, obtains the light yellow oil of 2.7g.Light yellow oil is by silica gel column chromatography (chloroform: methyl alcohol=90: 10 (by volume)) purify, obtain the compound 4 (productive rate: 60%) of the Liquid Paraffin form of 1.0g.
[0248]
Compound 4 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：J＝8.28(d，J＝8.8Hz，4H)，7.98(d，J＝2.8Hz，1H)，7.74-7.64(m，8H)，7.54(dd，J＝2.8Hz，J＝8.8Hz，1H)，7.33(d，J＝8.8Hz，1H)，7.28-7.217(m，4H)，6.43(dd，J＝1.2Hz，J＝17.2，2H)，6.36(dd，J＝1.2Hz，J＝17.4Hz，1H)，6.14(dd，J＝10.4Hz，J＝17.2Hz，2H)，6.04(dd，J＝10.2Hz，J＝17.4Hz，1H)，5.85(dd，J＝1.2Hz，J＝10.4Hz，2H)，5.79(dd，J＝1.2Hz，J＝10.2Hz，1H)，4.45(dd，J＝2.8Hz，J＝6.8Hz，2H)，4.39(s，8H)，4.27(dd，J＝2.8Hz，J＝6.8Hz，2H)，2.94(t，J＝6.7Hz，4H)，2.81(t，J＝6.7Hz，4H)
[0249]
Synthesizing of (embodiment 5) compound 5
[0250]
Figure A20088000672500901
[0251]
(step 1) intermediate compound F's is synthetic
[0252]
Figure A20088000672500902
[0253]
Add in four neck reaction vessels of condenser, thermometer and dropping funnel are housed by 2 of the β-methylallyl alcohol of 7g (97mmol) and 5g (32.4mmol), the 5-resorcylic acid is dissolved in formed solution among the THF of 100ml.At room temperature, the DMAP of 0.5g (4.1mmol) is dissolved in formed solution adds in this solution at leisure among the THF of 5ml.Then, will be by the N of 8g (39mmol), N-dicyclohexylcarbodiimide (DCC) is dissolved in that formed solution at room temperature dripped through 15 minutes among the THF of 50ml.After adding, mixture is heated to 50 ℃ and reaction 12 hours under uniform temp by using water-bath.After reaction was finished, reaction mixture filtered, to separate insoluble component.By using rotatory evaporator under reduced pressure from gained filtrate, to evaporate THF.
[0254]
The gained condensation product is dissolved in the ethyl acetate of 200ml, uses the water washing three times of 1l then, to remove unreacted β-methylallyl alcohol.The ethyl acetate layer anhydrous magnesium sulfate drying, and by filtering to isolate sal epsom.Use rotatory evaporator under reduced pressure from the filtrate ethyl acetate layer, to evaporate ethyl acetate, obtain the light yellow oil of 8g.The gained light yellow oil is by silica gel column chromatography (toluene: acetate ethyl ester=95: 5 (by volume)) purify, obtain the pale yellow crystals (productive rate: 65%) of the intermediate compound F of 4.4g.
[0255]
Intermediate compound F's 1H-NMR spectrum data presentation is as follows.
1H-NMR(500MHz，CDCl 3，TMS，δppm)：10.33(s，1H)，7.33(d，J＝3.0Hz，1H)，7.018(dd，J＝3.0，8.5Hz，1H)，6.89(d，J＝8.5Hz，1H)，5.08(dd，J＝1.0，31.0Hz，1H)，5.02(dd，J＝1.0，31.0Hz，1H)，4.76(s，2H)，1.84(s，3H)
[0256]
Synthesizing of (step 2) compound 5
In three neck reaction vessels, add the intermediate compound F of the above acquisition of 1g (4.8mmol), the intermediate compound C of synthetic in advance of 7.92g (19.2mol) and the N of 60ml, dinethylformamide (hereinafter to be referred as " DMF ").The mixture uniform dissolution.To be dissolved in that formed solution adds in the gained solution among the DMF of 10ml by the DMAP of 2.94g (24mmol).After further adding 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) of 4.6g (24mmol), mixture at room temperature stirred two hours.After this, the distilled water of 400ml and the ethyl acetate of 600ml are added, organic layer is separated with water layer.Water layer is used the ethyl acetate extraction of 600ml once more.Water layer and isolating organic layer merging in advance with the water washing of 100ml, and use the anhydrous magnesium sulfate dehydration.Filter to isolate sal epsom.Filtrate is condensed, condensation product is by silica gel column chromatography (initial acetate ethyl ester: toluene=2: 8 (by volume), in purification process, change over chloroform: ethyl acetate=95: 5 (by volume)) purify, obtain the compound 5 of 1.14g, be white solid (productive rate: 23.8%).
[0257]
Compound 5 1H-NMR spectrum data presentation is as follows.
1H-NMR(500MHz，CDCl 3，TMS，δppm)：8.26(dd，J＝2.0Hz，J＝8.3Hz，4H)，7.97(d，J＝2.9Hz，1H)，7.72-7.63(m，8H)，7.52(dd，J＝2.9Hz，J＝8.6Hz，1H)，7.32(d，J＝9.2Hz，1H)，7.23-7.20(m，4H)，6.42(dd，J＝1.7Hz，J＝17.2Hz，2H)，6.12(dd，J＝17.2Hz，J＝17.5Hz，2H)，5.82(dd，J＝1.5Hz，10.3Hz，2H)，4.91(s，1H)，4.82(s，1H)，4.61(s，2H)，4.38(s，8H)，2.92(t，J＝6.6Hz，4H)，2.81(t，J＝6.6Hz，4H)，1.68(s，3H)
[0258]
Synthesizing of (embodiment 6) compound 6
[0259]
Figure A20088000672500921
[0260]
(step 1) intermediate compound G's is synthetic
[0261]
Figure A20088000672500922
[0262]
Intermediate compound G only is to use vinyl carbinol to replace β-methylallyl alcohol (productive rate: 58%) according to synthetic with the synthetic identical mode of the intermediate compound F of embodiment 5.
[0263]
Intermediate compound G's 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：10.30(s，1H)，7.32(d，J＝4.0Hz，1H)，7.02(dd，J＝4.0Hz，J＝11.0Hz，1H)，6.88(d，J＝11.0Hz，1H)，6.07-5.97(m，1H)，5.44-5.31(m，2H)，4.86-4.82(m，2H)
[0264]
Synthesizing of (step 2) compound 6
In being housed, add by three neck reaction vessels of thermometer and dropping funnel the intermediate compound of the synthetic in advance C of 2.57g (6.24mmol), 0.4g the intermediate compound G of above acquisition (2.1mmol), 0.13g DMAP (1.1mmol), and the triethylamine of 1.26g (12.4mmol).The THF that adds 30ml comes dissolving mixt.1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) that at room temperature adds 1.50g (7.8mmol) afterwards, mixture at room temperature stirred three hours.
[0265]
After reaction, reaction mixture is poured onto in the mixture of concentrated hydrochloric acid of the saturated brine of 300ml and 30ml, uses the ethyl acetate extraction three times of 300ml subsequently.Ethyl acetate layer washs with saturated aqueous solution of sodium bicarbonate, uses anhydrous magnesium sulfate drying then.Remove by filter out sal epsom.Ethyl acetate layer uses rotatory evaporator condensation under reduced pressure, obtains the light yellow oil of 1.20g.Light yellow oil is by silica gel column chromatography (toluene: acetate ethyl ester=80: 20 (by volume)) purify, obtain the compound 6 (productive rate: 30%) of the white solid form of 0.62g.
[0266]
Compound 6 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：8.30-8.22(m，4H)，7.98(d，J＝2.8Hz，1H)，7.78-7.64(m，8H)，7.53(dd，J＝2.8Hz，J＝8.8Hz，1H)，7.34(d，J＝8.8Hz，1H)，7.24-7.22(m，4H)，6.46-6.41(m，2H)，6.17-6.10(m，2H)，5.87-5.84(m，2H)，5.83-5.76(m，1H)，5.27-5.22(m，1H)，5.14-5.11(m，1H)，4.96-4.67(m，2H)，4.39(s，8H)，2.95-2.79(m，8H)
[0267]
Synthesizing of (embodiment 7) compound 7
[0268]
[0269]
(step 1) intermediate compound H's is synthetic
[0270]
[0271]
Intermediate compound H only is to use 3-methyl-3-butene-1-alcohol to replace β-methylallyl alcohol (productive rate: 62%) according to synthesizing with the synthetic identical mode of intermediate compound F.
[0272]
Intermediate compound H's 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：10.33(s，1H)，7.27(d，J＝4.5Hz，1H)，7.00(dd，J＝4.5Hz，J＝11.0Hz，1H)，6.88(d，J＝11.0Hz，1H)，4.84(d，J＝23.5Hz，2H)，4.45(t，J＝8.5Hz，2H)，2.48(t，J＝8.0Hz，2H)，1.81(s，3H)
[0273]
Synthesizing of (step 2) compound 7
Compound 7 according to embodiment 6 in same method synthesize, just in the step 2 of synthetic compound 6, use intermediate compound H to replace intermediate compound G (productive rate: 54%).
[0274]
Compound 7 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：8.31-8.27(m，4H)，7.94(d，J＝3.2Hz，1H)，7.74-7.65(m，8H)，7.52(dd，J＝3.2Hz，J＝8.8Hz，1H)，7.32(d，J＝8.8Hz，1H)，7.25-7.16(m，4H)，6.44(d，J＝17.2Hz，2H)，6.14(dd，J＝10.4Hz，J＝17.2Hz，2H)，5.86(d，J＝10.4Hz，2H)，4.74(s，1H)，4.66(s，1H)，4.39(s，8H)，4.31(t，J＝7Hz，2H)，2.94(t，J＝6.6Hz，4H)，2.81(t，J＝6.6Hz，4H)，2.25(t，J＝6.6Hz，2H)，1.65(s，3H)
[0275]
Synthesizing of (embodiment 8) compound 8
[0276]
Figure A20088000672500951
[0277]
(step 1) intermediate compound I's is synthetic
[0278]
Figure A20088000672500952
[0279]
Add in four neck reaction vessels of condenser, thermometer and dropping funnel are housed by 2 of 5g (32.4mmol), the 5-resorcylic acid is dissolved in formed solution among the THF of 100ml.At room temperature, the DMAP of 0.5g (3.9mmol) is dissolved in formed solution adds in this solution among the THF of 5ml.Then, will be by the N of 8g (39mmol), N-dicyclohexylcarbodiimide (DCC) is dissolved in that formed solution at room temperature dripped through 15 minutes among the THF of 50ml.After adding, mixture at room temperature stirred 30 minutes, added the allyl amine of 5.6g (98mmol) then.The gained mixture at room temperature stirred 20 hours.After reaction is finished, by removing by filter insoluble component.Use rotatory evaporator under reduced pressure from gained filtrate, to evaporate THF.The gained condensation product is dissolved in the ethyl acetate of 200ml, uses the water washing three times of 1l then, to remove unreacted allyl amine.The organic layer anhydrous magnesium sulfate drying, and by filtering to isolate sal epsom.Use rotatory evaporator under reduced pressure from gained filtrate, to evaporate ethyl acetate, obtain the light yellow oil of 5.5g.Light yellow oil is by silica gel column chromatography (chloroform: methyl alcohol=90: 10 (by volume)) purify, obtain the intermediate compound I (productive rate: 30%) of the light grey crystalline form of 1.9g.
[0280]
Intermediate compound I's 1H-NMR spectrum data presentation is as follows.
1H-NMR(500MHz，CDCl 3，TMS，δppm)：11.66(brs，1H)，6.95-6.85(m，3H)，6.51(s，1H)，5.95-5.87(m，1H)，5.64(brs，1H)，5.29-5.20(m，2H)，4.05(t，J＝5.3Hz，2H)
[0281]
Synthesizing of (step 2) compound 8
The above intermediate compound I that obtains of 0.7g (3.6mmol) and the intermediate compound A that obtains in advance of 4.2g (10.9mmol) are dissolved in the pyridine of 30ml.To be dissolved in that formed solution adds in the gained solution in the pyridine of 10ml by the DMAP of 1.3g (10.6mmol).After further adding 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) of 2.1g (11mmol), mixture at room temperature stirred five hours.After reaction, add 1, the ethyl acetate of 000ml, the toluene of 100ml and the distilled water of 200ml separate organic layer with water layer.Water layer is used the ethyl acetate extraction of 300ml once more.Organic layer is merged, and uses anhydrous sodium sulfate drying, filters then.Filtrate is condensed, condensation product is by silica gel column chromatography (initial acetate ethyl ester: toluene=4: 6 (by volume), in purification process, change over chloroform: ethyl acetate=9: 1 (by volume)) purify, obtain the waxy compound 8 (productive rate: 9.2%) of 0.31g.
[0282]
Compound 8 1H-NMR spectrum data presentation is as follows.
1H-NMR(500MHz，CDCl 3，TMS，δppm)：8.77(m，3H)，8.28-8.15(m，2H)，8.06-7.80(m，6H)，7.69(s，1H)，7.18-7.06(m，4H)，6.42(d，J＝2.0，2H)，6.11(dd，J＝10.2Hz，J＝10.2Hz，2H)，6.0(m，1H)，5.83(dd，J＝0.8Hz，J＝10.5Hz，2H)，5.29(m，1H)，5.15(m，1H)，4.55(s，2H)，4.44-4.29(m，8H)，2.99(t，J＝6.2，4H)，2.81(t，J＝6.2，4H)
[0283]
Synthesizing of (embodiment 9) compound 9
[0284]
Figure A20088000672500961
[0285]
(step 1) intermediate compound J's is synthetic
[0286]
Figure A20088000672500971
[0287]
Intermediate compound J according to embodiment 1 in identical mode prepare, just in the step 1 of the synthetic compound 1 of embodiment 1, use P-hydroxybenzoic acid to replace 6-hydroxyl-2-naphthoic acid (productive rate: 73%).
[0288]
Synthesizing of (step 2) compound 9
In three neck reaction vessels, under nitrogen gas stream, at room temperature the intermediate compound E of 0.2g (0.84mmol) and the intermediate compound J of 1.0g (2.97mmol) are dissolved among the THF of 25ml.Add in the gained solution being dissolved in the triethylamine of the 0.3g (2.97mmol) among the 5ml THF and the dimethyl aminopyridine of 0.14g (1.13mmol).After reaction mixture is cooled off in ice-water bath, add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (WSC) of 0.64g (3.36mmol), mixture stirred 30 minutes.Mixture at room temperature stirred other four hours.After the ethyl acetate of adding 350ml, the water that adds 50ml comes the extractive reaction product.Organic layer filters then through dried over sodium sulfate.Filtrate is condensed, condensation product is by silica gel column chromatography (initial chloroform: acetate ethyl ester=9: 1 (by volume), in purification process, change over toluene: acetate ethyl ester=6: 4 (by volume)) purify, obtain the waxy compound 9 (productive rate: 26.8%) of 0.20g.
[0289]
Compound 9 1H-NMR spectrum data presentation is as follows.
1H-NMR(500MHz，CDCl 3，TMS，δppm)：8.32-8.21(m，5H)，7.90(d，J＝3.0Hz，1H)，7.42(dd，J＝3.2Hz，9.0Hz，1H)，7.30-7.25(m，4H)，6.45-6.35(m，3H)，6.17-6.01(m，3H)，5.87-5.79(m，3H)，4.52-4.40(m，4H)，4.39-4.25(m，8H)，2.93(t，J＝6.6，4H)，2.80(t，J＝6.6，4H)
[0290]
Synthesizing of (embodiment 10) compound 10
[0291]
Figure A20088000672500981
[0292]
In three neck reaction vessels, the intermediate compound E of 0.20g (0.84mmol) and the 4-of 0.86g (2.94mmol) (6-acryloxy-own-1-base oxygen base) phenylformic acid (by Japan SiebelHegner Co., Ltd makes) are dissolved among the THF of 25ml.Add in the gained solution being dissolved in the triethylamine of the 0.35g (3.42mmol) among the 5ml THF and the dimethyl aminopyridine of 0.14g (1.14mmol).After further adding 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (WSC) of 0.64g (3.36mmol), mixture at room temperature stirred three and a half hours under nitrogen gas stream.After the ethyl acetate of adding 350ml, the water that adds 50ml comes the extractive reaction product.Organic layer is through dried over sodium sulfate and filtration.Filtrate is condensed, and (chloroform: acetate ethyl ester=9: 1 (by volume)) purification obtains the white solid (productive rate: 50.5%) of the compound 10 of 0.34g to condensation product by silica gel column chromatography.
[0293]
Compound 10 1H-NMR spectrum data presentation is as follows.
1H-NMR(500MHz，CDCl 3，TMS，δppm)：8.14(d，J＝8.6Hz，4H)，7.90(d，J＝2.9Hz，1H)，7.47(dd，J＝2.9Hz，9.1Hz，1H)，7.27(d，J＝8.6Hz，1H)，6.96(t，J＝9.2Hz，4H)，6.38(m，3H)，6.15-6.01(m，3H)，5.83-5.79(m，3H)，4.42-4.40(m，2H)，4.23-4.21(m，2H)，4.18(t，J＝6.6Hz，4H)，4.05(dd，J＝6.1Hz，12.3Hz，4H)，1.85-1.83(m，4H)，1.75-1.70(m，4H)，1.55-1.45(m，8H)
[0294]
Synthesizing of (embodiment 11) compound 11
[0295]
Figure A20088000672500991
[0296]
(step 1) intermediate compound K's is synthetic
[0297]
Figure A20088000672500992
[0298]
According to embodiment 3 in identical mode synthetic mesophase compound K, just in the step 1 of synthetic compound 3, use ethylene glycol monoallyl ether to replace vinylformic acid 2-hydroxyethyl ester.
[0299]
Intermediate compound K's 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl3，TMS，δppm)：10.23(s，1H)，7.30(d，J＝3.1Hz，1H)，6.99(dd，J＝3.1，9.1Hz，1H)，6.84(d，J＝9.1Hz，1H)，5.93(ddt，J＝5.8，10.4，17.3Hz，1H)，5.59(br，1H)，5.32(ddd，J＝1.7，3.0，17.3Hz，1H)，5.23(ddd，J＝1.2，3.0，10.4Hz，1H)，4.49(t，J＝4.7Hz，2H)，4.10-4.08(m，2H)，3.80(t，J＝4.7Hz，2H)
[0300]
Synthesizing of (step 2) compound 11
In being housed, add by three neck reaction vessels of thermometer and dropping funnel the intermediate compound C of 1.19g (2.9mmol), 0.23g intermediate compound K (1.0mmol), 0.12g N (0.9mmol), N-dimethyl aminopyridine, and the triethylamine of 0.58g (5.7mmol).The THF that adds 20ml comes dissolving mixt.At room temperature add after 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride of 0.46g (2.4mmol), mixture at room temperature stirred three hours.
[0301]
After reaction, reaction mixture is poured onto in the mixture of concentrated hydrochloric acid of the saturated brine of 100ml and 10ml, uses the ethyl acetate extraction three times of 100ml subsequently.Ethyl acetate layer washs with saturated aqueous solution of sodium bicarbonate, uses dried over mgso then.By removing by filter sal epsom.The gained ethyl acetate layer uses the rotatory evaporator condensation, obtains the light yellow oil of 0.80g.Light yellow oil is by silica gel column chromatography (toluene: acetate ethyl ester=80: 20 (by volume)) purify, obtain the compound 11 (productive rate: 51%) of the white solid form of 0.50g.
[0302]
Compound 11 1H-NMR spectrum data presentation is as follows.
1H-NMR(400MHz，CDCl 3，TMS，δppm)：8.30(d，J＝8.4Hz，2H)，8.28(d，J＝8.4Hz，2H)，7.99(d，J＝3.2Hz，1H)，7.74-7.71(m，4H)，7.68-7.65(m，4H)，7.53(dd，J＝2.8，8.8Hz，1H)，7.33(d，J＝8.8Hz，1H)，7.24-7.22(m，4H)，6.44(d，J＝17.2Hz，2H)，6.14(dd，J＝10.8，17.2Hz，2H)，5.86(d，J＝10.8Hz，2H)，5.85-5.77(m，1H)，5.21(d，J＝17.2Hz，1H)，5.14(d，J＝10.4Hz，1H)，4.39(s，8H)，4.36(t，J＝4.8Hz，2H)，3.88(d，J＝6Hz，2H)，3.56(t，J＝4.8Hz，2H)，2.94(t，J＝6.6Hz，4H)，2.81(t，J＝6.6Hz，4H)
[0303]
The evaluation of＜compound 〉
(1) measurement of transformation temperature
The compound 1-11 (test compound) that in embodiment 1-11, obtains, each 10mg that takes a sample is inserted between the two sheet glass backing material plates, and the alignment film of polyimide that adopts friction treatment and provide is provided each plate.Base material is heated to 300 ℃ from 40 ℃ on hot-plate, be cooled to 40 ℃ then.Use the variation of the weave construction of deviation observation by light microscope in the heating and cooling process.Measured transformation temperature is shown in the following table 1.
[0304]
In table 1, C represents crystal, and S represents smectic, and N represents to represent isotropy to row and I." crystal " expression test compound is in solid phase, and " smectic " expression test compound is in the smectic liquid crystal phase, and " to row " expression test compound is in the nematic liquid crystal phase and " isotropy " expression test compound is in isotropic mesomorphic phase." r.t " represents room temperature (23 ℃).
[0305]
(2) measurement of optical anisotropy (Δ n)
The compound 1-11 (test compound) that will obtain in embodiment 1-11 is dissolved in and obtains 30wt%MEK solution or 30wt%CPN solution in methyl ethyl ketone (MEK) or the cyclopentanone (CPN).The Photoepolymerizationinitiater initiater of 1.2 weight parts (by Ciba Specialty Chemicals Co., " Irgacure 907 " that Ltd makes) is added and be dissolved in MEK solution or the CPN solution.Gained solution is as test sample.
The solubleness of test compound is estimated by following judgement criteria.That is to say, when preparing the 30wt% solution of test compound, be be evaluated as and have good solubleness and be expressed as " well " by being heated to 60 ℃ of test compounds that are dissolved among MEK or the CPN, otherwise test compound is be evaluated as and has bad solubleness and be expressed as " bad ".The results are shown in the table 1.
[0306]
(the SA-203 rod is coated with machine to prepared solution by using rod to be coated with machine, rod No.8, shaft diameter: 12.7mm is by Tester Sangyo Co., Ltd makes) be applied on the sheet glass with the polyvinyl alcohol film that adopts friction treatment and provide on 100 ℃ hot-plate dry five minutes then.Film and use UV light from mercury lamp, 000mJ/cm with 1 2Dosage carry out radiation, obtaining thickness is the cured film of 4 μ m." J " is identical with " Ws ".
[0307]
In order to measure retardation rate (Re), use opticmicroscope (" ECLIPSEE600POL " (penetrating/reflection type) of sensitive color test plate (panel), λ/4 wavelength plates, Sai Nameng (senarmont) loop expansion pipe and GIF strainer 546nm is housed, makes) to check the extinction position (θ) of cured film by Nikon Corp..Retardation rate (Re) uses formula Re=λ (546nm) * θ/180 to calculate.The thickness (d) of the independent mensuration by using liquid crystal layer, Δ n is calculated by equation Δ n=Re/d.
Calculation result is shown in the following table 1.
[0308]
(3) formation of cholesteric phase
The compound 1-11 that will obtain in embodiment 1-11 is dissolved in and obtains 30wt%MEK solution or 30wt%CPN solution among MEK or the CPN.Photoepolymerizationinitiater initiater (" Irgacure 907 " with 2.5 weight parts, by Ciba Specialty Chemicals Co., Ltd makes), the tensio-active agent (1wt%) of the chiral reagent of 5 weight parts and 8.5 weight parts adds and is dissolved in MEK solution or the CPN solution and obtains sample.As chipal compounds, use compound by above-mentioned formula (X) expression.As tensio-active agent, use by AGC Seimi Chemical Co. " KH-40 " that Ltd. makes.
[0309]
(the SA-203 rod is coated with machine to prepared solution by using rod to be coated with machine, rod No.8, shaft diameter: 12.7mm, by Tester Sangyo Co., Ltd makes) be applied on the sheet glass with the alignment film of polyimide that adopts friction treatment and provide, and on 100 ℃ hot-plate dry three minutes.Film and use UV light from mercury lamp, 000mJ/cm with 1 2Dosage carry out radiation, obtaining thickness is the cured film of 4 μ m.The UV-VIS spectrum of the film of measurement in the wavelength region of 400nm-750nm.When forming the cholesteric phase time, observing selective reflection zone (wherein transmissivity becomes about 50% zone) and its bandwidth is about 50-90nm.
[0310]
(4) measurement of film hardness
According to above (3) in the pencil hardness of the cured film that obtains of the same manner be to measure according to the method for JISK5600-5-4.Evaluation result is shown in the following table 1.
[0311]
Figure A20088000672501031
Figure A20088000672501041
[0312]
As shown in table 1, compound 1-11 is proved has high-dissolvability in solvent, and superior compatibility between additive such as polymerization starter and the chiral reagent and excellent handling property.In addition, whole good liquid crystal liquid crystal property of compound exhibits and form the cholesteric liquid crystal phase.Cured film is good liquid crystalline polymer film, and it demonstrates high optical anisotropy (Δ n) and very high pencil hardness.

Claims (8)

1. by the polymerisable liquid crystal compound of following formula (I) expression,
Figure A2008800067250002C1
M wherein 1Expression has replacement or the unsubstituted trivalent or the tetravalence aromatic hydrocarbon radical of 6-24 carbon atom; Y 1-Y 8Represent chemical single bond separately ,-O-,-S-,-O-C (=O)-,-C (=O)-O-,-O-C (=O)-and O-,-NR 1-C (=O)-,-C (=O)-NR 1-,-O-C (=O)-NR 1-,-NR 1-C (=O)-and O-,-NR 1-C (=O)-NR 1-,-O-NR 1-or-NR 1-O-, wherein R 1Expression hydrogen atom or have the alkyl of 1-6 carbon atom; G 1-G 3Expression has the replacement or the unsubstituted aliphatic divalent group of 1-20 carbon atom separately, and it can comprise-O-,-S-,-O-C (=O)-,-C (=O)-O-,-O-C (=O)-and O ,-NR 2-C (=O)-,-C (=O)-NR 2-,-NR 2-or-C (=O)-(getting rid of the situation that wherein two or more-O-and two or more-S-exist side by side), wherein R 2Expression hydrogen atom or have the alkyl of 1-6 carbon atom; Z 1-Z 3Expression has the thiazolinyl of 2-10 carbon atom separately, and it can be replaced by halogen atom; A 1And A 2Expression has the group that the replacement of 4-24 carbon atom or unsubstituted divalence or trivalent contain aromatic ring separately; A, b and c each naturally 1 or 2; And p, q and r each naturally 0 or 1.
2. according to the polymerisable liquid crystal compound of claim 1, wherein by M 1The aromatic hydrocarbon radical of expression is a phenyl ring, cyclohexyl biphenyl, naphthalene nucleus, terphenyl ring, or anthracene nucleus.
3. according to the polymerisable liquid crystal compound of claim 1 or 2, A wherein 1And A 2Represent phenyl ring separately, cyclohexyl biphenyl, naphthalene nucleus, or anthracene nucleus.
4. according to any one polymerisable liquid crystal compound among the claim 1-3, wherein by Z 1-Z 3Each CH naturally of the thiazolinyl of expression 2=CH-, CH 2=C (CH 3)-, CH 2=C (Cl)-, CH 2=CH-CH 2-, CH 2=C (CH 3)-CH 2-, CH 2=C (CH 3)-CH 2CH 2-, (CH 3) 2C=CH-CH 2-, CH 3-CH=CH-, or CH 3-CH=CH-CH 2-.
5. comprise according to the polymerisable liquid crystal compound of any one and the polymerizable liquid crystal composition of polymerizable chipal compounds among the claim 1-4.
By make according among the claim 1-4 any one the polymerisable liquid crystal compound or carry out the liquid crystalline polymers that polymerization obtained according to the polymerizable liquid crystal composition of claim 5.
7. according to the liquid crystalline polymers of claim 6, it has 2H or higher pencil hardness.
8. optically anisotropic substance, it comprises the liquid crystalline polymers according to claim 6 or 7.
CN200880006725A 2007-03-01 2008-02-29 Polymerizable liquid crystal compound, polymerizable liquid crystal composition, liquid crystal polymer and optically anisotropic substance Pending CN101622219A (en)

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