CN104592219A

CN104592219A - Compound, optical film and method for making optical film

Info

Publication number: CN104592219A
Application number: CN201410664138.1A
Authority: CN
Inventors: 大川春树; 美阿·布拉博·朴; 小林忠弘; 落合钢志郎
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2009-03-16
Filing date: 2010-03-12
Publication date: 2015-05-06
Anticipated expiration: 2030-03-12
Also published as: CN104592219B; KR20100105411A; CN101838264B; CN101838264A; TWI482769B; KR101641385B1; TW201100410A

Abstract

The invention relates to a compound, an optical film and a method for making the optical film. The invention provides a compound having a divalent group and represented by the following formula (1-1) or (1-2), wherein Z1 and Z2 respectively independently represent a hydrogen atom etc., Q1 and Q2 respectively independently represent -S- etc. Y1 represents a substituted or unsubstituted polycyclinc aromatic hydrocarbon group, or a substituted or unsubstituted poly cyclic aromatic heterocyclic group; D1 and D2 respectively independently represent a single bond or a divalent bonded group, G1 and G2 respectively independently represent a divalent aliphacyclic hydrocarbon group. This invention also provides an optical film by polymerizing the above compound.

Description

The manufacture method of compound, blooming and blooming

The divisional application (denomination of invention of original application is " manufacture method of compound, blooming and blooming ", and the applying date of original application is on March 12nd, 2010) of the application's to be Chinese application number be application for a patent for invention of 201010133280.5.

Technical field

The present invention relates to the manufacture method of compound, blooming and blooming.

Background technology

Employ the parts of blooming containing polaroid, polarizer etc. in panel display apparatus (FPD).As blooming, can enumerate solvent polymerization compound in a solvent and the solution coat obtained after supporting substrate, carry out being polymerized and the blooming obtained.As such polymerizable compound, at SID Symposium Digest of Technical Papers, 2006,37 volumes, disclosed the compound (LC242) shown in following formula p.1673.

Summary of the invention

The invention provides following scheme etc.

[1] there is the compound of divalent group shown in formula (1-1) or formula (1-2).

(in formula, Z ¹and Z ²represent the N-alkylamino of the alkylthio of the alkoxyl group of the fluoroalkyl of the alkyl sulphonyl of the alkyl sulphinyl of the alkyl of hydrogen atom, halogen atom, carbonatoms 1 ~ 6, cyano group, nitro, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, the N of carbonatoms 2 ~ 12 independently of one another; the N-alkylsulfamoyl group of N-dialkyl amido, carbonatoms 1 ~ 6, the N of carbonatoms 2 ~ 12, N-dialkyl sulfamine or-COOH.

Q ¹and Q ²expression-CR independently of one another ¹r ²-,-S-,-NR ²-,-CO-or-O-, R ¹and R ²represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4 independently of one another.

Y ¹represent substituted or unsubstituted polycycle aromatic hydrocarbyl or substituted or unsubstituted polycycle aromatic heterocycle.

D ¹and D ²represent singly-bound or divalent linker independently of one another.

G ¹and G ²represent divalence ester ring type alkyl independently of one another, this ester ring type alkyl can have halogen atom, the alkyl of carbonatoms 1 ~ 4, the fluoroalkyl of carbonatoms 1 ~ 4, the alkoxyl group of carbonatoms 1 ~ 4, cyano group or nitro ,-the CH of this ester ring type alkyl ₂--O-,-S-or-NH-can be used to replace.)

[2] compound as described in [1], wherein, has the divalent group that formula (2-1) or formula (2-2) represent.

(in formula, Z ¹, Z ², Q ¹, Q ², Y ¹, D ¹, D ², G ¹and G ²represent middle with [1] respectively and define the identical meaning.

E ¹and E ²represent singly-bound or divalent linker independently of one another.

B ¹and B ²represent singly-bound or divalent linker independently of one another.

A ¹and A ²represent divalence ester ring type alkyl or O divalent aromatic alkyl independently of one another, this ester ring type alkyl and this aromatic hydrocarbyl can have halogen atom, the alkyl of carbonatoms 1 ~ 4, the fluoroalkyl of carbonatoms 1 ~ 4, the alkoxyl group of carbonatoms 1 ~ 4, the Fluoroalkyloxy of carbonatoms 1 ~ 4, cyano group or nitro.

K and l represents the integer of 0 ~ 3 independently of one another.)

[3] compound as described in [1], represents by formula (3-1) or formula (3-2).

(in formula, Z ¹, Z ², Q ¹, Q ², Y ¹, D ¹, D ², G ¹, G ², E ¹, E ², B ¹, B ², A ¹, A ², k with l represent respectively and define the identical meaning with [1] and [2].

F ¹and F ²represent the alkane 2 basis of carbonatoms 1 ~ 12 independently of one another, this alkane 2 basis can have the alkyl of carbonatoms 1 ~ 5, the alkoxy or halogen atom of carbonatoms 1 ~ 5 ,-the CH of this alkane 2 basis ₂-can replace with-O-or-CO-.

P ¹and P ²represent hydrogen atom or polymerizable group independently of one another.)

[4] compound according to any one of [1] ~ [3], wherein, Y ¹for formula (Y ¹-1) or formula (Y ¹-4) group represented.

(in formula, Z ³represent the alkylthio of the alkoxyl group of the fluoroalkyl of the alkyl sulphinyl of the alkyl sulphonyl of the alkyl of halogen atom, carbonatoms 1 ~ 6, cyano group, nitro, nitroso-group, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, the N of carbonatoms 2 ~ 8 independently of one another; the N-alkylamino of N-dialkyl amido, carbonatoms 1 ~ 4, sulfamyl, the N-alkylsulfamoyl group of carbonatoms 1 ~ 6, the N of carbonatoms 2 ~ 12, N-dialkyl sulfamine or-COOH.

V ¹represent-CO-,-S-,-NR ³-,-O-,-Se-or-SO ₂-.

W ¹, W ², W ³, W ⁴and W ⁵expression-CR independently of one another ³=or-N=, R ³represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4 independently of one another.Wherein, V ¹, W ¹, W ², W ³, W ⁴and W ⁵in at least one contain S, N, O or Se.

A represents the integer of 0 ~ 3 independently of one another.)

[5] compound as described in [4], wherein, formula (Y ¹-1) group represented is with formula (Y ³-1) group represented, formula (Y ¹-4) group represented is with formula (Y ³-3) group represented.

(in formula, Z ³, a, V ¹and W ²represent middle with [4] respectively and define the identical meaning.)

[6] compound as described in [4] or [5], wherein, V ¹for-S-,-NR ³-or-O-.

[7] compound according to any one of [1] ~ [6], wherein, G ¹and G ²for trans-Isosorbide-5-Nitrae-hexanaphthene two base.

[8] compound according to any one of [2] ~ [7], wherein, A ¹and A ²represent Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-hexanaphthene two base independently of one another, this Isosorbide-5-Nitrae-phenylene and Isosorbide-5-Nitrae-hexanaphthene two base can have halogen atom, the alkyl of carbonatoms 1 ~ 4, trifluoromethyl, cyano group or nitro.

[9] compound according to any one of [3] ~ [8], wherein, only with A ¹in conjunction with B ¹only with A ²in conjunction with B ²be-CH independently of one another ₂-CH ₂-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-O-CH ₂-,-CH ₂-O-or singly-bound,

With F ¹in conjunction with B ¹and with F ²in conjunction with B ²be-O-,-CO-O-,-O-CO-,-O-CO-O-,-CO-NH-,-NH-CO-or singly-bound independently of one another.

[10] compound according to any one of [3] ~ [9], wherein, P ¹and P ²be hydrogen atom, acryloxy or methacryloxy independently of one another, and P ¹and P ²it is asynchronously hydrogen atom.

[11] composition, wherein, containing the compound according to any one of [1] ~ [10] and liquid crystalline cpd (but being different from above-claimed cpd).

[12] composition as described in [11], wherein, liquid crystalline cpd is the liquid crystalline cpd shown in formula (20).

(in formula, A ¹¹represent O divalent aromatic alkyl, divalence ester ring type alkyl or divalent heterocycle independently of one another, this aromatic hydrocarbyl, this ester ring type alkyl and this heterocyclic radical can have halogen atom, the alkyl of carbonatoms 1 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6, the N-alkylamino of carbonatoms 1 ~ 6, the N of carbonatoms 2 ~ 12, N-dialkyl amido, nitro, cyano group or sulfenyl.B ¹¹and B ¹²expression-CR independently of one another ¹⁴r ¹⁵-,-C ≡ C-,-CH=CH-,-CH ₂-CH ₂-,-O-,-S-,-C (=O)-,-C (=O)-O-,-O-C (=O)-,-O-C (=O)-O-,-C (=S)-,-C (=S)-O-,-O-C (=S)-,-CH=N-,-N=CH-,-N=N-,-C (=O)-NR ¹⁶-,-NR ¹⁶-C (=O)-,-OCH ₂-,-OCF ₂-,-NR ¹⁶-,-CH ₂o-,-CF ₂o-,-CH=CH-C (=O)-O-,-O-C (=O)-CH=CH-or singly-bound, R ¹⁴and R ¹⁵represent the alkyl of hydrogen atom, fluorine atom or carbonatoms 1 ~ 4 independently of one another, or R ¹⁴and R ¹⁵in conjunction with and represent the alkane 2 basis of carbonatoms 4 ~ 7.R ¹⁶represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4.

E ¹¹represent the alkane 2 basis of carbonatoms 1 ~ 12, this alkane 2 basis can have the alkyl of carbonatoms 1 ~ 6, the alkoxy or halogen atom of carbonatoms 1 ~ 6.

P ¹¹represent polymerizable group.

G represents alkyl, the alkoxyl group of carbonatoms 1 ~ 13, the fluoroalkyl of carbonatoms 1 ~ 13, the N-alkylamino of carbonatoms 1 ~ 13, the N of carbonatoms 2 ~ 26 of hydrogen atom, halogen atom, carbonatoms 1 ~ 13, N-dialkyl amido, cyano group or nitro, or represent the alkyl with the carbonatoms 1 ~ 18 of polymerizable group, this alkyl can have the alkoxy or halogen atom of carbonatoms 1 ~ 6.

T represents the integer of 1 ~ 5.)

[13] composition as described in [11] or [12], wherein, also containing polymerization starter.

[14] composition as described in [13], wherein, polymerization starter contains methyl phenyl ketone based compound.

[15] blooming, by obtaining the compound polymerization according to any one of [1] ~ [10].

[16] blooming, by obtaining the composition polymerization according to any one of [11] ~ [14].

[17] blooming as described in [15] or [16], the phase difference value (Re (550)) for wavelength 550nm place is λ/4 plate of 113 ~ 163nm.

[18] blooming as described in [15] or [16], the phase difference value (Re (550)) for wavelength 550nm place is λ/2 plate of 250 ~ 300nm.

[19] polaroid, wherein, containing the blooming according to any one of [15] ~ [18] and polarizing coating.

[20] colour filter, wherein, is coating the blooming alignment films on filter substrate is formed with according to any one of [15] ~ [18].

[21] liquid crystal indicator, wherein, containing the colour filter described in [20].

[22] panel display apparatus, wherein, possesses the liquid crystal panel containing the polaroid described in [19].

[23] organic EL display, wherein, possesses the organic electroluminescence panel containing the polaroid described in [19].

[24] manufacture method for non-polymeric membrane, is characterized in that, by the solution coat containing the compound according to any one of [1] ~ [10] on supporting substrate or be coated in the alignment films that is formed on supporting substrate, and makes it dry.

[25] manufacture method for blooming, is characterized in that, makes the non-polymeric membrane solidification obtained by the manufacture method described in [24].

Accompanying drawing explanation

Fig. 1 is the schematic diagram representing colour filter 1 of the present invention.

Fig. 2 is the schematic diagram representing liquid crystal indicator 5 of the present invention.

Fig. 3 is the schematic diagram representing polaroid 30 of the present invention.

Fig. 4 is the schematic diagram representing the liquid crystal panel 20 of liquid crystal indicator of the present invention and the laminating product 21 of polaroid 30.

Fig. 5 is the schematic diagram of the organic EL plate 23 representing organic EL display of the present invention.

Nomenclature

1,1 ' colour filter

2,2 ' blooming

3,3 ' alignment films

4,4 ' color-filter layer

5 liquid crystal indicators

6,10 polaroids

7,11 substrates

8 comparative electrodes

9 liquid crystal layers

12 TFT, insulation layer

13 transparency electrodes

13 ' reflecting electrode

30,30a, 30b, 30c, 30d, 30e polaroid

14,14 ' duplexer

15 polarizing coatings

16,16 ' supporting substrate

17,17 ' alignment films

18,18 ' blooming

19,19 ', 22,25 binder layers

20 liquid crystal panels

21 laminating product

23 organic EL plates

24 luminescent layers

Embodiment

Compound of the present invention contains the divalent group that following formula (1-1) or formula (1-2) represent.

In formula (1-1) and formula (1-2), Z ¹and Z ²represent the N-alkylamino of the alkylthio of the alkoxyl group of the fluoroalkyl of the alkyl sulphonyl of the alkyl sulphinyl of the alkyl of hydrogen atom, halogen atom, carbonatoms 1 ~ 6, amino, nitro, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, the N of carbonatoms 2 ~ 12 independently of one another; the N-alkylsulfamoyl group of N-dialkyl amido, carbonatoms 1 ~ 6, the N of carbonatoms 2 ~ 12, N-dialkyl sulfamine or-COOH.

As halogen atom, fluorine atom, chlorine atom, bromine atoms and atomic iodine can be enumerated, preferred fluorine atom, chlorine atom and bromine atoms.

As the alkyl of carbonatoms 1 ~ 6, methyl, ethyl, propyl group, sec.-propyl, sound of chopping wood base, isobutyl-, sec-butyl, the tertiary butyl, amyl group and hexyl can be enumerated, the alkyl of preferred carbonatoms 1 ~ 4, the more preferably alkyl of carbonatoms 1 ~ 2, particularly preferably methyl.

As the alkyl sulphinyl of carbonatoms 1 ~ 6; methylsulfinyl, ethylsulfinyl, propylsulfenyl, isopropylsulphinyl, butylsulfinyl, isobutyl-sulfinyl, sec-butyl sulfinyl, terf-butylsulfinyl, pentylsulfinyl and hexylsulfinyl can be enumerated; the alkyl sulphinyl of preferred carbonatoms 1 ~ 4; more preferably the alkyl sulphinyl of carbonatoms 1 ~ 2, particularly preferably methylsulfinyl.

As the alkyl sulphonyl of carbonatoms 1 ~ 6; methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropelsulfonyl, butyl alkylsulfonyl, iso-butylsulfonyl, sec-butylsulfonyl, tert. butylsulfonyl, pentylsulfonyl and hexyl alkylsulfonyl can be enumerated; the alkyl sulphonyl of preferred carbonatoms 1 ~ 4; more preferably the alkyl sulphonyl of carbonatoms 1 ~ 2, particularly preferably methyl sulphonyl.

As the fluoroalkyl of carbonatoms 1 ~ 6, methyl fluoride, trifluoromethyl, fluoro ethyl, pentafluoroethyl group, seven fluoropropyls and nine fluorine butyl can be enumerated, the fluoroalkyl of preferred carbonatoms 1 ~ 4, the more preferably fluoroalkyl of carbonatoms 1 ~ 2, particularly preferably trifluoromethyl.

As the alkoxyl group of carbonatoms 1 ~ 6, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy and hexyloxy can be enumerated, the alkoxyl group of preferred carbonatoms 1 ~ 4, more preferably the alkoxyl group of carbonatoms 1 ~ 2, particularly preferably methoxyl group.

As the alkylthio of carbonatoms 1 ~ 6, methylthio group, ethylmercapto group, rosickyite base, isopropyisulfanyl, butylthio, isobutylthio, secondary butylthio, tertiary butylthio, penta sulfenyl and own sulfenyl can be enumerated, the alkylthio of preferred carbonatoms 1 ~ 4, more preferably the alkylthio of carbonatoms 1 ~ 2, particularly preferably methylthio group.

As the N-alkylamino of carbonatoms 1 ~ 6, N-methylamino, N-ethylamino, N-propylcarbamic, N-isopropylamino, N-butyl amino, N-isobutylamino, N-s-butylamino, N-tert-butylamino, N-pentyl amino and N-hexylamino can be enumerated, the N-alkylamino of preferred carbonatoms 1 ~ 4, more preferably the N-alkylamino of carbonatoms 1 ~ 2, particularly preferably N-methylamino.

As the N of carbonatoms 2 ~ 12, N-dialkyl amido, N can be enumerated, N-dimethylamino, N-methyl-N-ethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylaminoethyl, N, N-dibutylamino, N, N-diisobutylamino, N, N-dipentylamino and N, N-dihexyl amino, the N of preferred carbonatoms 2 ~ 8, N-dialkyl amido, the more preferably N of carbonatoms 2 ~ 4, N-dialkyl amido, particularly preferably N, N-dimethylamino.

As the N-alkylsulfamoyl group of carbonatoms 1 ~ 6; N-Methylsulfamoyl, N-ethylsulfamovl, N-propylsulfamov, N-isopropylsulfamoyl base, N-Butylsulfamoyl base, N-isobutyl-sulfamyl, N-sec-butyl sulfamyl, N-tertiary butyl sulfamyl, N-amyl group sulfamyl and N-hexyl sulfamyl can be enumerated; the N-alkylsulfamoyl group of preferred carbonatoms 1 ~ 4; more preferably the N-alkylsulfamoyl group of carbonatoms 1 ~ 2, particularly preferably N-Methylsulfamoyl.

As the N of carbonatoms 2 ~ 12, N-dialkyl sulfamine, N can be enumerated, N-DimethylsuIfamoyl, N-methyl-N ethyl sulfamyl, N, N-diethyl amino alkylsulfonyl, N, N-dipropyl sulfamyl, N, N-di-isopropyl sulfamyl, N, N-dibutylamine alkylsulfonyl, N, N-diisobutyl sulfamyl, N, N-diamyl sulfamyl and N, N-dihexyl sulfamyl, the N of preferred carbonatoms 2 ~ 8, N-dialkyl sulfamine, more preferably the N of carbonatoms 2 ~ 4, N-dialkyl sulfamine, particularly preferably N, N-DimethylsuIfamoyl.

Z ¹and Z ²be preferably hydrogen atom, halogen atom, methyl, cyano group, nitro, methyl sulphonyl, trifluoromethyl, methoxyl group, methylthio group, N-methylamino, N independently of one another; N-dimethylamino, N-Methylsulfamoyl, N, N-DimethylsuIfamoyl or-COOH.

In formula (1-1) and formula (1-2), Q ¹and Q ²expression-CR independently of one another ¹r ²-,-S-,-NR ²-,-CO-or-O-, R ¹and R ²represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4 independently of one another.As R ¹and R ²the alkyl of carbonatoms 1 ~ 4, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-and the tertiary butyl can be enumerated, the alkyl of preferred carbonatoms 1 ~ 2, more preferably methyl.

Q ¹and Q ²be preferably-S-,-CO-,-NH-,-N (CH independently of one another ₃)-, is more preferably-S-or-CO-.

As the group that the formula (1-1-A) in the divalent group shown in formula (1-1) represents, the group shown in following formula (1-1-1) ~ formula (1-1-18) can be enumerated.

As the group that the formula (1-2-A) in the divalent group shown in formula (1-2) represents, the group shown in following formula (1-2-1) ~ formula (1-2-5) can be enumerated.

In formula (1-1) and formula (1-2), Y ¹represent substituted or unsubstituted polycycle aromatic hydrocarbyl or substituted or unsubstituted polycycle aromatic heterocycle." polycycle aromatic hydrocarbyl " means the aromatic hydrocarbyl with at least 2 aromatic nucleus, can enumerate the aromatic hydrocarbyl that more than 2 aromatic nucleus condense and the fused aromatic alkyl that formed and more than 2 aromatic nucleus combine and formed." polycycle aromatic heterocycle " means to have at least 1 aromatic heterocycle and the aromatic heterocycle with at least 1 ring be selected from aromatic nucleus and aromatic heterocycle, can enumerate the aromatic heterocycle that more than 1 heteroaromatic and 1 of being selected from aromatic nucleus and aromatic heterocycle condense with pressed on ring and the aromatic heterocycle that formed and at least 1 aromatic heterocycle close with at least 1 loops be selected from aromatic nucleus and aromatic heterocycle and formed.

Polycycle aromatic hydrocarbyl and polycycle aromatic heterocycle both can be without replacing, also can having substituting group.Alternatively base; halogen atom, the alkyl of carbonatoms 1 ~ 6, cyano group, nitro, nitroso-group, the alkyl sulphinyl of carbonatoms 1 ~ 6, the alkyl sulphonyl of carbonatoms 1 ~ 6, the fluoroalkyl of carbonatoms 1 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6, the alkylthio of carbonatoms 1 ~ 6, the N-alkylamino of carbonatoms 1 ~ 4, the N of carbonatoms 2 ~ 8 can be enumerated; the N-alkylsulfamoyl group of N-dialkyl amido, sulfamyl, carbonatoms 1 ~ 6, the N of carbonatoms 2-12, N-dialkyl sulfamine and-COOH.

Y ¹be preferably formula (Y ¹-1) ~ formula (Y ¹-7) group shown in, is more preferably formula (Y ¹-1) or formula (Y ¹-4) group shown in.

V ¹and V ²represent-CO-,-S-,-NR independently of one another ³-,-O-,-Se-or-SO ₂-.

W ¹, W ², W ³, W ⁴and W ⁵expression-CR independently of one another ³=or-N=, R ³represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4 independently of one another.Wherein, V ¹, V ², W ¹, W ², W ³, W ⁴and W ⁵in at least one contain S, N, O or Se.

A represents the integer of 0 ~ 3 independently of one another, and b represents the integer of 0 ~ 2 independently of one another.)

Formula (Y ¹-1) group shown in is preferably formula (Y ²-1) ~ formula (Y ²-6) any one in the group shown in.

Formula (Y ¹-2) group shown in is preferably formula (Y ²-7) or formula (Y ²-9) group shown in, formula (Y ¹-3) group shown in is preferably formula (Y ²-8) or formula (Y ²-10) group shown in.

Formula ((Y ¹-4) group shown in is preferably formula (Y ²-11) ~ formula (Y ²-13) any one in the group shown in.

Formula (Y ¹-5) group shown in is preferably formula (Y ²-14) ~ formula (Y ²-16) any one in the group shown in.

Wherein, formula (Y is more preferably ³-1) ~ formula (Y ³-6) any one in the group shown in.

(in formula, Z ³, V ¹, V ², W ¹, W ², W ³, W ⁴, W ⁵, a and b represent implication same as described above.)

As Z ³in halogen atom, the alkyl of carbonatoms 1 ~ 6, the alkyl sulphonyl of carbonatoms 1 ~ 6, the alkyl sulphinyl of carbonatoms 1 ~ 6, the fluoroalkyl of carbonatoms 1 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6, the alkylthio of carbonatoms 1 ~ 6, the N of carbonatoms 2 ~ 8; the N of the N-alkylamino of N-dialkyl amido, carbonatoms 1 ~ 4, the N-alkylsulfamoyl group of carbonatoms 1 ~ 6 and carbonatoms 2 ~ 12; N-dialkyl sulfamine, can enumerate group same as described above respectively.

Wherein, Z ³be preferably halogen atom, methyl, ethyl, sec.-propyl, sec-butyl, amyl group, hexyl, amino, nitro, methyl sulphonyl, nitroso-group, trifluoromethyl, methoxyl group, methylthio group, N; N-dimethylamino, N-methylamino or-COOH; be more preferably halogen atom, methyl, ethyl, sec.-propyl, sec-butyl, amyl group, hexyl, cyano group, nitro or trifluoromethyl, be particularly preferably methyl, ethyl, sec.-propyl, sec-butyl, amyl group or hexyl.

V ¹and V ²be preferably-S-,-NR independently of one another ³-or-O-.

W ¹~ W ⁵be preferably-CR independently of one another ³=or-N=.

V ¹, V ²and W ¹~ W ⁵in at least one preferably containing S, N or O.

A be preferably 0 or 1, b be preferably 0.

As Y ¹concrete example, the group shown in formula (ar-1) ~ (ar-840) can be enumerated.Should illustrate, in following group, Me represents methyl, and Et represents ethyl, and * represents combining site.

In formula (1-1) and formula (1-2), D ¹and D ²represent singly-bound or divalent linker independently of one another.As divalent linker, can enumerate-CO-O-,-O-CO-,-C (=S)-O-,-O-C (=S)-,-CR ⁴r ⁵-,-CR ⁴r ⁵-CR ⁶r ⁷-,-O-CR ⁴r ⁵-,-CR ⁴r ⁵-O-,-CR ⁴r ⁵-O-CR ⁶r ⁷-,-CR ⁴r ⁵-O-CO-,-O-CO-CR ⁴r ⁵-,-CR ⁴r ⁵-O-CO-CR ⁶r ⁷-,-CR ⁴r ⁵-CO-O-CR ⁶r ⁷-,-NR ⁸-CR ⁴r ⁵-,-CR ⁴r ⁵-NR ⁸-,-CO-NR ⁸-,-NR ⁸-CO-,-O-,-S-,-NR ⁸-and-CR ⁴=CR ⁵-.Described R ⁴, R ⁵, R ⁶and R ⁷represent the alkyl (such as methyl, ethyl, propyl group, sec.-propyl, butyl etc.) of hydrogen atom, fluorine atom or carbonatoms 1 ~ 4 independently of one another, R ⁸represent the alkyl (such as methyl, ethyl, propyl group, sec.-propyl, butyl etc.) of hydrogen atom or carbonatoms 1 ~ 4.

D ¹and D ²be preferably *-O-CO-, *-O-C (=S)-, *-O-CR ⁴r ⁵-, *-NR ⁸-CR ⁴r ⁵-or *-NR ⁸-CO-, is more preferably *-O-CO-, *-O-C (=S)-or *-NR ⁸-CO-.Herein, * represents the combining site with the group shown in the group shown in formula (1-1-A) or formula (1-2-A).R ⁴, R ⁵, R ⁶and R ⁷be preferably the alkyl of hydrogen atom or carbonatoms 1 ~ 4 independently of one another, be more preferably hydrogen atom, methyl or ethyl.R ⁸be preferably hydrogen atom, methyl or ethyl.

In formula (1-1) and formula (1-2), G ¹and G ²represent divalence ester ring type alkyl independently of one another, the hydrogen atom of this ester ring type alkyl can use the alkoxyl group of the fluoroalkyl of the alkyl of halogen atom, carbonatoms 1 ~ 4, carbonatoms 1 ~ 4, carbonatoms 1 ~ 4, cyano group or nitration ,-the CH of this ester ring type alkyl ₂--O-,-S-or-NH-can be used to replace.

As divalence ester ring type alkyl, can enumerate and form the divalence ester ring type alkyl that the carbon atom of ring and heteroatomic number are respectively 3 ~ 10 and 0 ~ 2, group shown in preferred formula (g-1) ~ formula (g-10), is more preferably 5 rings or 6 rings.

The hydrogen atom of the group shown in above-mentioned formula (g-1) ~ (g-10) can use the alkyl of the carbonatomss 1 ~ 4 such as methyl, ethyl, sec.-propyl, the tertiary butyl; The alkoxyl group of the carbonatoms such as methoxyl group, oxyethyl group 1 ~ 4; The fluoroalkyl of the carbonatomss such as trifluoromethyl 1 ~ 4; The Fluoroalkyloxy of the carbonatomss such as trifluoromethoxy 1 ~ 4; Cyano group; Nitro; The halogen atom displacements such as fluorine atom, chlorine atom, bromine atoms.

G ¹and G ²be preferably the group shown in formula (g-1), be more preferably Isosorbide-5-Nitrae-hexanaphthene two base, be particularly preferably trans-Isosorbide-5-Nitrae-hexanaphthene two base.

Compound of the present invention is preferably the compound containing formula (2-1) or the divalent group shown in formula (2-2).

(in formula, Z ¹, Z ², Q ¹, Q ², Y ¹, D ¹, D ², G ¹and G ²represent the meaning same as described above respectively.

K and l represents the integer of 0 ~ 3 independently of one another.)

As E ¹and E ²divalent linker, can-CR be enumerated ⁹r ¹⁰-,-CH ₂-CH ₂-,-O-,-S-,-CO-O-,-O-CO-,-O-CO-O-,-C (=S)-O-,-O-C (=S)-,-O-C (=S)-O-,-CO-NR ¹¹-,-NR ¹¹-CO-,-O-CH ₂-,-CH ₂-O-,-S-CH ₂-,-CH ₂-S-,-NR ¹¹-and-CR ⁹=CR ¹⁰-.R ⁹and R ¹⁰represent the alkyl of hydrogen atom, fluorine atom or carbonatoms 1 ~ 4 independently of one another, R ¹¹represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4.

E ¹and E ²be preferably-CO-O-,-O-CO-,-O-CO-O-,-CO-NR independently of one another ¹¹-,-NR ¹¹-CO-,-CH ₂-O-,-CH ₂-S-or singly-bound, be more preferably-CO-O-.

As B ¹and B ²divalent linker, can-CR be enumerated ⁹r ¹⁰-,-CH ₂-CH ₂-,-O-,-S-,-CO-O-,-O-CO-,-O-CO-O-,-C (=S)-O-,-O-C (=S)-,-O-C (=S)-O-,-CO-NR ¹¹-,-NR ¹¹-CO-,-O-CH ₂-,-CH ₂-O-,-S-CH ₂-,-CH ₂-S-,-NR ¹¹-and-CR ⁹=CR ¹⁰-.

Easily manufacture from the view point of compound of the present invention, only with A ¹in conjunction with B ¹only with A ²in conjunction with B ²be preferably-CH independently of one another ₂-CH ₂-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-O-CH ₂-,-CH ₂-O-or singly-bound, show high liquid crystal liquid crystal property from the view point of compound of the present invention, is preferably-CO-O-or-O-CO-.

More easily manufacture from the view point of compound of the present invention, preferred B ¹with B ²identical.

As A ¹and A ²divalence ester ring type alkyl or O divalent aromatic alkyl, the O divalent aromatic alkyl of the group shown in above-mentioned formula (g-1) ~ formula (g-10), the carbonatoms 6 ~ 20 shown in following formula (a-1) ~ formula (a-8) can be enumerated.

The hydrogen atom of the group shown in above-mentioned formula (a-1) ~ formula (a-8) can use the alkyl of the carbonatomss 1 ~ 4 such as methyl, ethyl, sec.-propyl, the tertiary butyl; The alkoxyl group of the carbonatoms such as methoxyl group, oxyethyl group 1 ~ 4; The fluoroalkyl of the carbonatomss such as trifluoromethyl 1 ~ 4; The Fluoroalkyloxy of the carbonatomss such as trifluoromethoxy 1 ~ 4; Cyano group; Nitro; The halogen atom displacements such as fluorine atom, chlorine atom, bromine atoms.

Wherein, A ¹and A ²be preferably Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-hexanaphthene two base independently of one another, easily manufacture from the view point of compound of the present invention, more preferably Isosorbide-5-Nitrae-phenylene.

More easily manufacture from the view point of compound of the present invention, preferred A ¹with A ²identical.

From the view point of the liquid crystal liquid crystal property of compound of the present invention, preferred k and l is 0 ~ 2.Preferred k and l's and be less than 5, be more preferably less than 4.

Compound of the present invention is more preferably the compound that formula (3-1) or formula (3-2) represent.

(in formula, Z ¹, Z ², Q ¹, Q ², Y ¹, D ¹, D ², G ¹, G ², E ¹, E ², B ¹, B ², A ¹, A ², k and l represent implication same as described above respectively.

As F ¹and F ²the alkane 2 basis of carbonatoms 1 ~ 12, preferably-(CH ₂) ₃-,-(CH ₂) ₄-,-(CH ₂) ₅-,-(CH ₂) ₆-,-(CH ₂) ₇-,-(CH ₂) ₈-,-(CH ₂) ₉-,-(CH ₂) ₁₀-,-(CF ₂) ₄-,-(CF ₂) ₆-and-(CF ₂) ₈-, more preferably-(CH ₂) ₄-and-(CH ₂) ₆-.

With F ¹in conjunction with B ¹and with F ²in conjunction with B ²be preferably-O-,-CO-O-,-O-CO-,-O-CO-O-,-CO-NH-,-NH-CO-or singly-bound independently of one another.

Preferred P ¹and P ²in at least one be polymerizable group, from the view point of the film hardness of the blooming obtained by compound of the present invention, there is excellent tendency, more preferably P ¹and P ²be polymerizable group.

As long as polymerizable group can participate in the group of the polyreaction of the compounds of this invention, vinyl, vinyloxy group, styryl, p-(2-phenyl vinyl) phenyl, acryl, methacryloyl, acryloxy, methacryloxy, carboxyl, ethanoyl, hydroxyl, formamyl, the N-alkylamino of carbonatoms 1 ~ 4, amino, epoxy group(ing), oxetanyl (oxetanyl group), formyl radical, isocyanate base and isothiocyanic acid foundation specifically can be enumerated.Wherein, from being suitable for photopolymerisable viewpoint, preferred free-radical polymerised group or cationic polymerizable group, also easily manufacture from the view point of processing ease, compound of the present invention, more preferably acryloxy or methacryloxy, particularly preferably acryloxy.

Polymerizable group can directly and F ¹and F ²in conjunction with, but preferably by divalent linker (the such as described B of more than 1 ¹and B ²divalent linker etc.) combine.

As-D ¹-G ¹-E ¹-(A ¹-B ¹) _k-F ¹-P ¹with-D ²-G ²-E ²-(A ²-B ²) _l-F ²-P ²concrete example, the group that formula (R-1) ~ formula (R-134) represents can be enumerated.Should illustrate, in following formula, * represents the combining site with the group shown in formula (1-1-A) or formula (1-2-A), and n represents the integer of 2 ~ 12.

As compound of the present invention, the compound shown in formula (A1-1) ~ formula (A73-8) can be enumerated.Should illustrate, in following formula, * represents combining site, and the compound that such as formula (A1-1) represents is following compound.

Next, the manufacture method of the compounds of this invention is described.

Compound of the present invention can according to its structure, by by Methoden derOrganischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, known organic synthesis (the such as condensation reaction recorded in new experimental chemistry lecture etc., esterification, Williamson reacts, ullmann reaction, witig reaction, schiff bases formation reaction, Benzylation reaction, Yuan head reacts, Suzuki-Pu, palace reaction, root bank reacts, bear field is reacted, Hui Shan reacts (Hiyama reaction), Buchwald-Hartwig reacts, Friedel-Crafts reaction, He Ke reacts, Aldol reaction etc.) appropriately combined and manufacture.

Such as D ¹and D ²for the compound shown in the formula (3-1) of *-O-CO-or formula (3-2) can manufacture by the following method: react by making the compound shown in the compound shown in formula (11-1) and formula (11-2), obtain the compound shown in formula (11-3), then make the obtained compound shown in formula (11-3) and the compound shown in formula (11-4) react.

HO-Ar-OH (11-1)

(in formula, Ar represents described formula (1-1) or the divalent group shown in described formula (1-2).)

(in formula, G ¹, E ¹, A ¹, B ¹, F ¹, P ¹implication same as described above is represented with k.)

(in formula, Ar, G ¹, E ¹, A ¹, B ¹, F ¹, P ¹implication same as described above is represented with k.)

(in formula, G ², E ², A ², B ², F ², P ²implication same as described above is represented with l.)

In addition, G ¹with G ², E ¹with E ², A ¹with A ², B ¹with B ², F ¹with F ², P ¹with P ², and k and l respectively in identical situation, can react by making formula (11-2) compound of more than the compound shown in formula (11-1) and 2 equivalents, with a step manufacturing objective compound.

The reaction of the compound shown in the compound shown in formula (11-1) and formula (11-2) and the reaction of the compound shown in the compound shown in formula (11-3) and formula (11-4) are preferably implemented under the existence of condensing agent.

As condensing agent, 1-cyclohexyl-3-(2-morpholinoethyl) carbodiimide tosilate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, two (2 can be enumerated, 6-diisopropyl phenyl) carbodiimide, two (trimethyl silyl) carbodiimide, N, N ' carbodiimide compound such as-DIC; 2-methyl-6-nitrobenzoyl acid anhydrides, 2; 2 '-carbonyl diurethane-1H-imidazoles, 1; 1 '-oxalyl group diimidazole, diphenyl phosphate azide, 1 (4-nitrobenzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazole-1-base oxygen base tripyrrole alkyl hexafluorophosphate, 1H-benzotriazole-1-base oxygen base three (dimethylamino) hexafluorophosphate, N, N, N ', N '-tetramethyl--O-(N-succinimido) urea a tetrafluoro borate, N-(1,2,2,2-tetra-chloroethoxycarbonyl oxygen base) succinimide, N-benzene methoxy carbonyl acyl succinimide, O-(6-chlorinated benzotriazole-1-base)-N, N, N ', N '-tetramethyl-urea a tetrafluoro borate, O-(6-chlorinated benzotriazole-1-base)-N, N, N ', N '-tetramethyl-urea the bromo-1-ethylpyridine of hexafluorophosphate, 2- chloro-1, the 3-methylimidazole of a tetrafluoro borate, 2- chloro-1, the 3-methylimidazole of muriate, 2- the chloro-1-picoline of hexafluorophosphate, 2- the chloro-1-picoline of iodide, 2- the fluoro-1-picoline of tosilate, 2- tosilate, trichoroacetic acid(TCA) five chlorophenyl ester etc.Select many from the view point of reactive, cost and the solvent that can use, preferred dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, two (2,6-diisopropyl phenyl) carbodiimide, two (trimethyl silyl) carbodiimide, N, N '-DIC and 2,2 '-carbonyl diurethane-1H-imidazoles.

Then, composition of the present invention is described.Composition of the present invention contains compound of the present invention and is different from the liquid crystalline cpd of the compounds of this invention.

As the concrete example of liquid crystalline cpd, the compound in the compound described in " liquid crystal brief guide (liquid crystal brief guide is compiled the council and compiled, the distribution on October 30th, 12 of kind (strain) Heisei of ball), 3 chapter molecular structures and liquid crystal liquid crystal property, 3.2 achirality rod shaped liquid crystal molecules, 3.3 chirality rod shaped liquid crystal molecules " with polymerizable group can be enumerated.

A kind of liquid crystalline cpd can be used, also can use two or more liquid crystalline cpd.

By using the composition containing the compounds of this invention and liquid crystalline cpd, optical characteristics, the hot physical property such as wavelength dispersion value, phasic difference value of the blooming that can obtain making said composition be polymerized are adjusted to desired value.

As liquid crystalline cpd, the liquid crystalline cpd (hereinafter sometimes referred to " compound (20) ") etc. shown in formula (20) can be enumerated.

P ¹¹represent polymerizable group.

T represents the integer of 1 ~ 5.)

Particularly as P ¹¹with the polymerizable group in G; as long as can with the group of compound polymerization of the present invention, the N-alkylamino, epoxy group(ing), oxetanyl, formyl radical ,-N=C=O or-N=C=S etc. of vinyl, vinyl oxygen base, styryl, p-(2-phenyl vinyl) phenyl, acryl, acryloxy, methacryloyl, methacryloxy, carboxyl, ethanoyl, hydroxyl, formamyl, amino, carbonatoms 1 ~ 4 can be enumerated.Wherein, high from the view point of photopolymerisable reactivity, preferred free-radical polymerised group or cationic polymerizable group, from processing ease and the manufacture of liquid crystalline cpd be also easy to viewpoint, preferred acryloxy, methacryloxy or vinyloxy group.

In addition, A ¹¹aromatic hydrocarbyl, ester ring type alkyl and heterocyclic radical carbonatoms be preferably 3 ~ 18 separately, be more preferably 5 ~ 12, be particularly preferably 5 or 6.

As compound (20), the compound shown in formula (20-1) and formula (20-2) can be enumerated.

P ¹¹-E ¹¹-(B ¹¹-A ¹¹) _t1-B ¹²-E ¹²-P ¹²(20-1)

P ¹¹-E ¹¹-(B ¹¹·A ¹¹) _t2-B ¹²-F ¹¹(20-2)

(in formula, P ¹¹, E ¹¹, B ¹¹, A ¹¹, B ¹²represent the meaning same as described above.

F ¹¹represent hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 13, the alkoxyl group of carbonatoms 1 ~ 13, the fluoroalkyl of carbonatoms 1 ~ 13, the N-alkylamino of carbonatoms 1 ~ 13, the N of carbonatoms 2 ~ 26, N-dialkyl amido, cyano group or nitro.

E ¹²represent the alkane 2 basis of carbonatoms 1 ~ 12, this alkane 2 basis can have the alkyl of carbonatoms 1 ~ 6, the alkoxy or halogen atom of carbonatoms 1 ~ 6.

P ¹²represent polymerizable group.

T ¹and t ²represent the integer of 1 ~ 5.)

As the compound shown in formula (20-1) and (20-2), formula (I), formula (II), formula (III), formula (IV) or the compound shown in formula (V) can be enumerated.

P ¹¹-E ¹¹-B ¹¹-A ¹¹-B ¹²-A ¹²-B ¹³-A ¹³-B ¹⁴-A ¹⁴-B ¹⁵-A ¹⁵-B ¹⁶-E ¹²-P ¹²(I)

P ¹¹-E ¹¹-B ¹¹-A ¹¹-B ¹²-A ¹²-B ¹³-A ¹³-B ¹⁴-A ¹⁴-B ¹⁵-E ¹²-P ¹²(II)

P ¹¹-E ¹¹-B ¹¹-A ¹¹-B ¹²-A ¹²-B ¹³-A ¹³-B ¹⁴-E ¹²-P ¹²(III)

P ¹¹-E ¹¹-B ¹¹-A ¹¹-B ¹²-A ¹²-B ¹³-A ¹³-B ¹⁴-F ¹¹(IV)

P ¹¹-E ¹¹·B ¹¹-A ¹¹-B ¹²-A ¹²-B ¹³-F ¹¹(V)

(in formula, A ¹²~ A ¹⁵represent and A ¹¹identical implication, B ¹³~ B ¹⁶represent and B ¹¹identical implication.)

In the compound shown in formula (20-1), formula (20-2), formula (I), formula (II), formula (III), formula (lV) and formula (V), preferred P ¹¹with E ¹¹key be ehter bond or ester bond, P ¹²with E ¹²key be ehter bond or ester bond.

As the concrete example of liquid crystalline cpd, following formula (I-1) ~ formula (I-5), formula (B1-1) ~ formula (B20-8) and the compound shown in compound equation (I) shown in formula (C1-1) ~ formula (C4-8) can be enumerated; The compound shown in compound equation (II) shown in formula (II-1) ~ formula (II-6); The compound shown in compound equation (III) shown in formula (III-1) ~ formula (III-19); The compound shown in compound equation (IV) shown in formula (IV-1) ~ formula (IV-14); The compounds etc. shown in formula V such as the compound shown in formula (V-1) ~ formula (V-5).Should illustrate, in following formula, k represents the integer of 1 ~ 11, and * represents combining site.These liquid crystalline cpds synthesize easily from the view point of it or have commercially available and easily obtain, and are preferred liquid crystalline cpds.

When in order to control the hot physical property of obtained blooming and use the composition containing liquid crystalline cpd, excellent in reliability from the view point of gained blooming, preferred formula (I-1) ~ formula (I-5), formula (B1-1) ~ formula (B20-8), formula (C1-1) ~ formula (C4-8), liquid crystalline cpd shown in formula (II-1) ~ formula (II-6) and formula (III-1) ~ formula (III-19), from the view point of the intermiscibility excellence to the compounds of this invention, preferred formula (I-1) ~ formula (I-5), formula (B1-1) ~ formula (B20-8), liquid crystalline cpd shown in formula (Cl-1)-Shi (C4-8) and formula (III-1) ~ formula (III-19).From the view point of the blooming that can obtain the dispersion of display inverse wave length, the liquid crystalline cpd shown in preferred formula (B1-1)-Shi (B20-8) and formula (C1-1) ~ formula (C4-8).

Relative to total 100 weight part of liquid crystalline cpd and the compounds of this invention, the usage quantity of liquid crystalline cpd is generally below 90 weight parts.

Composition of the present invention is preferably also containing polymerization starter.Polymerization starter preferably containing Photoepolymerizationinitiater initiater, as Photoepolymerizationinitiater initiater, produces the Photoepolymerizationinitiater initiater of free radical preferably by rayed.

As Photoepolymerizationinitiater initiater, bitter almond oil camphor compound, benzophenone cpd, acetophenone compound, acylphosphine oxide compound, triaizine compounds, iodine can be enumerated salt and sulfonium salt.

As bitter almond oil camphor compound, bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether and benzoin isobutyl ether can be enumerated.

As benzophenone cpd; benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 can be enumerated '-dimethyl diphenyl sulfide, 3; 3 '; 4; 4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone and 2; 4,6-tri-methyl benzophenone.

As acetophenone compound, α can be enumerated, α-diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-methylthio group phenyl) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1, 2-phenylbenzene-2, 2-dimethoxy-1-ethyl ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, the oligopolymer of 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone.

As acylphosphine oxide compound, TMDPO and two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide can be enumerated.

As triaizine compounds, can 2 be enumerated, two (the trichloromethyl)-6-(4-p-methoxy-phenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl group naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(5-methyl furan-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(furans-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylin-2-aminomethyl phenyl) vinyl]-1 of 4-, 3, 5-triazine and 2, two (trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl-1, 3, 5-triazine.

As Photoepolymerizationinitiater initiater, IRGACURE907 (Ciba Japan Co., Ltd. system) also can be used, IRGACURE184 (Ciba Japan Co., Ltd. system), IRGACURE651 (Ciba Japan Co., Ltd. system), IRGACURE819 (Ciba Japan Co., Ltd. system), IRGACURE250 (Ciba Japan Co., Ltd. system), IRGACURE369 (Ciba Japan Co., Ltd. system), SEIKUOL BZ (Seiko KCC system), SEIKUOL Z (Seiko KCC system), SEIKUOL BEE (Seiko KCC system), KAYACURE BP100 (Nippon Kayaku K. K's system), KAYACURE UVI-6992 (DOW Inc.), ADEKA OPTOMER SP-152 (ADEKA Corp.'s system), ADEKA OPTOMER SP-170 (ADEKA Corp.'s system), TAZ-A (Japanese Siber Hegner Inc.), TAZ-PP (Japanese Siber Hegner Inc.), the commercially available products such as TAZ-104 (three and chemical company's system).

Have from the view point of the thermotolerance of gained blooming and humidity resistance the tendency increased, as Photoepolymerizationinitiater initiater, preferably use acetophenone compound, more preferably 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone.

Relative to total 100 weight part of liquid crystalline cpd and the compounds of this invention, in composition of the present invention, the content of polymerization starter is generally 0.1 ~ 30 weight part, is preferably 0.5 ~ 10 weight part.As long as in above-mentioned scope, just compound polymerization of the present invention can be made when not upsetting the orientation of liquid crystalline cpd.

Composition of the present invention can contain photosensitizers.As photosensitizers, the xanthone such as xanthone, thioxanthone compound (such as 2,4-diethyl thioxanthones, ITX etc.), anthracene can be enumerated, there is the substituent anthracene compounds such as alkoxyl group (such as dibutoxy anthracene etc.), thiodiphenylamine and rubrene.

By using photosensitizers, the polyreaction of the compounds of this invention can be carried out with highly sensitive, the ageing stability of obtained blooming can also be made to improve.Relative to total 100 weight part of liquid crystalline cpd and the compounds of this invention, the content of photosensitizers is generally 0.1 ~ 30 weight part, is preferably 0.5 ~ 10 weight part.As long as in above-mentioned scope, just compound polymerization of the present invention can be made when not upsetting the orientation of liquid crystalline cpd.

Composition of the present invention can contain polymerization retarder.As polymerization retarder, Resorcinol can be enumerated, there are substituent Resorcinol compound, the butyl-catechols etc. such as alkoxyl group there is substituent pyrocatechol compound, the pyrogallol compounds, 2 such as alkyl, 2, radical scavenger, thiophenol compound, beta-naphthylamine compound, the 2-Naphthol compounds etc. such as 6,6-tetramethyl piperidine-1-oxyradical.

By using polymerization retarder, the control of the polyreaction of liquid crystalline cpd, the compounds of this invention becomes easy, can improve the stability of obtained blooming.Relative to total 100 weight part of liquid crystalline cpd and the compounds of this invention, the content of polymerization retarder is 0.1 ~ 30 weight part, is preferably 0.5 ~ 10 weight part.As long as in above-mentioned scope, just compound polymerization of the present invention can be made when not upsetting the orientation of liquid crystalline cpd.

Composition of the present invention can contain flow agent.As flow agent, radiation-curing additive for coatings (BYK-Chemie Japan system: BYK-352 can be enumerated, BYK-353, BYK-361N), paint additive (TORAY DOW CORNING Co., Ltd. system: SH28PA, DC11PA, ST80PA), paint additive (Shin-Etsu Chemial Co., Ltd's system: KP321, KP323, X22-161A, KF6001), fluorine system additive (Dainippon Ink Chemicals's system: F-445, F-470, F-479) etc.

By using flow agent, more level and smooth blooming can be obtained.In addition, in the manufacturing processed of blooming, also can control the mobility of composition of the present invention, or adjust the cross-linking density in the blooming that obtains.Relative to total 100 weight part of liquid crystalline cpd and the compounds of this invention, the content of flow agent is generally 0.01 ~ 30 weight part, is preferably 0.05 ~ 10 weight part.As long as in above-mentioned scope, just compound polymerization of the present invention can be made when not upsetting the orientation of liquid crystalline cpd.

Composition of the present invention from the viewpoint of its mobility, preferably containing organic solvent.As organic solvent, as long as the organic solvent of the compounds of this invention, liquid crystalline cpd etc. can be dissolved and be the solvent of inertia to polyreaction, specifically the alcoholic solvents such as methyl alcohol, ethanol, ethylene glycol, Virahol, propylene glycol, ethylene glycol monomethyl ether, butyl glycol ether can be enumerated; The ester solvents such as ethyl acetate, butylacetate, ethylene glycol monomethyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; The ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, pimelinketone, 2-heptanone, methyl iso-butyl ketone (MIBK); The non-chlorinated aliphatic solventss such as pentane, hexane, heptane; The non-chlorinated aromatic hydrocarbon solvents such as toluene, dimethylbenzene, phenol; The nitrile solvents such as acetonitrile; The ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran (THF), glycol dimethyl ether; The chlorinated hydrocarbon solvent such as chloroform, chlorobenzene; Phenol etc.These organic solvents can be used alone, and also can be used in combination of two or more.Particularly compound of the present invention and composition intermiscibility of the present invention excellence, alcoholic solvent, ester solvent, ketone solvent, non-chlorinated aliphatic solvents and non-chlorinated aromatic hydrocarbon solvent can be dissolved in, so film forming can be carried out when not using the chlorinated hydrocarbon solvents such as chloroform.

Relative to compound 100 weight part of the present invention, the content of organic solvent is generally 10 ~ 10000 weight parts, is preferably 100 ~ 5000 weight parts.

When composition of the present invention contains organic solvent, have from the thickness inequality of blooming the tendency not easily produced, its viscosity is generally 0.1 ~ 10Pas, is preferably 0.1 ~ 7Pas.

In addition, in composition of the present invention, the concentration of solids component is generally 2 ~ 50 % by weight, is preferably 5 ~ 50 % by weight.When the concentration of solids component is more than 2 % by weight, blooming can not be excessively thin, there is the tendency easily obtaining and have the blooming of the necessary degree of birefringence of optical compensation of liquid crystal panel.In addition, when the concentration of solids component is below 50 % by weight, the viscosity of composition can not be too small, there is the tendency not easily producing the thickness inequality of blooming.Herein, so-called " solids component " refers to and remove the composition after organic solvent from composition of the present invention.

Then, blooming of the present invention is described.

In the present invention, so-called " blooming " refer to transmissive light, the film with optical function.So-called optical function refers to refraction, double refraction etc.A kind of phase retardation film as blooming is used for rectilinearly polarized light to be converted to circularly polarized light, elliptically polarized light, or on the contrary circularly polarized light or elliptically polarized light is converted to rectilinearly polarized light.

Blooming of the present invention has the structural unit deriving from the compounds of this invention, can be adjusted the wavelength dispersion characteristics of blooming by the content adjusting this structural unit.If the content deriving from the structural unit of the compounds of this invention in blooming increases, then show more flat wavelength dispersion characteristics, and then display inverse wave length dispersing characteristic.

Specifically, modulation can obtain the composition of the present invention of blooming, and said composition is polymerized, described blooming contains the content of structural unit that determined by the operation shown in following (a) ~ (e), that derive from the compounds of this invention.

The different composition of the present invention about 2 ~ 5 kinds of content of (a) modulation the compounds of this invention,

(b) to each composition of modulation, the blooming that the content of structural unit that manufacture identical thickness, that derive from the compounds of this invention is different,

C () obtains the phase difference value of the blooming obtained in (b),

D (), based on the phase difference value obtained in (c), obtains the correlationship of the content of the structural unit deriving from the compounds of this invention and the phase difference value of blooming,

E (), by the correlationship obtained in (d), being determined that the phase difference value desired by the blooming in order to give above-mentioned thickness is necessary, being derived from the content of the structural unit of the compounds of this invention.

Usually, value (Re (λ)/Re (the 550)) wavelength region close to 1 obtained divided by the phase difference value Re (550) at 550nm place at the phase difference value Re (λ) of certain af at wavelength lambda, [Re (450)/Re (550)] <1 and the wavelength region of the display inverse wave length dispersiveness of [Re (650)/Re (550)] >1, same polarisation conversion is possible.

Blooming of the present invention is by obtaining compound polymerization of the present invention.Can by compound polymerization of the present invention for one, also can by two or more compound polymerizations of the present invention.In addition, composition of the present invention is polymerized, also can manufactures blooming of the present invention.

From the easiness aspect of film forming, preferably use the solution that compound dissolution of the present invention obtains in organic solvent, by by this solution coat on supporting substrate, make it dry, polymerization, and obtain blooming.In described solution, the concentration of solids component is generally 2 ~ 50 % by weight, and preferably 5 ~ 50 % by weight.

By being coated with the solution of compound of the present invention and carrying out drying on supporting substrate, non-polymeric membrane can be obtained.During the mesomorphic phases such as non-polymeric membrane display nematic phase, the birefringence of blooming display caused by single domain orientation obtained.

By suitably adjusting the content of the compounds of this invention in the compounds of this invention solution, this solution to the glue spread on supporting substrate, the thickness of blooming can be adjusted.When the amount of compound of the present invention is certain, phase difference value (the length of delay of the blooming obtained, Re (λ)) determined by formula (7), so in order to obtain desired Re (λ), adjustment thickness d and △ n (λ).

Re(λ)＝d×Δn(λ) (7)

(in formula, Re (λ) represents the phase difference value at wavelength X nm place, and d represents thickness, and △ n (λ) represents the degree of birefringence at wavelength X nm place.)

As the solution of the compounds of this invention to the coating process of supporting substrate, extrusion coating methods, directly gravure coating process, reverse rotating gravure coating method, CAP coating method and mouth mould coating method can be enumerated.The method that coating machines such as using dip coater, metering bar coater, spin coater carries out being coated with can also be enumerated.

As supporting substrate, glass, plastic sheet, plastic film and light transmissive film can be enumerated.As light transmissive film, the polyolefin films such as polyethylene, polypropylene, norbornene-based polymer can be enumerated; Polyvinyl alcohol film; Polyethylene terephthalate film; Polymethacrylate film; Polyacrylic ester film; Cellulose ester membrane; Poly (ethylene naphthalate) film; Polycarbonate membrane; Polysulfone membrane; Poly (ether sulfone) film; Polyetherketone film; Polyphenylene sulfide film; Polyphenylene oxide film etc.

Even if blooming bonding process, transport operation, preserve operation etc. and require in the operation of blooming intensity, by using supporting substrate, also easily can operate when not making blooming damaged etc.

After preferably forming alignment films on supporting substrate, this alignment films is coated with the solution of compound of the present invention.Alignment films preferably has the solvent resistance being insoluble to this solution when being coated with the solution of the compounds of this invention.In addition, alignment films preferably have to for except desolventizing, make the thermotolerance of the heat treated of liquid crystal molecular orientation.And then, the alignment films of the stripping caused because friction waits etc. preferably can not be produced when rubbing.As this alignment films, preferably formed by orientation polymkeric substance or the composition containing orientation polymkeric substance.

As above-mentioned orientation polymkeric substance, the polymeric amide in molecule with amido linkage or gelatinization compound can be enumerated, there is the polyimide of imide bond in molecule and as the polyamic acid of its hydrolyzate, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, poly- azoles, polymine, polystyrene, Polyvinylpyrolidone (PVP), polyacrylic acid and polyacrylic ester.These orientation polymkeric substance can be used alone, and also can mix two or more use.In addition, can also be the multipolymer of these orientation polymkeric substance.These orientation polymkeric substance easily can be obtained by the chain polymerizations such as polycondensation, radical polymerization, anionoid polymerization, cationoid polymerisation, polycoordination, ring-opening polymerizations etc. such as dehydrating polycondensation, de-amine polycondensations.

These orientation polymkeric substance usually dissolve and use as solution in a solvent.Solvent is not limited.Specifically, water can be enumerated; The alcoholic solvents such as methyl alcohol, ethanol, ethylene glycol, Virahol, propylene glycol, ethylene glycol monomethyl ether, butyl glycol ether; The ester solvents such as ethyl acetate, butylacetate, ethylene glycol monomethyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; The ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, pimelinketone, 2-heptanone, methyl iso-butyl ketone (MIBK); The non-chlorinated aliphatic solventss such as pentane, hexane, heptane; The non-chlorinated such as toluene, dimethylbenzene aromatic hydrocarbon solvent; The nitrile solvents such as acetonitrile; The ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran (THF), glycol dimethyl ether; The chlorinated hydrocarbon solvent such as chloroform, chlorobenzene etc.These organic solvents may be used singly or in combination of two or more use.

Can directly use commercially available aligning film material to form alignment films.As commercially available aligning film material, SUNEVER (registered trademark, Nissan Chemical Ind Ltd's system), OPTOMER (registered trademark, JSR Corp.'s system) etc. can be enumerated.

When using such alignment films, owing to controlling based on the specific refractory power stretched without the need to carrying out, therefore unevenly in birefringent to reduce, the large blooming can tackled supporting substrate upper flat plate display unit (FPD) and maximize can be provided.

As the method forming alignment films on supporting substrate, can enumerate commercially available aligning film material, make after solvent as the compound of aligning film material and be coated on supporting substrate, then carry out the method for annealing.

The thickness of alignment films is generally 10 ~ 10000nm, is preferably 10 ~ 1000nm.When above-mentioned scope, the compounds of this invention etc. can be made in this alignment films to be orientated to desired angle.As required, friction treatment can be carried out to alignment films, also can carry out polarized light UV irradiation to alignment films, the compounds of this invention etc. can be made to be orientated to desired direction by described process.That is, shape, the slope of the indicatrix of the display double refraction state of manufactured blooming can be adjusted.

As the method for alignment films being carried out to friction treatment, the method that can be listed below: make the friction roller being wound with friction cloth of rotation and platform to carry and the alignment films of transporting contacts.

Be laminated in the method for stacked non-polymeric membrane in the alignment films on described supporting substrate, and making liquid crystal cells and compared with the method injecting liquid crystalline cpd in this liquid crystal cells, can production cost be reduced, and can carry out adopting the film of roller film to produce.

The removing of solvent can be carried out abreast with polyreaction, but from the view point of film-forming properties, preferably before carrying out polyreaction, removes most solvent.

As the removing method of solvent, the methods such as seasoning, air seasoning, drying under reduced pressure can be enumerated.Temperature when carrying out heating and remove desolventizing is generally 0 ~ 250 DEG C, is preferably 50 ~ 220 DEG C, is more preferably 80 ~ 170 DEG C.Be preferably 10 seconds ~ 60 minutes heat-up time, be more preferably 30 seconds ~ 30 minutes.When Heating temperature and heat-up time are in above-mentioned scope, as supporting substrate, thermotolerance not necessarily sufficient supporting substrate can be used.

By making, the non-polymeric membrane obtained is polymerized, solidification, can obtain the immobilized film of orientation, the i.e. polymeric membrane of the compounds of this invention.The film of heat on birefringent impact can not be vulnerable to.

The method that non-polymeric membrane is polymerized suitably can determine according to the kind of liquid crystalline cpd and the compounds of this invention.Use light polymerization method when polymerizable group in the compounds of this invention and liquid crystalline cpd is optical polymerism group, when this polymerizable group is thermopolymerization group, use thermal polymerization.Adopt light polymerization method, non-polymeric membrane can be made at low temperatures to be polymerized, the viewpoint wide from the view point of the range of choice of the thermotolerance of supporting substrate and industrial easy to manufacture, preferably uses the compounds of this invention and the liquid crystalline cpd with optical polymerism polymerizable group.In addition, from the viewpoint also preferred light polymerization of film-forming properties.Photopolymerization reaction is undertaken by irradiating visible ray, UV-light or laser to non-polymeric membrane.Operationally, particularly preferably UV-light.Rayed can be carried out under the compounds of this invention becomes the temperature of mesomorphic phase.At this moment, mask etc. can also be utilized polymeric membrane patterning.

Can be adjusted degree of birefringence △ n (λ) by exposure when suitably adjustment is polymerized, Heating temperature, heat-up time, to make the phase differential desired by imparting.

With given the stretched film of phase differential by strained polymer compared with, the thickness of blooming of the present invention is thinner.

By peeling off supporting substrate, the film being laminated with alignment films and blooming can be obtained.And then, peel off alignment films, can blooming be obtained.

The blooming transparency obtained like this is excellent, can use as various indicating meter film.The thickness of blooming is described above, different because of the difference of the phase difference value of blooming, but thickness is preferably 0.1 ~ 10 μm, from the stress optic viewpoint of reduction, is more preferably 0.2 ~ 5 μm, is particularly preferably 0.5 ~ 3 μm.

The phase difference value of the blooming of display birefringence is generally about 50 ~ 500nm, is preferably 100 ~ 300nm.

The blooming of same polarization conversion can be carried out in wider wavelength region for such film, can use as optical compensation films in the FPD such as all liquid crystal panels, organic EL.

Blooming of the present invention can use as broadband λ/4 plate or λ/2 plate.When using as broadband λ/4 plate or λ/2 plate, suitably can select the content of the structural unit deriving from the compounds of this invention in blooming and the thickness of blooming.When using as λ/4 plate, can thickness be adjusted, be generally 113 ~ 163nm to make the Re of the blooming obtained (550), be preferably 135 ~ 140nm, be particularly preferably about about 137.5nm.When using as λ/2 plate, can thickness be adjusted, be generally 250 ~ 300nm to make the Re of the blooming obtained (550), be preferably 273 ~ 277nm, be particularly preferably about about 275nm.

Blooming of the present invention can also use as VA (Vertical Alingment) pattern blooming.When using as VA pattern blooming, suitably can select the content of the structural unit deriving from the compounds of this invention in blooming.Can thickness be adjusted, to make the Re (550) of the blooming obtained be preferably 40 ~ 100nm, be more preferably about 60 ~ 80nm.

Only use a small amount of the compounds of this invention, the wavelength dispersion characteristics of blooming just can be made to be displaced to value close to 1, can by the wavelength dispersion characteristics desired by the adjustment of easy method.

Blooming of the present invention can also be used for the viewing angle compensation optical compensation films etc. of the antireflection films such as antireflection (AR) film, polarizing coating, phase retardation film, elliptical polarization film, visual angle expansion film or transmission type lcd device.

Even blooming of the present invention 1 also shows excellent optical characteristics, but also can stacked multi-disc use.In addition, can combinationally use with other film.As the concrete example combined with other film, the ellipsoidal polarizing plate of blooming of the present invention that polarizing coating fits can be set forth in, on this ellipsoidal polarizing plate further using broadband circular polarizing disk etc. that blooming of the present invention is fitted as broadband λ/4 plate.

Blooming of the present invention can be formed by being coated with, making it polymerization on supporting substrate or in alignment films, therefore as shown in Figure 1, can form the blooming of broadband, such as λ/4, λ/2 more easily on colour filter.

Colour filter 1 is sequentially laminated with color-filter layer 4, alignment films 3 and blooming of the present invention 2.

Below record an example of the manufacture method of this colour filter 1.First, on color-filter layer 4, stacked orientation polymkeric substance, carries out friction treatment, forms alignment films 3.It is stacked that orientation polymkeric substance can use ink jet method to carry out.

Then, modulation have adjusted the solution of the compounds of this invention of the compounds of this invention content in order to make the blooming obtained have desired wavelength dispersion characteristics, in the alignment films 3 obtained, be coated with this solution in the mode of the thickness forming the phase difference value reaching desired, form blooming 2.

By using this colour filter 1, more slim liquid crystal indicator can be manufactured.As one example, will represent that the schematic diagram of liquid crystal indicator 5 of the present invention is shown in Fig. 2.

In the liquid crystal indicator 5 shown in Fig. 2, on polaroid 6, be fixed with the substrate 7 relative with backlight such as glass substrate via tackiness agent.Substrate 7 on the color-filter layer 4 ' made, be formed with blooming 2 ' via alignment films 3 '.And then, blooming 2 ' is formed comparative electrode 8, comparative electrode 8 is formed mesomorphic phase 9.In backlight side, polaroid 10 is fixed with the substrates such as glass substrate 11 via tackiness agent.And then, be formed with the thin film transistor (TFT) for making liquid crystal layer active matrix driving and insulation layer 12 on the substrate 11, and then on TFT, be formed with the transparency electrode 13 and/or reflecting electrode 13 ' that use Ag, Al or ITO (Indium Tin Oxide, tin indium oxide).Compared with liquid crystal indicator in the past, the formation of the liquid crystal indicator 5 shown in Fig. 2 is formations that the sheet number of blooming is few, can manufacture more slim liquid crystal indicator.

Below record the example that colour filter 1 ' is formed at the method for making of the liquid crystal indicator 5 of the liquid crystal layer side of side's substrate.Can carry out as follows: on the substrate of backlight side, pyrex is piled up grid, gate insulating film and the amorphous silicon patterning that are formed by Mo, MoW etc., then amorphous silicon excimer laser is carried out annealing thus crystallization and form semiconductor film, then, at region doping P, B etc. of grid both sides, form the TFT of N-shaped passage, p-type passage.And then, by being formed by SiO ₂the insulation layer 12 formed, thus obtain the substrate of backlight side.And then, by sputtering ITO on backlight side substrate 11, thus on the substrate of backlight side the transparency electrode 13 of stacked total transmissivity type display unit.In addition, similarly, by using Ag, Al etc. to replace ITO, the reflecting electrode 13 ' of fully-reflected type display unit can be obtained.And then, by appropriately combined reflecting electrode, transparency electrode, the electrode of the backlight side of transflective liquid crystal display device also can be obtained.

On the other hand, on relative substrate 7, form color-filter layer 4 '.By also with R, G, B colour filter, color liquid crystal display arrangement can also be obtained.Then, at color-filter layer 4 ' upper coating orientation polymkeric substance, rub, thus form alignment films 3 '.At the solution of the upper coating of this alignment films 3 ' compound of the present invention, be heated to the temperature range obtaining mesomorphic phase, while be polymerized by uviolizing, form blooming 2 '.After forming blooming, by sputtering ITO, comparative electrode 8 can be formed.And then alignment films is formed on this comparative electrode, form mesomorphic phase 9, finally assemble together with the substrate of above-mentioned backlight side, thus liquid crystal indicator 5 can be made.

And then blooming of the present invention can also be used for the polarizer of reflection LCD and OLED display and have the FPD of this polarizer, above-mentioned blooming.Above-mentioned FPD is not particularly limited, and can enumerate such as liquid crystal indicator (LCD), organic EL.

Then, polaroid of the present invention and the FPD with this polaroid are described.

Polaroid of the present invention contains blooming of the present invention and has the film (polarizing coating) of polarization function, is usually obtained by stacked blooming of the present invention and polarizing coating.Specifically, by the one or two sides at polarizing coating directly or use tackiness agent to fit blooming of the present invention and obtaining.In this manual, " tackiness agent " means tackiness agent and tackiness agent.Below, use Fig. 3 ~ Fig. 5, polaroid of the present invention is described.

Fig. 3 (a) ~ Fig. 3 (e) is the schematic diagram representing polaroid 1 of the present invention.

In polaroid 30a shown in Fig. 3 (a), duplexer 14 and polarizing coating 15 are directly fitted, and duplexer 14 is made up of supporting substrate 16, alignment films 17 and blooming 18.Polaroid 30a press supporting substrate 16, alignment films 17, blooming 18, polarizing coating 15 order stacked.

In polaroid 30b shown in Fig. 3 (b), duplexer 14 and polarizing coating 15 are fitted via binder layer 19.

In polaroid 30c shown in Fig. 3 (c), duplexer 14 and duplexer 14 ' are directly fitted, and then duplexer 14 ' and polarizing coating 15 are directly fitted.

In polaroid 30d shown in Fig. 3 (d), duplexer 14 and duplexer 14 ' are fitted via binder layer 19, and then, duplexer 14 ' is directly fitted with polarizing coating 15.

Polaroid 30e shown in Fig. 3 (e) has following formation: duplexer 14 and duplexer 14 ' are fitted via binder layer 19, and then duplexer 14 ' and polarizing coating 15 are fitted via binder layer 19 '.

Can use from duplexer 14 peeled off supporting substrate 16 and alignment films 17 and the blooming 18 obtained to replace duplexer 14, also can use peeled off supporting substrate 16 from duplexer 14 and the film be made up of alignment films 17 and blooming 18 obtained to replace duplexer 14.Can use and peel off supporting substrate 16 ' and alignment films 17 ' from duplexer 14 ' and the blooming 18 ' that obtain replaces duplexer 14 ', also can use peeled off supporting substrate 16 ' from duplexer 14 ' and the film be made up of alignment films 17 ' and blooming 18 ' that obtains to replace duplexer 14 '.

Polaroid of the present invention can stacked multiple duplexer, and the plurality of duplexer can be all identical, also can be different.

As long as polarizing coating 15 has the film of polarization function, specifically can be set forth in polyvinyl alcohol mesentery and adsorb iodine, the back draft of dichroism pigment and the film obtained; Iodine, dichroism pigment and the film etc. that obtains is adsorbed after being stretched by polyvinyl alcohol mesentery.

The tackiness agent of the tackiness agent used in binder layer 19 and binder layer 19 ' preferably high, the excellent heat resistance of the transparency.As this tackiness agent, acrylic adhesive, epoxy adhesive, polyurethane series tackiness agent etc. can be enumerated.

Panel display apparatus of the present invention possesses blooming of the present invention, specifically, the liquid crystal indicator possessing the laminating product of polaroid of the present invention and liquid crystal panel being fitted, the organic EL display possessing organic EL plate of polaroid of the present invention and luminescent layer being fitted can be enumerated.

As the embodiment of panel display apparatus of the present invention, be described as follows for liquid crystal indicator and organic EL display.

Fig. 4 is the schematic diagram representing the liquid crystal panel 20 of liquid crystal indicator of the present invention and the laminating product 21 of polaroid 30.Polaroid 30 of the present invention and liquid crystal panel 20 form via bonding coat 22 laminating by laminating product 21.By using not shown electrode, voltage being applied to liquid crystal panel 20, can liquid crystal molecule be driven, carry out white and black displays.

Fig. 5 is the schematic diagram of the organic EL plate 23 representing organic EL display of the present invention.Polarizing coating 30 of the present invention and luminescent layer 24 form via bonding coat 25 laminating by organic EL plate 23.

In above-mentioned organic EL plate, polarizing coating 30 plays a role as broadband circular polarizing disk.And above-mentioned luminescent layer 24 is at least 1 layer the layers formed by electroconductibility organic compound.

Embodiment

Below, in further detail the present invention is described by embodiment, but the present invention is not by the restriction of these embodiments.

The synthesis example > of embodiment 1< compound (A1-1)

(1) synthesis example of compound (1-a)

2,5-dimethoxyaniline 21.5g, thionaphthene-2-carboxylic acid 25.0g and anhydrous chloroform 125.3g are mixed, makes it reaction.N is added, N-dimethyl aminopyridine 1.71g in the mixture obtained.Obtained mixture is cooled with an ice bath, adds N, N '-dicyclohexylcarbodiimide 31.8g, react 1 hour.Thereafter, mixture is returned to room temperature, obtained mixture is filtered by silica gel, after removing precipitation, concentrating under reduced pressure.In residue, add 1/2 (v/v) solution of ethyl acetate-heptane, make its crystallization.Filter the crystallization of separating out, vacuum-drying, obtains compound (1-a) 33.4g as pale yellow powder.With 2,5-dimethoxyaniline for benchmark, yield is 76%.

(2) synthesis example of compound (1-b)

By compound (1-a) 33.35g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (2,4-bis (4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide) (lawesson reagent) 22.4g and toluene 200g mixes, obtained mixture is warmed up to 80 DEG C, makes it reaction.Concentrated after cooling, obtaining take the resolvent of compound (1-b) and lawesson reagent as the red thick solid of principal constituent.

(3) synthesis example of compound (1-c)

The mixture containing compound (1-b) obtained in preceding paragraph, sodium hydroxide 25.5g and water 580g are mixed, makes obtained mixture reaction under ice-cooling.Then, under ice-cooling the aqueous solution containing the 95.6g Tripotassium iron hexacyanide is added in mixture, in room temperature reaction 12 hours.The yellow mercury oxide that leaching is separated out.By the precipitation use water of leaching, then with hexane cleaning, and with ethanol purge, vacuum-drying, the faint yellow solid 19.5g that to obtain with compound (1-c) be principal constituent.With compound (1-a) for benchmark, yield is 56%.

(4) synthesis example of compound (1-d)

By compound (1-c) 19.5g and pyridinium chloride 97.5g mixes, and is warmed up to 180 DEG C, reacts 2 hours.After obtained mixture is cooled, add water, the precipitation that leaching obtains, with water, then with hexane cleaning, the solid 18g that to obtain with compound (1-d) be principal constituent.With compound (1-c) for benchmark, yield is 95%.

(5) synthesis example of compound (A1-1)

Compound (1-d) 5.00g, compound (A) 14.68g, dimethyl aminopyridine 0.20g and chloroform 60mL are mixed.1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 7.68g is added under ice-cooling in the mixture obtained.Stir the reaction soln obtained, after filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol carry out crystallization process.Leaching crystallization, makes it be dissolved in chloroform again.Stir obtained solution while add methyl alcohol, the white precipitate that leaching generates, after vacuum-drying, obtain compound (A1-1) 10.9g as white powder.With compound (1-d) for benchmark, yield is 59%.

Compound (A1-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.85 (m, 24H), 2.35 ~ 2.83 (m, 12H), 3.92 ~ 3.97 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.87 ~ 7.02 (m, 8H), 7.22 (s, 2H), 7.40 ~ 7.46 (m, 2H), 7.83 ~ 7.89 (m, 3H)

The phase transition temperature of the compound (A1-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A1-1), when heating up, from 147 DEG C to 155 DEG C in smectic phase, from 155 DEG C to more than 180 DEG C in nematic phase, is nematic phase and crystallization when lowering the temperature till 93 DEG C.

The synthesis example > of embodiment 2< compound (A5-1)

(1) synthesis example of compound (5-a)

2,5-dimethoxyaniline 18.9g, cumarone-2-carboxylic acid 20.0g and anhydrous chloroform 125.0g are mixed, makes it reaction.N is added, N-dimethyl aminopyridine 1.51g in the mixture obtained.Obtained mixture is cooled with an ice bath, adds N, N '-dicyclohexylcarbodiimide 28.0g, react 1 hour.Then, return to room temperature, react a night.Obtained mixture is filtered by silica gel, after removing white precipitate and brown composition, concentrating under reduced pressure.In residue, add ethyl acetate/heptane solution (v/v=1/2), make its crystallization.Filter the crystallization of separating out, vacuum-drying, obtains compound (5-a) 14.4g as pale yellow powder.With 2,5-dimethoxyaniline for benchmark, yield is 39%.

(2) synthesis example of compound (5-b)

By compound (5-a) 13.0g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 100g mixes, obtained mixture is warmed up to 80 DEG C, reacts 5 hours.Concentrated after cooling, obtaining take the resolvent of compound (5-b) and lawesson reagent as the red thick solid of principal constituent.

(3) synthesis example of compound (5-c)

The mixture containing compound (5-b) obtained in preceding paragraph, sodium hydroxide 10.5g and water 250g are mixed, makes obtained mixture reaction under ice-cooling.Then, add the aqueous solution containing the 39.3g Tripotassium iron hexacyanide under ice-cooling, make it reaction.In room temperature reaction after 12 hours, the yellow mercury oxide that leaching is separated out.By the precipitation use water of leaching, then with hexane cleaning, and with ethanol purge, vacuum-drying, the faint yellow solid 9.3g that to obtain with compound (5-c) be principal constituent.With compound (5-a) for benchmark, yield is 69%.

(4) synthesis example of compound (5-d)

By compound (5-c) 7.0g and pyridinium chloride 35.0g mixes, and is warmed up to 180 DEG C, reacts 2 hours.After obtained mixture is cooled, add water, the precipitation that leaching obtains, with water, hexane cleaning, the solid 6.5g that to obtain with compound (5-d) be principal constituent.With compound (5-c) for benchmark, yield is 100%.

(5) synthesis example of compound (A5-1)

Compound (5-d) 1.60g, compound (A) 4.96g, dimethyl aminopyridine 0.07g and chloroform 30mL are mixed.N is added under ice-cooling, N '-DIC 1.71g in the mixture obtained.Obtained reaction soln is made to react a night in room temperature, after filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol make its crystallization.Leaching crystallization, makes it be dissolved in chloroform again.Stir obtained solution while add methyl alcohol, the white precipitate that leaching generates, with ethanol purge, after vacuum-drying, obtain compound (A5-1) 4.73g as white powder.With compound (5-d) for benchmark, yield is 77%.

Compound (A5-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.91 (m, 24H), 2.35 ~ 2.83 (m, 12H), 3.92 ~ 3.97 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.87 ~ 7.01 (m, 8H), 7.25 (s, 2H), 7.31 ~ 7.34 (t, 1H), 7.40 ~ 7.42 (t, 1H), 7.55 ~ 7.60 (m, 2H), 7.68 ~ 7.71 (d, 1H)

The phase transition temperature of the compound (A5-1) obtained can confirm by adopting polarized light microscope observing structure.Compound (A5-1), when heating up, from 139 DEG C to more than 180 DEG C in nematic phase, is nematic phase and crystallization when lowering the temperature till 93 DEG C.

The synthesis example > of embodiment 3< compound (A6-1)

(1) synthesis example of 5-methyl benzofuran-2 carboxylic acid

By 5-cresotinic acid aldehyde 50g, salt of wormwood 101.51g, Tetrabutylammonium bromide 11.84g, potassiumiodide 30.48g and toluene mixing, be heated to 80 DEG C.In obtained dispersion liquid, drip bromo diethyl malonate 114.1g, react 24 hours in 110 DEG C (toluene boiling under reflux).The solution that 3mL is dissolved with 3g potassium hydroxide is added, further reaction 24 hours in the brown solution obtained.After obtained reaction solution cool to room temperature, use vaporizer concentrating under reduced pressure.In residue, add potassium hydroxide 40g, ethanol 400mL, stir 1 hour in 80 DEG C.After cool to room temperature, with vaporizer distillation removing ethanol.Residue is dissolved in pure water 500mL, ice 500g, with 2N sulfuric acid, pH is adjusted to 3.Adopt the yellow mercury oxide that collecting by filtration is separated out, and then clean with pure water 1000mL, vacuum-drying, obtain 5-methyl benzofuran-2 carboxylic acid 43.7g as pale yellow powder.Take 4-Methyl Salicylaldehyde as benchmark, yield is 68%.

(2) synthesis example of compound (6-a)

By 2,5-dimethoxyaniline 30.4g, 5-methl-benzofuran-2-carboxylic acid 35.0g, triethylamine 20.1g, N, N '-dimethyl aminopyridine 4.85g and dehydration N, N '-dimethyl ethanamide 175.0g mix.After being cooled by obtained solution with ice bath, add 1H-benzotriazole-1-base oxygen base three (dimethylamino) hexafluorophosphate (hereinafter referred to as bop reagent) 92.28g, in room temperature reaction 24 hours.In obtained mixture, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water and methyl alcohol, make crystallization.The precipitation that leaching obtains, cleans with the mixing solutions (water 1 parts by volume, methyl alcohol 1 parts by volume) of water and methyl alcohol, carries out vacuum-drying, obtain compound (6-a) 23.8g as pale yellow powder.With 2,5-dimethoxyaniline for benchmark, yield is 39%.

(3) synthesis example of compound (6-b)

By compound (6-a) 23.8g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 16.1g and toluene 80g mixes, obtained mixture is warmed up to 80 DEG C, reacts 8 hours.Concentrated after cooling, obtaining take the resolvent of compound (6-b) and lawesson reagent as the red thick solid of principal constituent.

(4) synthesis example of compound (6-c)

The mixture containing compound (6-b) obtained in preceding paragraph, sodium hydroxide 18.4g and water 400g are mixed, stirs the mixture obtained under ice-cooling.Then, add the aqueous solution containing the 68.7g Tripotassium iron hexacyanide under ice-cooling, make it reaction.In room temperature reaction 24 hours, the yellow mercury oxide that leaching is separated out.By the precipitation use water of leaching, then with hexane cleaning, with ethanol purge, carry out vacuum-drying, the faint yellow solid 14.8g that to obtain with compound (6-c) be principal constituent.With compound (6-a) for benchmark, yield is 59%.

(5) synthesis example of compound (6-d)

By compound (6-c) 14.8g and pyridinium chloride 74.0g (5 times of quality) mixes, and is warmed up to 180 DEG C, reacts 2 hours.After obtained mixture is cooled, add water, the precipitation that leaching obtains, with water, toluene cleaning, the solid 10.4g that to obtain with compound (6-d) be principal constituent.With compound (6-c) for benchmark, yield is 77%.

(6) synthesis example of compound (A6-1)

Compound (6-d) 1.70g, compound (A) 5.02g, dimethyl aminopyridine 0.07g and chloroform 30mL are mixed.N is added under ice-cooling, N '-diisopropylcarbodiimide 1.73g in obtained mixture.At room temperature make obtained reaction soln react a night, after filtered through silica gel, carry out concentrating under reduced pressure.In residue, add methyl alcohol make its crystallization.Leaching crystallization, makes it be dissolved in chloroform again.Stir obtained solution while add methyl alcohol, the white precipitate that leaching generates, with washed with heptane, vacuum-drying, obtain compound (A6-1) 4.72g as white powder.With compound (6-d) for benchmark, yield is 75%.

Compound (A6-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.85 (m, 24H), 2.34 ~ 2.83 (m, 12H), 2.84 (s, 3H), 3.92 ~ 3.97 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.87 ~ 7.01 (m, 8H), 7.22 (m, 3H), 7.44 ~ 7.47 (m, 3H)

The phase transition temperature of the compound (A6-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A6-1), when heating up, from 146 DEG C to more than 190 DEG C in nematic phase, is nematic phase and crystallization when lowering the temperature till 100 DEG C.

The synthesis example > of embodiment 4< compound (A10-1)

(1) synthesis example of 5-isobutyl-cumarone

4-isopropyl-phenol 40g is made to be dissolved in N, in N '-dimethyl ethanamide 240.0g.After utilizing ice bath to be cooled by solution, divide and add sodium hydroxide 10.9g 10 times.In stirring at room temperature 1 hour, after the phenomenon producing hydrogen terminates, drip monochloroacetaldehyde dimethyl acetal 33.17g.Stir 5 hours in 80 DEG C, after confirming reaction terminating, reaction solution is added in water 1000mL, methyl iso-butyl ketone (MIBK) 400mL, carry out separatory.Reclaim organic layer, and then, 2 cleaning of the pure water with 800mL organic layers.After reclaiming organic layer, with anhydrous sodium sulfate dehydration, use vaporizer concentrating under reduced pressure, obtain red thick liquid.On the other hand, the toluene of 400g and ortho-phosphoric acid 2.61g are mixed, is heated to 110 DEG C.The solution by being obtained in 100mL toluene by red thick liquid dissolves is dripped in this solution.After stirring 3 hours in 110 DEG C, be cooled to room temperature.With 1N-sodium bicarbonate aqueous solution cleaning reaction liquid 2 times, finally with pure water 500mL cleaning.Reclaim organic layer, after anhydrous sodium sulfate dehydration, use vaporizer concentrating under reduced pressure, vacuum-drying, obtain the 5-isobutyl-cumarone 41.9g as incarnadine thick liquid.With 4-isopropyl-phenol for benchmark, yield is 90%.

(2) synthesis example of 2-formyl radical-5-isobutyl-cumarone

5-isobutyl-cumarone 25.77g is dissolved in N, in N '-dimethyl methane amide 28.4g.After utilizing ice bath to be cooled by solution, drip phosphoryl chloride 25g.Pink solution, is stirred 10 hours in 100 DEG C after 1 hour in stirring at room temperature.Reaction solution is let cool to room temperature, add pure water 100mL, stir after 1 hour, neutralize with 1N sodium bicarbonate.Be after 8 by pH regulator, with toluene separatory.Reclaim organic layer, add gac 2.6g, filter.Use vaporizer concentrating under reduced pressure, residue is dissolved in chloroform, carry out silica gel column chromatography analysis (elutriant: chloroform/heptane=1/1 (v/v) → chloroform 100vol%).Get fore portion composition vaporizer to concentrate, vacuum-drying, obtains the 2-formyl radical-5-isobutyl-cumarone 8.5g as incarnadine thick liquid.With 5-isobutyl-cumarone for benchmark, yield is 28%.

(3) synthesis example of 5-isobutyl-cumarone-2-carboxylic acid

The pure water of 2-formyl radical-5-isobutyl-cumarone 16.40g, thionamic acid 9.43g and 60mL is mixed.Be cooled with an ice bath, drip the aqueous solution (water is 50mL) of Textone 8.78g.React 36 hours under water-bath.In reaction soln, add toluene 100mL, potassium hydroxide 5g, pH is adjusted to 12.Carry out separatory, reclaim water layer, and then clean water layer with the toluene of 300mL.Reclaim water layer, be after 2 by pH regulator with 2N-hydrochloric acid, add toluene 300mL and carry out separatory.Reclaim organic layer, after anhydrous sodium sulfate dehydration, use vaporizer concentrating under reduced pressure, vacuum-drying, obtain the 5-isobutyl-cumarone-2-carboxylic acid 6.7g as incarnadine thick liquid.With 2-formyl radical-5-isobutyl-cumarone for benchmark, yield is 38%.

(4) synthesis example of compound (10-a)

By 2,5-dimethoxyaniline 4.71g, 5-isobutyl-cumarone-2-carboxylic acid 8.71g, triethylamine 3.11g, N, N '-dimethyl aminopyridine 0.75g and dehydration N, N '-dimethyl ethanamide 35.0g mix.Be cooled with an ice bath after obtained solution, add bop reagent 14.28g, in room temperature reaction 24 hours.In obtained mixture, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water and methyl alcohol, make crystallization.The precipitation that leaching obtains, clean with the mixing solutions (water 1 parts by volume, methyl alcohol 1 parts by volume) of water and methyl alcohol, vacuum-drying, obtains compound (10-a) 5.7g as pale yellow powder.With 2,5-dimethoxyaniline for benchmark, yield is 53%.

(5) synthesis example of compound (10-b)

By compound (10-a) 4.7g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 100g mixes, obtained mixture is warmed up to 80 DEG C, reacts 5 hours.Concentrated after cooling, obtaining take the resolvent of compound (10-b) and lawesson reagent as the red thick solid of principal constituent.

(6) synthesis example of compound (10-c)

The mixture containing compound (10-b) obtained in preceding paragraph, sodium hydroxide 3.1g and water 50g are mixed, stirs the mixture obtained under ice-cooling.Then, add the aqueous solution containing the 11.94g Tripotassium iron hexacyanide under ice-cooling, make it react.In room temperature reaction 24 hours, the yellow mercury oxide that leaching is separated out.By the precipitation use water of leaching, then with hexane cleaning, use washed with methanol.Yellow powder is added to the solvent of heptane-ethyl acetate 1:1 (volume ratio), in stirring at room temperature after 1 hour, under ice bath, leave standstill a night.The pale yellow powder that leaching obtains, vacuum-drying, the faint yellow solid 2.5g that to obtain with compound (10-c) be principal constituent.With compound (10-a) for benchmark, yield is 51%.

(7) synthesis example of compound (10-d)

By compound (10-c) 2.5g and pyridinium chloride 12.5g mixes, and is warmed up to 180 DEG C, reacts 2 hours.After obtained mixture is cooled, add water, the precipitation that leaching obtains, with water, toluene, hexane cleaning, the solid 1.8g that to obtain with compound (10-d) be principal constituent.With compound (10-c) for benchmark, yield is 77%.

(8) synthesis example of compound (A10-1)

Compound (10-d) 1.80g, compound (A) 4.92g, dimethyl aminopyridine 0.07g and chloroform 30mL are mixed.N is added under ice-cooling, N '-DIC 1.70g in obtained mixture.At room temperature make obtained reaction soln react a night, after filtered through silica gel, carry out concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.Leaching crystallization, makes it be dissolved in chloroform again.Stir obtained solution while add methyl alcohol, the white precipitate that leaching generates, with ethanol purge, carry out silica gel column chromatography analysis, reclaim the first composition with chloroform 80vol%-acetone 20vo1% wash-out, after vaporizer concentrating under reduced pressure, make its crystallization with cold methanol.The pale yellow powder that leaching generates, vacuum-drying, obtains compound (A10-1) 4.60g as white powder.With compound (10-d) for benchmark, yield is 72%.

Compound (A10-1) ¹h-NMR (CDCl ₃): δ (ppm) 0.81 ~ 0.87 (t, 3H), 1.29 ~ 1.31 (d, 3H), 1.48 ~ 1.79 (m, 26H), 2.35 ~ 2.47 (m, 8H), 2.63 ~ 2.83 (m, 5H), 3.93 ~ 3.97 (m, 4H), 4.15 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.87 ~ 7.02 (m, 8H), 7.23 (m, 3H), 7.48 ~ 7.50 (m, 3H)

The phase transition temperature of the compound (A10-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A10-1), when heating up, shows the phase that viscosity is high from 144 DEG C, at 169 DEG C of display brocken spectrums.When lowering the temperature, from 167 DEG C, there is clear and definite nematic phase, till 105 DEG C, being nematic phase and crystallization.

The synthesis example > of embodiment 5< compound (A11-1)

The synthesis example of (1) 4,6-dimethyl benzofuran

MX 25g is made to be dissolved in N, in N '-dimethyl ethanamide 150.0g.After utilizing ice bath to be cooled by solution, add sodium hydroxide 9.82.In stirring at room temperature 1 hour, drip monochloroacetaldehyde dimethyl acetal 25.49g.Stir 15 hours in 100 DEG C, reaction solution is added in water 1000mL, methyl iso-butyl ketone (MIBK) 400mL, carry out separatory.Reclaim organic layer, 2 cleaning of the 1N-aqueous sodium hydroxide solution with 500mL organic layers, and then 2 cleaning of the pure water with 800mL organic layers.After reclaiming organic layer, with anhydrous sodium sulfate dehydration, use vaporizer concentrating under reduced pressure, obtain incarnadine thick liquid.On the other hand, by the toluene of 400g and the mixing of 3.01g ortho-phosphoric acid, 110 DEG C are heated to.Drip in this solution by incarnadine thick liquid being dissolved in the solution obtained in 100mL toluene.After stirring 3 hours in 110 DEG C, be cooled to room temperature.With 1N-sodium bicarbonate aqueous solution cleaning reaction liquid 2 times, finally with pure water 500mL cleaning.Reclaim organic layer, after anhydrous sodium sulfate dehydration, use vaporizer concentrating under reduced pressure, vacuum-drying, obtain 4, the 6-dimethyl benzofuran 16.5g as incarnadine thick liquid.Take MX as benchmark, yield is 55%.

(2) synthesis example of 2-formyl radical-4,6-dimethyl benzofuran

4,6-dimethyl benzofuran 21.62g is dissolved in N, in N '-dimethyl methane amide 28.4g.After utilizing water-bath to be cooled by solution, drip phosphoryl chloride 25g.Pink solution, is stirred 10 hours in 100 DEG C after 1 hour in stirring at room temperature.Reaction solution is let cool to room temperature, add pure water 100mL, stir after 1 hour, neutralize with 1N sodium bicarbonate.Be after 8 by pH regulator, with toluene separatory.Reclaim organic layer, add gac 2.6g, filter.Use vaporizer concentrating under reduced pressure, residue is dissolved in chloroform, make its crystallization with heptane.Leaching crystallization, obtains 2-formyl radical-4, the 6-dimethyl benzofuran 19.5g as pale yellow powder after vacuum-drying.With 4,6-dimethyl benzofuran for benchmark, yield is 76%.

The synthesis example of (3) 4,6-dimethyl benzofuran-2-carboxylic acids

The pure water of 2-formyl radical-4,6-dimethyl benzofuran 19.50g, thionamic acid 13.04g and 100mL is mixed.Be cooled with an ice bath, drip the aqueous solution (water is 100mL) of Textone 12.15g.React 36 hours under water-bath.In reaction soln, add toluene 100mL, potassium hydroxide 25g, pH is adjusted to 12.Carry out separatory, reclaim water layer, and then clean water layer with the toluene of 200mL.Reclaim water layer, be after 2 by pH regulator with 2N-hydrochloric acid, add toluene 400mL, carry out separatory.Reclaim organic layer, after anhydrous sodium sulfate dehydration, use vaporizer concentrating under reduced pressure, vacuum-drying, obtain 4, the 6-dimethyl benzofuran-2-carboxylic acid 14.27g as yellow powder.With 2-formyl radical-4,6-dimethyl benzofuran for benchmark, yield is 67%.

The synthesis example of (4) 4,6-dimethyl benzofuran-2-carboxylic acids

MX 150g, paraformaldehyde 230.1g, Magnesium Chloride Anhydrous 175.4g are dispersed in 900mL acetonitrile.Stir under ice bath after 30 minutes, dripped triethylamine 474g with 2 hours.Mixture is reacted 8 hours under water-bath, in room temperature reaction 14 hours.In reaction solution, add cold 5N-hydrochloric acid 1500mL, after becoming acidity, carry out separatory by the ethyl acetate of 400mL, reclaim organic layer.And then, by the ethyl acetate of 400mL, separatory is carried out to water layer.Reclaim organic layer, merge with organic layer before, after anhydrous sodium sulfate dehydration, use vaporizer concentrating under reduced pressure.Residue is dissolved in 400mL toluene, adds gac 3g, silica gel 20g, in stirring at room temperature 30 minutes, filter.Reclaim filtrate, use vaporizer concentrating under reduced pressure, vacuum-drying, obtain 4, the 6-dimethyl salicylic aldehyde 170g as orange thick liquid thus.Take MX as benchmark, yield is 92%.

Make 4,6-dimethyl salicylic aldehyde 45.0g, salt of wormwood 101.g is dispersed in N, in N '-dimethyl ethanamide 360mL.After being heated to 80 DEG C, dripped ethyl bromoacetate 50.0g with 1 hour.Mixture reaction is made 4 hours in 80 DEG C.After reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 400mL, after being adjusted to acidity with cold 1N-hydrochloric acid 1000mL, carry out separatory.3 cleaning of the pure water with 1000mL organic layers, reclaim organic layer.After anhydrous sodium sulfate dehydration, with vaporizer distillation except desolventizing.In residue, add potassium hydroxide 40g, ethanol 400mL, stir 1 hour in 80 DEG C.Let cool to room temperature, with vaporizer distillation except desolventizing, add pure water 1000mL.Confirm that pH is after more than 12, water layer toluene is cleaned 2 times, by washed with heptane 1 time.Reclaiming water layer, with the neutralization of 4N-sulfuric acid, is 3 by pH regulator.The yellow mercury oxide that leaching is separated out, after pure water suspension washing, vacuum-drying, obtains 4, the 6-dimethyl benzofuran-2-carboxylic acid 48.1g as yellow powder thus.With 4,6-dimethyl salicylic aldehyde for benchmark, yield is 83%.

(5) synthesis example of compound (11-a)

By 2,5-dimethoxyaniline 11.49g, 4,6-dimethyl benzofuran-2-carboxylic acid 14.27g, triethylamine 7.59g, N, N '-dimethyl aminopyridine 1.83g and dehydration N, N '-dimethyl ethanamide 100.0g mix.With ice bath by after the solution cooling that obtains, add bop reagent 34.85g, in room temperature reaction 24 hours.In obtained mixture, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water and methyl alcohol, make crystallization.The precipitation that leaching obtains, clean with the mixing solutions (water 3 parts by volume, methyl alcohol 2 parts by volume) of water and methyl alcohol, vacuum-drying, obtains compound (11-a) 16.2g as pale yellow powder.With 2,5-dimethoxyaniline for benchmark, yield is 66%.

(6) synthesis example of compound (11-b)

By compound (11-a) 16.0g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 100g mixes, obtained mixture is warmed up to 80 DEG C, reacts 12 hours.Concentrated after cooling, obtaining take the resolvent of compound (11-b) and lawesson reagent as the red thick solid of principal constituent.

(7) synthesis example of compound (11-c)

The mixture containing compound (11-b) obtained in preceding paragraph, sodium hydroxide 11.8g and water 250g are mixed, makes the mixture reaction obtained under ice-cooling.Then, add the aqueous solution containing the 44.17g Tripotassium iron hexacyanide under ice-cooling, make it react.In 60 DEG C of reactions 12 hours, the yellow mercury oxide that leaching is separated out.By the precipitation use water of leaching, then with hexane cleaning, make its crystallization with toluene.By the yellow substance vacuum-drying obtained, the khaki color solid 4.1g that to obtain with compound (11-c) be principal constituent.With compound (11-a) for benchmark, yield is 25%.

(8) synthesis example of compound (11-d)

By compound (11-c) 4.0g and pyridinium chloride 40.0g mixes, and is warmed up to 180 DEG C, reacts 3 hours.The mixture obtained is added in ice, the precipitation that leaching obtains.After aqueous suspension washing, with toluene cleaning, vacuum-drying, the khaki color solid 3.4g that to obtain with compound (11-d) be principal constituent.With compound (11-c) for benchmark, yield is 93%.

(9) synthesis example of compound (A11-1)

Compound (11-d) 3.00g, compound (A) 8.47g, dimethyl aminopyridine 0.12g and chloroform 40mL are mixed.Under ice-cooling, in obtained mixture, add N, N '-DIC 2.92g.Obtained reaction soln is at room temperature made to react a night, after filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.Leaching crystallization, made it be dissolved in chloroform again, adds 0.3g gac, in stirring at room temperature 1 hour.Filtering solution, after concentrating filtrate to 1/3, stirs and adds methyl alcohol with vaporizer, the white precipitate that leaching generates, and with washed with heptane, vacuum-drying, obtains compound (A11-1) 7.60g as white powder.With compound (11-d) for benchmark, yield is 71%.

Compound (A11-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.85 (m, 24H), 2.36 ~ 2.87 (m, 18H), 3.93 ~ 3.97 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.45 (m, 2H), 6.87 ~ 7.01 (m, 9H), 7.20 (s, 1H), 7.23 (s, 2H), 7.53 (s, 1H)

The phase transition temperature of the compound (A11-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A11-1), when heating up, shows the high mesophase spherule of viscosity from 105 DEG C to 137 DEG C.Although be difficult to distinguish mesomorphic phase, in clear and definite nematic liquid crystal phase more than 137 DEG C.Nematic liquid crystal is maintained to more than 180 DEG C mutually, is nematic phase and crystallization when lowering the temperature till 61 DEG C.

The synthesis example > of embodiment 6< compound (A15-1)

(1) synthesis example of 5-Fluorobenzofur-2 carboxylic acid

5-fluorine salicylic aldehyde 25g, salt of wormwood 49.32g and 2-butanone 200g are mixed, is heated to 80 DEG C.Bromo diethyl malonate 55.5g is dripped, in 100 DEG C of reactions 24 hours in obtained dispersion liquid.Obtained red tan solution is let cool to room temperature, with pure water, the cleaning of 1mol/L wet chemical.Reclaim organic layer, with anhydrous sodium sulfate dehydration, use vaporizer concentrating under reduced pressure.In residue, add potassium hydroxide 25g, ethanol 250mL, stir 2 hours in 80 DEG C.After being cooled to room temperature cooling, with vaporizer distillation removing ethanol.Residue is dissolved in pure water 500mL, ice 500g, with 2N sulfuric acid, pH is adjusted to 3.Adopt the pale purple precipitation that collecting by filtration is separated out, and then, clean with pure water 1000mL, vacuum-drying, obtain 5-Fluorobenzofur-2 carboxylic acid 23.4g as pale yellow powder.With 4-fluorine salicylic aldehyde for benchmark, yield is 73%.

(2) synthesis example of compound (15-a)

By 2,5-dimethoxyaniline 17.01g, 5-Fluorobenzofur-2 carboxylic acid 20.0g, triethylamine 11.24g, N, N '-dimethyl aminopyridine 2.71g and dehydration N, N '-dimethyl ethanamide 100.0g mix.After being cooled by obtained solution with ice bath, add bop reagent 51.57g, in room temperature reaction 24 hours.In the mixture obtained, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water, methyl alcohol, make crystallization.The precipitation that leaching obtains, clean with the mixing solutions (water 1 parts by volume, methyl alcohol 1 parts by volume) of water-methanol, vacuum-drying, obtains compound (15-a) 32.1g as pale yellow powder.With 2,5-dimethoxyaniline for benchmark, yield is 92%.

(3) synthesis example of compound (15-b)

By compound (15-a) 32.0g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 24.6g and toluene 320g mixes, the mixture obtained is warmed up to 80 DEG C, reacts 24 hours.Concentrated after cooling, obtaining with the resolvent of compound (15-b) and lawesson reagent is the yellow solid of principal constituent.

(4) synthesis example of compound (15-c)

The mixture containing compound (15-b) obtained in preceding paragraph, sodium hydroxide 21.7g and water 500g are mixed, stirs the mixture obtained under ice-cooling.Then, add Tripotassium iron hexacyanide 81.3g, make it react.In room temperature reaction 2 hours, the yellow mercury oxide that leaching is separated out.By the precipitation use water of leaching, then with hexane cleaning, with toluene cleaning, vacuum-drying, the khaki color solid 27.1g that to obtain with compound (15-c) be principal constituent.With compound (15-a) for benchmark, yield is 91%.

(5) synthesis example of compound (15-d)

By compound (15-c) 10.0g and pyridinium chloride 50.0g mixes, and is warmed up to 180 DEG C, reacts 2 hours.After obtained mixture is cooled, add water, the precipitation that leaching obtains, with water, hexane, toluene cleaning, the solid 6.0g that to obtain with compound (15-d) be principal constituent.With compound (15-c) for benchmark, yield is 66%.

(6) synthesis example of compound (A15-1)

Compound (15-d) 3.00g, compound (A) 8.75g, dimethyl aminopyridine 0.12g and chloroform 50mL are mixed.N is added under ice-cooling, N '-DIC 3.02g in obtained mixture.Obtained reaction soln is at room temperature made to react a night, after filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol make its crystallization.Leaching crystallization, makes it be dissolved in chloroform again.Add gac 0.3g, stir after 1 hour, filter.After vaporizer concentrated filtrate, stir and add methyl alcohol, the white precipitate that leaching generates.By precipitation washed with heptane, vacuum-drying, obtains compound (A15-1) 8.20g as white powder.With compound (15-d) for benchmark, yield is 75%.

Compound (A15-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.46 ~ 1.90 (m, 24H), 2.36 ~ 2.84 (m, 12H), 3.93 ~ 3.98 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.80 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.87 ~ 7.02 (m, 8H), 7.14 ~ 7.19 (dt, 1H), 7.28 (s, 2H), 7.38 ~ 7.37 (dd, 1H), 7.50 ~ 7.55 (m, 2H)

The phase transition temperature of the compound (A15-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A15-1), when heating up, shows the high phase of viscosity, is difficult to distinguish mesomorphic phase from 143 DEG C to 178 DEG C.But, more than 178 DEG C, show clear and definite nematic phase, until more than 200 DEG C in nematic liquid crystal phase.Till 110 DEG C, be nematic phase and crystallization when lowering the temperature.

The synthesis example > of embodiment 7< compound (A57-1)

(1) synthesis example of 5-propyl group cumarone-2 carboxylic acid

By 4-propyl group salicylic aldehyde 27.8g, salt of wormwood 46.81g, Tetrabutylammonium bromide 11.84g, potassiumiodide 30.48g and toluene mixing, be heated to 80 DEG C.In the dispersion liquid obtained, drip the hexaoxacyclooctadecane-6-6 of 52.6g bromo diethyl malonate, 2.8g, react 24 hours in 110 DEG C (toluene boiling under reflux).After obtained sorrel reaction solution is cooled to room temperature, use vaporizer concentrating under reduced pressure.In residue, add potassium hydroxide 27.8g, ethanol 278mL, stir 1 hour in 80 DEG C.After cool to room temperature, with vaporizer distillation removing ethanol.Residue is dissolved in pure water 500mL, ice 500g, with 2N sulfuric acid, pH is adjusted to 3.Adopt the yellow mercury oxide that collecting by filtration is separated out, and then clean with pure water 1000mL, vacuum-drying, obtain 5-propyl group cumarone-2 carboxylic acid 5.8g as pale yellow powder.With 4-propyl group salicylic aldehyde for benchmark, yield is 17%.

(2) synthesis example of compound (57-a)

By 2,5-dimethoxyaniline 4.3g, 5-propyl group-cumarone-2-carboxylic acid 5.7g, triethylamine 2.82g, N, N '-dimethyl aminopyridine 0.68g and dehydration N, N '-dimethyl ethanamide 30.0g mix.After being cooled by obtained solution with ice bath, add bop reagent 12.96g, in room temperature reaction 24 hours.In obtained mixture, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water and methyl alcohol, crystal is separated out.The precipitation that leaching obtains, clean with the mixing solutions (water 1 parts by volume, methyl alcohol 1 parts by volume) of water and methyl alcohol, vacuum-drying, obtains compound (57-a) 6.33g as pale yellow powder.With 2,5-dimethoxyaniline for benchmark, yield is 67%.

(3) synthesis example of compound (57-b)

By compound (57-a) 6.0g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 100g mixes, obtained mixture is warmed up to 80 DEG C, reacts 5 hours.Concentrated after cooling, obtaining take the resolvent of compound (57-b) and lawesson reagent as the red thick solid of principal constituent.

(4) synthesis example of compound (57-c)

The mixture containing compound (57-b) obtained in preceding paragraph, sodium hydroxide 4.5g and water 50g are mixed, stirs the mixture obtained under ice-cooling.Then, add Tripotassium iron hexacyanide 16.8g under ice-cooling, make it react.In room temperature reaction 48 hours, the yellow mercury oxide that leaching is separated out.By the precipitation use water of leaching, then with hexane cleaning, with ethanol purge, vacuum-drying, the faint yellow solid 2.8g that to obtain with compound (57-c) be principal constituent.With compound (57-a) for benchmark, yield is 42%.

(5) synthesis example of compound (57-d)

By compound (57-c) 2.70g and pyridinium chloride 13.5g mixes, and is warmed up to 180 DEG C, reacts 2 hours.After obtained mixture is cooled, add water, the precipitation that leaching obtains, with water, hexane cleaning, the solid 2.4g that to obtain with compound (57-d) be principal constituent.With compound (57-c) for benchmark, yield is 97%.

(6) synthesis example of compound (A57-1)

Compound (57-d) 1.85g, compound (A) 5.00, dimethyl aminopyridine 0.07g and chloroform 20mL are mixed.N is added under ice-cooling, N '-DIC 1.72g in obtained mixture.Obtained reaction soln is at room temperature made to react a night, after filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.Leaching crystallization, makes it be dissolved in chloroform again.Stir obtained solution while add methyl alcohol, the white precipitate that leaching generates, with ethanol purge, vacuum-drying, obtain compound (A57-1) 3.85g as white powder.With compound (57-d) for benchmark, yield is 77%.

Compound (A57-1) ¹h-NMR (CDCl ₃): δ (ppm) 0.94 ~ 0.99 (t, 3H), 1.45 ~ 1.86 (m, 26H), 2.35 ~ 2.47 (m, 8H), 2.67 ~ 2.83 (m, 6H), 3.92 ~ 3.97 (m, 4H), 4.15 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.87 ~ 7.01 (m, 8H), 7.25 (s, 2H), 7.46 ~ 7.49 (m, 4H)

The phase transition temperature of the compound (A57-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A57-1), when heating up, shows the high phase of viscosity, from 143 DEG C, presents clear and definite nematic phase from 131 DEG C to 143 DEG C.And then compound (A57-1), until more than 180 DEG C in nematic phase, when lowering the temperature, is nematic phase and crystallization till 100 DEG C.

The synthesis example > of embodiment 8< compound (A25-1)

(1) synthesis example of compound (25-a)

By 2,5-dimethoxyaniline 15.8g, thieno-[3,2-b] thiophene-2-carboxylic acid 19.0g, triethylamine 10.4g, N, N '-dimethyl aminopyridine 4.85g and dehydration N, N '-dimethyl ethanamide 95.0g mix.With ice bath by after the solution cooling that obtains, add bop reagent 47.9g, in room temperature reaction 24 hours.In obtained mixture, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water and methyl alcohol, crystal is separated out.The precipitation that leaching obtains, clean with the mixing solutions (water 1 parts by volume, methyl alcohol 1 parts by volume) of water and methyl alcohol, vacuum-drying, obtains compound (25-a) 21.0g as yellow powder.With 2,5-dimethoxyaniline for benchmark, yield is 64%.

(2) synthesis example of compound (25-b)

By compound (25-a) 27.0g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 17.8g and toluene 122g mixes, obtained mixture is warmed up to 80 DEG C, reacts 5 hours.The precipitation separated out after leaching cooling, obtaining with the resolvent of compound (25-b) and lawesson reagent is the brown solid of principal constituent.

(3) synthesis example of compound (25-c)

Mixture 26.4g, the sodium hydroxide 18.9g containing the compound (25-b) that obtain in preceding paragraph and water 450g are mixed, makes obtained mixture reaction under ice-cooling.Then, add the aqueous solution containing the 70.7g Tripotassium iron hexacyanide under ice-cold, make it react.In room temperature reaction 12 hours, the yellow mercury oxide that leaching is separated out.By the precipitation use water of leaching, then with hexane cleaning, with ethanol purge, vacuum-drying, the yellow solid 15g that to obtain with compound (25-c) be principal constituent.With compound (25-a) for benchmark, yield is 58%.

(4) synthesis example of compound (25-d)

By compound (25-c) 15.0g and pyridinium chloride 75.0g mixes, and is warmed up to 180 DEG C, reacts 3 hours.After obtained mixture is cooled, add water, the precipitation that leaching obtains, with water, hot toluene, hexane cleaning, the solid 6.6g that to obtain with compound (25-d) be principal constituent.With compound (25-c) for benchmark, yield is 45%.

(5) synthesis example of compound (A25-1)

Compound (25-d) 2.0g, compound (A) 5.76g, dimethyl aminopyridine 0.08g and chloroform 30mL are mixed.In obtained mixture, N is added, N '-DIC 1.98g under ice-cold.At room temperature make obtained reaction soln react a night, add 0.8g gac, after leaving standstill a night, filtered through silica gel, then concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.Leaching crystallization, makes it be dissolved in chloroform again.Stir obtained solution while add methyl alcohol, the tan precipitate that leaching generates, with ethanol purge, vacuum-drying, obtain compound (A25-1) 4.30g as brown powder.With compound (25-d) for benchmark, yield is 60%.

Compound (A25-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.26 ~ 1.87 (m, 24H), 2.33 ~ 2.81 (m, 12H), 3.92 ~ 3.96 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.87 ~ 7.01 (m, 8H), 7.18 (s, 2H), 7.23 ~ 7.31 (d, 1H), 7.52 ~ 7.54 (d, 1H), 7.82 (s, 1H)

The phase transition temperature of the compound (A25-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A25-1), when heating up, from 175 DEG C to 180 DEG C in smectic phase, from 180 DEG C to more than 238 DEG C in nematic phase, shows brocken spectrums at 238 DEG C.When lowering the temperature, till 168 DEG C, be nematic phase and crystallization.

The synthesis example > of embodiment 9< compound (A41-1)

(1) synthesis example of compound (41-a)

In a reservoir 2,5-dimethoxyaniline 35.4g, triethylamine 46.7g and anhydrous chloroform 400g are mixed, while making it react, drop into 4-Phenylbenzoyl chloride 50.0g.This mixing solutions is warmed up to 60 DEG C, and slaking, after 3 hours, is cooled to room temperature, puts in water.Taking out being separated the organic layer obtained, with water, then using hydrochloric acid cleaning.The concentrated organic layer obtained, obtains the solid 76.6g of compound (41-a).With 2,5-dimethoxyaniline for benchmark, yield is 98%.

(2) synthesis example of compound (41-b)

Operate in the same manner as the synthesis example of compound (1-b), obtaining with the resolvent of compound (41-b) and lawesson reagent is the solid of principal constituent.

(3) synthesis example of compound (41-c)

Operate in the same manner as the synthesis example of compound (1-c), the solid that to obtain with compound (41-c) be principal constituent.

(4) synthesis example of compound (41-d)

Operate in the same manner as the synthesis example of compound (1-d), the solid that to obtain with compound (41-d) be principal constituent.

(5) synthesis example of compound (A41-1)

Operate in the same manner as the synthesis example of compound (A1-1), obtain compound (A41-1).With compound (41-d) for benchmark, yield is 68%.

Compound (A41-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.44 ~ 1.82 (m, 24H), 2.32 ~ 2.64 (m, 12H), 3.91 ~ 3.97 (t, 4H), 4.14 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (m, 2H), 6.07 ~ 6.18 (m, 2H), 6.36 ~ 6.44 (m, 2H), 6.85 ~ 7.01 (m, 8H), 7.37 ~ 7.90 (m, 9H), 8.13 ~ 8.17 (m, 2H)

The phase transition temperature of the crystallization of compound (A41-1) confirms by adopting polarized light microscope observing structure.If raised temperature, then near 214 DEG C, change smectic phase into.Further raised temperature, then become nematic phase near 234 DEG C.Further raised temperature, then become isotropic phase near 275 DEG C.Reduce temperature by this temperature, then near 269 DEG C, become nematic phase, near 227 DEG C, become smectic phase, return near 204 DEG C as crystallization.That is, known compound (A41-1) when heating up from 214 DEG C to 234 DEG C in smectic phase, from 234 DEG C to 275 DEG C in nematic phase.And known, when lowering the temperature, from 269 DEG C to 227 DEG C in nematic phase, from 227 DEG C to 204 DEG C in smectic phase.

The synthesis example > of embodiment 10< compound (A43-1)

(1) synthesis example of compound (43-d)

In the synthesis example of compound (41-d), use the replacement of 4-(4-n-propyl phenyl) Benzoyl chloride as the 4-Phenylbenzoyl chloride of raw material, carry out amidation, in addition, make to use the same method, according to above-mentioned reacting flow chart, synthetic compound (43-d).

(2) synthesis example of compound (A43-1)

Change into except compound (43-d) except by the starting compound (1-d) in the synthesis example of compound (1-1), use the same method and obtain compound (A43-1).With compound (43-d) for benchmark, yield is 65%.

Compound (A43-1) ¹h-NMR (CDCl ₃): δ (ppm) 0.95 ~ 1.01 (t, 3H) 1.44 ~ 1.87 (m, 26H), 2.34 ~ 2.83 (m, 14H), 3.92 ~ 3.98 (t, 4H), 4.14 ~ 4.21 (t, 4H), 5.79 ~ 5.84 (m, 2H), 6.07 ~ 6.18 (m, 2H), 6.36 ~ 6.44 (m, 2H), 6.86 ~ 7.02 (m, 8H), 7.20 ~ 7.31 (m, 4H), 7.56 ~ 7.60 (d, 2H), 7.69 ~ 7.73 (d, 2H), 8.07 ~ 8.11 (d, 2H)

The phase transition temperature of the crystallization of compound (A43-1) confirms by adopting polarized light microscope observing structure.Raised temperature, then become isotropic phase near 143 DEG C.Reduce temperature by this temperature, then near 118 DEG C, be returned as crystallization.That is, known compound (A43-1) does not show mesomorphic phase.

The synthesis example > of embodiment 11< compound (A66-1)

(1) synthesis example of compound (66-a)

2,3-dicyano Resorcinol 10.0g, potassium hydroxide 35.0g and water 70.0g are mixed, by mixture while stirring 100 DEG C of heating.Obtained mixture is cooled to room temperature, adds sulfuric acid 40.0g, stir further.In obtained mixture, add ethyl acetate, take out organic layer.By obtained organic layer concentrating under reduced pressure, after desolventizing, vacuum-drying, obtains compound (66-a) 8.5g.With 2,3-dicyano Resorcinol for benchmark, yield is 68%.

(2) synthesis example of compound (66-b)

Compound (66-a) 10.0g, 2-amino-6-methoxybenzothiazole 19.1g and tetrahydrofuran (THF) 200.0g is mixed, by mixture while stirring 70 DEG C of heating.Obtained mixture is cooled to room temperature, makes N, N '-dicyclohexylcarbodiimide 12.5g is dissolved in tetrahydrofuran (THF) 37.5g, after room temperature drips, while stirring 80 DEG C of heated and stirred 36 hours.Obtained mixture is let cool to room temperature, adopted after filtering white precipitate, by obtained filtrate reduced in volume, after desolventizing, make residue crystallization with chloroform.Filter the pale green powder generated, clean with chloroform.The pale green powder obtained is dissolved in tetrahydrofuran (THF) again, adds methyl alcohol, crystal is separated out.After filtering the green precipitate generated, vacuum-drying, obtains compound (66-b) 2.8g.With compound (66-a) for benchmark, yield is 16%.

(3) synthesis example of compound (A66-1)

Compound (66-b) 2.1g, 4-dimethylaminopyridine 0.18, compound (A) 6.16g, chloroform 123g are mixed.Then, drip in obtained mixture in room temperature and make N, N '-dicyclohexylcarbodiimide 4.56g is dissolved in the liquid obtained in chloroform 10.7g, stirs.After filtering the mixture obtained, add 2N hydrochloric acid 62g, stir, by liquid separatory, take out organic layer.After above separatory operation repetition 2 times, the organic layer obtained by separatory reclaims, and with anhydrous sodium sulfate drying, with vaporizer distillation except after desolventizing, adds methyl alcohol, stirs.After filtering the precipitation generated, vacuum-drying, obtains compound (A66-1) 4.1g.With compound (66-b) for benchmark, yield is 59%.

Compound (A66-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.85 (m, 12H), 2.29 ~ 2.56 (m, 8H), 2.56 ~ 2.75 (2tt, 4H), 3.89 (s, 3H), 3.92 ~ 3.97 (t, 4H), 4.16 ~ 4.19 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.86 ~ 7.01 (m, 8H), 7.08 ~ 7.13 (dd, 1H), 7.32 (d, 1H), 7.50 ~ 7.53 (m, 2H), 8.00 (d, 1H)

The phase transition temperature of the compound (A66-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A66-1), when heating up, shows the high phase of viscosity, is difficult to distinguish mesomorphic phase from 125 DEG C to 140 DEG C.But, more than 140 DEG C, show clear and definite mesomorphic phase.

Embodiment 12 ~ 24 and comparative example 1

The Production Example > of < blooming

The 2 quality % aqueous solution of pva coating (the fully saponified type of polyvinyl alcohol 1000, Wako Pure Chemical Industries, Ltd.'s system) on the glass substrate, after drying, form the film of thickness 89nm.Then, friction treatment is implemented to the surface of obtained film, by the composition of the composition of spin-coating method coating table 1 on the face implementing friction treatment, with the drying temperature drying described in table 21 minute.Next, be heated to the temperature during rayed described in table 2, the ultraviolet of the integrating light quantity simultaneously described in exposure chart 2, form the blooming of the thickness described in table 3.

[table 1]

LC242: by the liquid crystalline cpd of the commercially available following formula of BASF AG

Polymerization starter: IRGACURE 819 (Ciba Japan Co., Ltd. system; Acylphosphine oxide compound)

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

[table 2]

	Drying temperature after coating	Temperature during rayed	Integrating light quantity (mJ/cm ²)
				Embodiment 12	150℃	140℃	2400
Embodiment 13	145℃	110℃	2400
				Embodiment 14	220℃	210℃	2400
Embodiment 15	220℃	150℃	2400
				Embodiment 16	140℃	80℃	2400
Embodiment 17	220℃	165℃	2400
				Embodiment 18	175℃	110℃	2400
Embodiment 19	220℃	135℃	2400
				Embodiment 20	110℃	80℃	2400
Embodiment 21	115℃	80℃	2400
				Embodiment 22	115℃	80℃	2400
Embodiment 23	120℃	80℃	2400
				Embodiment 24	120℃	80℃	2400
Comparative example 1	45℃	Room temperature	1200

The mensuration > of < optical characteristics

Measuring machine (KOBRA-WR, prince measures machines corporation system) is used to measure the front phase difference value of blooming.It should be noted that, because the glass substrate used in base material does not have birefringence, so measure the film of subsidiary glass substrate by measuring machine, the front phase difference value of the blooming that just can be made on the glass substrate.The optical detecting front phase difference value obtained measures respectively at wavelength 447.3nm, 546.9nm and 627.8nm, calculates [Re (447.3)/Re (546.9)] (as α) and [Re (627.8)/Re (546.9)] (as β).Further, laser microscope (LEXT, Olympus Corp's system) is used to measure the thickness d (μm) of blooming.Show the result in table 3.△ n (△ n=Re (546.9)/d) is calculated divided by thickness by the value of Re (546.9).

[table 3]

	Re(546.9)	α	β	d(μm)	Δn
						Embodiment 12	142.5	0.923	1.016	2.431	0.059
Embodiment 13	117.2	0.857	1.030	1.588	0.074
						Embodiment 14	106.5	0.844	1.036	1.519	0.070
Embodiment 15	102.9	0.887	1.024	1.741	0.059
						Embodiment 16	155.5	0.805	1.043	2.635	0.059
Embodiment 17	121.2	0.903	1.023	1.581	0.077
						Embodiment 18	84.1	0.914	1.017	1.707	0.049
Embodiment 19	111.8	0.800	1.037	1.670	0.067
						Embodiment 20	105.4	1.007	0.989	1.086	0.097
Embodiment 21	99.4	0.988	0.989	1.113	0.089
						Embodiment 22	97.3	0.963	1.000	1.150	0.085
Embodiment 23	90.3	0.930	1.008	1.187	0.076
						Embodiment 24	80.1	0.887	1.018	1.189	0.067
Comparative example 1	141.0	1.075	0.978	1.001	0.141

Synthesis example-the 2> of embodiment 25< compound (A11-1)

The synthesis example of (1) 4,6-dimethyl benzofuran-2-carboxylic acid

Make 4,6-dimethyl salicylic aldehyde 146.6g, salt of wormwood 330.7g is dispersed in N, in N '-dimethyl ethanamide 700mL.After being heated to 80 DEG C, dripped bromo-acetic acid tert-butyl 190.5g with 30 minutes.Mixture reaction is made 2 hours in 130 DEG C.After reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 600mL, carry out separatory with pure water 1200mL.And then 2 cleaning of the pure water with 1000mL organic layers, reclaim organic layer.After anhydrous sodium sulfate dehydration, with vaporizer distillation except desolventizing.Residue is dissolved in acetic acid 240g, adds hydrobromic acid aqueous solution 72g, stir 1 hour in 40 DEG C.Let cool to room temperature, add 1N-hydrochloric acid 150g, the white powder that leaching is separated out.After obtained white powder is used 1N-hydrochloric acid cleaning further, vacuum-drying, obtains 4, the 6-dimethyl benzofuran-2-carboxylic acid 81.7g as yellow powder thus.With 4,6-dimethyl salicylic aldehyde for benchmark, yield is 44%.

(2) synthesis example of compound (11-a)

2,5-dimethoxyaniline 96.6g, 4,6-dimethyl benzofuran-2-carboxylic acid 80.0g and chloroform 400.0g are mixed.After being cooled with an ice bath by obtained suspension, added the mixture of 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 88.7g and chloroform 300g with 4 hours, in room temperature reaction 48 hours.Obtained mixture is concentrated, adds the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of 1N-hydrochloric acid, methyl alcohol, crystal is separated out.The precipitation that leaching obtains, adds the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water and methyl alcohol.The pale yellow precipitate that leaching is separated out, clean with the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water-methanol, vacuum-drying, obtains compound (11-a) 124.2g as pale yellow powder.With 4,6-dimethyl benzofuran-2-carboxylic acid for benchmark, yield is 91%.

(3) synthesis example of compound (11-b)

By compound (11-a) 123.0g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 1200g mixes, obtained mixture is warmed up to 110 DEG C, reacts 8 hours.After cool to room temperature, with 1N-aqueous sodium hydroxide solution separatory.Reclaim organic layer, add heptane 800mL.The yellow mercury oxide that leaching is separated out, with washed with heptane, vacuum-drying, the bright-yellow powder 109.2g that to obtain with compound (11-b) be thus principal constituent.With compound (11-a) for benchmark, yield is 85%.

(4) synthesis example of compound (11-c)

Compound (11-b) 60.0g, potassium hydroxide 53.8g and water 1000g are mixed, stirs the mixture obtained under ice-cooling.Then, add Tripotassium iron hexacyanide 133.0g, methyl alcohol 51g, make it react.In room temperature reaction 36 hours, the yellow mercury oxide that leaching is separated out.The mixed solvent (heptane 3 parts by volume, toluene 1 parts by volume) of the precipitation heptane of leaching, toluene is cleaned, by obtained yellow powder vacuum-drying, the yellow solid 51.3g that to obtain with compound (11-c) be principal constituent.With compound (11-b) for benchmark, yield is 86%.

(5) synthesis example of compound (11-d)

By compound (11-c) 40.0g and pyridinium chloride 400.0g mixes, and is warmed up to 180 DEG C, reacts 3 hours.Ice is added, the precipitation that leaching obtains in the mixture obtained.After aqueous suspension washing, with toluene cleaning, vacuum-drying, the yellow solid 36.6g that to obtain with compound (11-d) be principal constituent.With compound (11-c) for benchmark, yield is 99%.

(6) synthesis example of compound (A11-1)

Compound (11-d) 35.0g, compound (A) 98.8g, Dimethylamino pyridine 1.37g and toluene 700mL are mixed.N is added under ice-cooling, N '-dicyclohexylcarbodiimide 55.6g in obtained mixture.Obtained reaction soln is at room temperature made to react a night, after filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.Leaching crystallization, made it be dissolved in chloroform again, adds 2.3g gac, in stirring at room temperature 1 hour.Filtering solution, after concentrating filtrate to 1/3, stirs and adds methyl alcohol with vaporizer, the white precipitate that leaching generates, and with washed with heptane, vacuum-drying, obtains compound (A11-1) 74.5g as white powder.With compound (11-d) for benchmark, yield is 60%.

Synthesis example-the 3> of embodiment 26< compound (A11-1)

Use ethyl chloroacetate to replace bromo-acetic acid tert-butyl, operate in the same manner as the synthesis example-2 of compound (A11-1) in addition, synthetic compound (A-11).

The synthesis example > of embodiment 27< compound (A61-1)

The synthesis example of (1) 3,6-dimethyl salicylic aldehyde

2,5-xylenol 50g, paraformaldehyde 30.7g, Magnesium Chloride Anhydrous 58.4g are dispersed in tetrahydrofuran (THF) 500mL.Stir in ice bath after 30 minutes, dripped triethylamine 82.83g with 2 hours.Mixture is reacted 8 hours in a water bath, room temperature reaction 120 hours.In reaction solution, add cold 5N-hydrochloric acid 1500mL, formed after acidity, with the extraction into ethyl acetate 2 times of 400mL, collected organic layer.By anhydrous sodium sulphate by after organic layer, carry out diatomite filtration, with vaporizer below 40 DEG C by filtrate reduced in volume.Residue is dissolved in 100mL toluene, adds the heptane of 600mL in the solution.Add silica gel 30g in the solution, stir after 1 hour, filter.By filtrate reduced in volume, and then in residue, add heptane extract, make heptane distill removing, obtain 3, the 6-dimethyl salicylic aldehyde 10.5g as yellow liquid.With 2,5-xylenol for benchmark, yield is 17%.

The synthesis example of (2) 4,7-dimethyl benzofuran-2-carboxylic acids

Make 3,6-dimethyl salicylic aldehyde 10.48g, salt of wormwood 23.63g is dispersed in N, in N '-dimethyl ethanamide 70mL.After being heated to 80 DEG C, dripped bromo-acetic acid tert-butyl 13.61g with 10 minutes.Mixture reaction is made 3 hours in 130 DEG C.After reaction solution is cooled to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then, with the pure water of 300mL, organic layer is cleaned for 2 times, reclaim organic layer.After anhydrous sodium sulfate dehydration, with vaporizer distillation except desolventizing.Residue is dissolved in 40g acetic acid, adds hydrobromic acid aqueous solution 8g, stir 1 hour in 40 DEG C.Let cool to room temperature, add 1N-hydrochloric acid water 10g, the white powder that leaching is separated out.Obtained white powder is used further 1N-hydrochloric acid water, then with after washed with heptane, vacuum-drying, obtains 4, the 7-dimethyl benzofuran-2-carboxylic acid 7.31g as white powder thus.With 3,6-dimethyl salicylic aldehyde for benchmark, yield is 55%.

(3) synthesis example of compound (61-a)

Make 2,5-dimethoxyaniline 8.82g, 4,7-dimethyl benzofuran-2-carboxylic acid 7.30g are dispersed in chloroform 38g.After being cooled by obtained suspension with ice bath, added the mixture of 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 8.09g and chloroform 50g with 4 hours, in room temperature reaction 24 hours.In reaction soln, add 2,5-dimethoxyaniline 1.18g further, react 48 hours.Obtained mixture is concentrated, in residue, adds mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) 400g, the heptane 150g of 1N-hydrochloric acid, methyl alcohol, make its crystallization.The precipitation that leaching obtains, adds the mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.The pistac precipitation that leaching is separated out, cleans further with the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water-methanol.By the obtained pistac precipitation mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, methyl alcohol 2 parts by volume) of the 1N-KOH aqueous solution-methyl alcohol, then with leaching after water 150g cleaning.Vacuum-drying, obtains compound (61-a) 8.82g as pale yellow powder.With 4,7-dimethyl benzofuran-2-carboxylic acid for benchmark, yield is 71%.

(4) synthesis example of compound (61-b)

By compound (61-a) 8.82g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 6.58g and toluene 88g mixes, obtained mixture is warmed up to 110 DEG C, reacts 12 hours.After cooling, adopted and filtered separated out orange solids, in filtrate, added heptane, made its crystallization.The yellow mercury oxide that leaching is separated out, vacuum-drying, obtains compound (61-b) 4.7g as bright-yellow powder thus.With compound (61-a) for benchmark, yield is 51%.

(5) synthesis example of compound (61-c)

Compound (61-b) 4.27g, potassium hydroxide 3.83g and water 73g are mixed, makes obtained mixture reaction under ice-cooling.Then, under ice-cold, add Tripotassium iron hexacyanide 11.23g, then add methyl alcohol 15g, make it react.In room temperature reaction 12 hours, the yellow mercury oxide that leaching is separated out.By precipitation use water, methyl alcohol, the ethanol purge of leaching, leaching pale yellow precipitate.By the yellow powder vacuum-drying obtained, the faint yellow solid 3.08g that to obtain with compound (61-c) be principal constituent.Compound (61-a) is benchmark, and yield is 73%.

(6) synthesis example of compound (61-d)

By compound (61-c) 3.08g and pyridinium chloride 15.4g mixes, and is warmed up to 190 DEG C, reacts 7 hours.Ice is added, the precipitation that leaching obtains in obtained mixture.After aqueous suspension washing, with toluene cleaning, vacuum-drying, the khaki color solid 2.41g that to obtain with compound (61-d) be principal constituent.With compound (61-c) for benchmark, yield is 85%.

(7) synthesis example of compound (A61-1)

Compound (61-d) 2.41g, compound (A) 6.80g, dimethyl aminopyridine 0.09g and chloroform 38mL are mixed.N is added under ice-cooling, N '-DIC 2.34g in obtained mixture.Make obtained reaction soln at room temperature reaction one night, after filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.Leaching crystallization, made it be dissolved in chloroform again, adds 0.3g gac, in stirring at room temperature 1 hour.Filtering solution, after concentrating filtrate to 1/3 with vaporizer, vigorous stirring limit, limit adds methyl alcohol, the white precipitate that leaching generates, and with washed with heptane, vacuum-drying, obtains compound (A61-1) 4.52g as cream-coloured powder.With compound (61-d) for benchmark, yield is 53%.

Compound (A61-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.82 (m, 24H), 2.34 ~ 2.85 (m, 18H), 3.92 ~ 3.97 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.80 ~ 5.84 (dd, 2H), 6.07 ~ 6.18 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.87 ~ 7.02 (m, 8H), 7.02 ~ 7.13 (m, 2H), 7.24 (s, 2H), 7.57 (s, 1H)

The one after another of the compound (A61-1) obtained moves temperature and confirms by adopting polarized light microscope observing structure.Compound (A61-1), when heating up, shows the high phase of viscosity, from 138 DEG C, provides clear and definite nematic phase from 136 DEG C to 138 DEG C.And then compound (A61-1), until more than 150 DEG C in nematic phase, when lowering the temperature, is nematic phase and crystallization till 90 DEG C.

The synthesis example > of embodiment 28< compound (A69-1)

(1) synthesis example of 3-cyclohexyl-6-cresotinic acid aldehyde

Make 2-cyclohexyl-5-methylphenol 100g, paraformaldehyde 39.5g, Magnesium Chloride Anhydrous 75.0g be dispersed in tetrahydrofuran (THF) 900mL.Stir under ice bath after 30 minutes, dripped triethylamine 106.4g with 2 hours.Mixture is reacted 8 hours under water-bath, room temperature reaction 96 hours.Cold 5N-hydrochloric acid 1500mL is added in reaction solution, after becoming acidity, with the extraction into ethyl acetate 2 times of 400mL, collected organic layer.After organic over anhydrous sodium sulfate, with vaporizer concentrating under reduced pressure below 40 DEG C.Residue is dissolved in 100mL toluene, adds the heptane of 600mL in the solution.Add silica gel 38g in the solution, with vaporizer except desolventizing.In residue, add heptane extract, then distillation removing heptane, obtains yellow crystal 4, the 6-dimethyl salicylic aldehyde 35.2g of slow crystallization thus.With 2-cyclohexyl-5-methylphenol for benchmark, yield is 31%.

(2) synthesis example of 4-methyl-7-cyclohexyl cumarone-2-carboxylic acid

Make 3-cyclohexyl-6-cresotinic acid aldehyde 35.0g, salt of wormwood 72.2g is dispersed in N, in N '-dimethyl ethanamide 300mL.After being heated to 80 DEG C, dripped bromo-acetic acid tert-butyl 41.6g with 30 minutes.Mixture reaction is made 3 hours at 130 DEG C.After reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then 2 cleaning of the pure water with 500mL organic layers, reclaim organic layer.After anhydrous sodium sulfate dehydration, with vaporizer distillation except desolventizing.Residue is dissolved in 240g acetic acid, adds hydrobromic acid aqueous solution 72g, stir 1 hour in 40 DEG C.Let cool to room temperature, add 1N-hydrochloric acid 150g, the white powder that leaching is separated out.And then by obtained white powder 1N-hydrochloric acid, then with after washed with heptane, vacuum-drying, obtains the 4-methyl-7-cyclohexyl cumarone-2-carboxylic acid 25.8g as white powder thus.With 3-cyclohexyl-6-cresotinic acid aldehyde for benchmark, yield is 59%.

(3) synthesis example of compound (69-a)

Make 2,5-dimethoxyaniline 22.2g, 4-methyl-7-cyclohexyl cumarone-2-carboxylic acid 25.00g, triethylamine 9.79g is dispersed in chloroform 125g.After being cooled with an ice bath by obtained suspension, added the mixture of 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 20.4g and chloroform 100g with 4 hours, in room temperature reaction 72 hours.Obtained mixture is concentrated, in residue, adds mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) 400g, the heptane 150g of 1N-hydrochloric acid, methyl alcohol, make its crystallization.The precipitation that leaching obtains, adds the mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.The pistac precipitation that leaching is separated out, cleans further with the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water-methanol.By the mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, methyl alcohol 2 parts by volume) of the pistac precipitation 1N-KOH aqueous solution-methyl alcohol obtained, then clean with methyl alcohol 150g, leaching.Vacuum-drying, obtains compound (69-a) 12.3g as pale yellow powder.With 4-methyl-7-cyclohexyl cumarone-2-carboxylic acid for benchmark, yield is 32%.

(4) synthesis example of compound (69-b)

By compound (69-a) 12.3g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 7.6g and toluene 120g mixes, obtained mixture is warmed up to 110 DEG C, reacts 6 hours.After cooling, after toluene solution 2N-aqueous sodium hydroxide solution 500mL is cleaned three times, reclaim organic layer, then concentrated, add heptane, and then with vaporizer distillation except desolventizing.In residue, add methyl alcohol 50g, make its crystallization.The aureus crystallization that leaching obtains, vacuum-drying, obtains compound (69-b) 11.5g as bright-yellow powder thus.With compound (69-a) for benchmark, yield is 90%.

(5) synthesis example of compound (69-c)

Compound (69-b) 11.5g, potassium hydroxide 9.58g and the water 182g that obtain in preceding paragraph are mixed, makes obtained mixture reaction under ice-cooling.Then, Tripotassium iron hexacyanide 28.09g is added, the dispersion liquid of modulation containing compound (69-b).Methyl alcohol 40g is added in dispersion liquid, in 40 DEG C of reactions 2 hours, in room temperature reaction 24 hours, the yellow mercury oxide that leaching is separated out.By the precipitation water of leaching, then clean with hexane.And then, be dispersed in mixed solvent (toluene 1 parts by volume, the heptane 2 parts by volume) 400ml of toluene-heptane, reclaimed flaxen insoluble composition.By obtained faint yellow vacuum-drying, the faint yellow solid 4.5g that to obtain with compound (69-c) be principal constituent.With compound (69-a) for benchmark, yield is 36%.

(6) synthesis example of compound (69-d)

By compound (69-c) 4.54g and pyridinium chloride 45.4g mixes, and is warmed up to 180 DEG C, reacts 3 hours.Ice is added, the precipitation that leaching obtains in obtained mixture.After aqueous suspension washing, with toluene cleaning, vacuum-drying, the khaki color solid 3.4g that to obtain with compound (69-d) be principal constituent.With compound (69-c) for benchmark, yield is 80%.

(7) synthesis example of compound (A69-1)

Compound (69-d) 3.40g, compound (A) 7.87g, dimethyl aminopyridine 0.11g and chloroform 40mL are mixed.N is added under ice-cooling, N '-DIC 2.71g in obtained mixture.Obtained reaction soln is at room temperature made to react a night, after filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.Leaching crystallization, made it be dissolved in chloroform again, adds 0.3g gac, in stirring at room temperature 1 hour.Solution is filtered, after concentrating filtrate to 1/3 with vaporizer, stirs and add methyl alcohol, the white precipitate that leaching generates, with washed with heptane, vacuum-drying, obtain compound (A69-1) 4.84g as cream-coloured powder.With compound (69-d) for benchmark, yield is 45%.

Compound (A69-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.87 (m, 34H), 2.34 ~ 2.54 (m, 11H), 2.65 ~ 2.85 (m, 4H), 3.10 ~ 3.14 (tt, 1H), 3.92 ~ 3.97 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.86 ~ 7.14 (m, 10H), 7.25 (s, 2H), 7.56 (s, 1H)

The phase transition temperature of the compound (A69-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A69-1) shows the high phase of viscosity when heating up from 207 DEG C, carries out thermopolymerization at 220 DEG C.

The synthesis example > of embodiment 29< compound (A70-1)

(1) synthesis example of 3-propyl group salicylic aldehyde

2-propylphenol 75g, paraformaldehyde 41.3g, Magnesium Chloride Anhydrous 78.7g are dispersed in tetrahydrofuran (THF) 900mL.Stir under ice bath after 30 minutes, dripped triethylamine 111.5g with 2 hours.Mixture is reacted 8 hours under water-bath, in room temperature reaction 96 hours.Cold 5N-hydrochloric acid 1500mL is added in reaction solution, after becoming acidity, with the extraction into ethyl acetate 2 times of 400mL, collected organic layer.After organic over anhydrous sodium sulfate, with vaporizer concentrating under reduced pressure below 40 DEG C.Residue is dissolved in 100mL toluene, adds the heptane of 600mL in the solution.Add silica gel 90g in the solution, with vaporizer except desolventizing.In residue, add heptane extract, then distillation removing heptane, obtains the 3-propyl group salicylic aldehyde 28.8g as yellow liquid thus.With 2-propylphenol for benchmark, yield is 32%.

(2) synthesis example of 7-propyl group cumarone-2-carboxylic acid

Make 3-propyl group salicylic aldehyde 28.8g, salt of wormwood 59.3g is dispersed in N, in N '-dimethyl ethanamide 200mL.After being heated to 80 DEG C, dripped bromo-acetic acid tert-butyl 34.2g with 30 minutes.By mixture in 130 DEG C of reactions 2 hours.After reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then 2 cleaning of the pure water with 500mL organic layers, reclaim organic layer.After anhydrous sodium sulfate dehydration, with vaporizer distillation except desolventizing.Residue is dissolved in 150g acetic acid, adds hydrobromic acid aqueous solution 45g, stir 1 hour in 40 DEG C.Let cool to room temperature, add 1N-hydrochloric acid 150g, the white powder that leaching is separated out.And then by obtained white powder 1N-hydrochloric acid, then with after washed with heptane, vacuum-drying, obtains the 7-propyl group cumarone-2-carboxylic acid 28.1g as white powder thus.With 3-propyl group salicylic aldehyde for benchmark, yield is 78%.

(3) synthesis example of compound (70-a)

Make 2,5-dimethoxyaniline 20.25g, 7-propyl group cumarone-2-carboxylic acid 18.0g, triethylamine 8.92g is dispersed in chloroform 90g.After being cooled by obtained suspension with ice bath, added the mixture of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 18.6g and chloroform 100g with 4 hours, in room temperature reaction 72 hours.The concentrated mixture obtained, adds mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) 400g, the heptane 150g of 1N-hydrochloric acid, methyl alcohol, makes its crystallization in residue.The precipitation that leaching obtains, adds in the mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.Leaching pistac precipitates, and cleans, leaching with the mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, methyl alcohol 2 parts by volume) of the 1N-KOH aqueous solution-methyl alcohol.Vacuum-drying, obtains compound (70-a) 19.8g as pale yellow powder.With 7-propyl group cumarone-2-carboxylic acid for benchmark, yield is 66%.

(4) synthesis example of compound (70-b)

By compound (70-a) 19.8g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 14.2g and toluene 198g mixes, obtained mixture is warmed up to 110 DEG C, reacts 6 hours.After cooling, after toluene solution 2N-aqueous sodium hydroxide solution 500mL is cleaned three times, reclaim organic layer, then concentrated, add heptane, make its crystallization.The aureus crystallization that leaching obtains, vacuum-drying, obtains compound (70-b) 18.6g as bright-yellow powder thus.With compound (70-a) for benchmark, yield is 90%.

(5) synthesis example of compound (70-c)

Compound (70-b) 18.6g, potassium hydroxide 17.86g and water 320g are mixed, makes the mixture reaction obtained under ice-cooling.Then, Tripotassium iron hexacyanide 52.41g is added, the dispersion liquid of modulation containing compound (70-b).Methyl alcohol 70g is added in dispersion liquid, in 40 DEG C of reactions 2 hours, in room temperature reaction 24 hours, the yellow mercury oxide that leaching is separated out.By the precipitation water of leaching, then use washed with methanol.And then, yellow powder hot ethanol is cleaned, leaching.By obtained yellow powder vacuum-drying, the faint yellow solid 15.8g that to obtain with compound (70-c) be principal constituent.With compound (70-a) for benchmark, yield is 76%.

(6) synthesis example of compound (70-d)

By compound (70-c) 15.8g and pyridinium chloride 158g mixes, and is warmed up to 180 DEG C, reacts 3 hours.Obtained mixture is added in ice, the precipitation that leaching obtains.After aqueous suspension washing, with toluene cleaning, make its vacuum-drying, the khaki color solid 13.6g that to obtain with compound (70-d) be principal constituent.With compound (70-c) for benchmark, yield is 94%.

(7) synthesis example of compound (A70-1)

Compound (70-d) 5.00g, compound (A) 13.5g, Dimethylamino pyridine 0.19g and chloroform 60mL are mixed.N is added under ice-cooling, N '-DIC 4.65g in obtained mixture.Obtained reaction soln is made to react a night in room temperature, after filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.Leaching crystallization, made it be dissolved in chloroform again, adds 0.3g gac, in stirring at room temperature 1 hour.Solution is filtered, after concentrating filtrate to 1/3 with vaporizer, stirs and add methyl alcohol, the white precipitate that leaching generates, with washed with heptane, vacuum-drying, obtain compound (A70-1) 8.38g as cream-coloured powder.With compound (70-d) for benchmark, yield is 48%.

Compound (A70-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.01 ~ 1.06 (t, 3H), 1.45 ~ 1.84 (m, 26H), 2.34 ~ 2.48 (m, 8H), 2.63 ~ 2.71 (m, 4H), 2.94 ~ 3.00 (t, 2H), 3.92 ~ 3.97 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.36 ~ 6.44 (m, 2H), 6.87 ~ 6.98 (m, 8H), 7.22 ~ 7.24 (m, 4H), 7.52 ~ 7.53 (m, 2H)

The phase transition temperature of the compound (A70-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A70-1), when heating up, shows the high phase of viscosity, from 142 DEG C, provides clear and definite nematic phase from 137 DEG C to 142 DEG C.And then compound (A70-1), until more than 220 DEG C is all nematic phase, is nematic phase and crystallization when lowering the temperature till 125 DEG C.Embodiment 30 ~ 33 and comparative example 1

The Production Example > of < blooming

The 2 quality % aqueous solution of pva coating (the fully saponified type of polyvinyl alcohol 1000, Wako Pure Chemical Industries, Ltd.'s system) on the glass substrate, after drying, form the film of thickness 89nm.Then, friction treatment is implemented to the surface of obtained film, by the composition of the composition of spin-coating method coating table 4 on the face implementing friction treatment, with the drying temperature drying described in table 51 minute.Next, be heated to the temperature during rayed described in table 5, the ultraviolet of the integrating light quantity simultaneously described in exposure chart 5, form the blooming of the thickness described in table 6.

[table 4]

B1-1: the liquid crystalline cpd shown in formula (B1-1)

LC242: the same

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

[table 5]

	Drying temperature after coating	Temperature during rayed	Integrating light quantity (mJ/cm ²)
				Embodiment 30	150℃	110℃	2400
Embodiment 31	150℃	95℃	1200
				Embodiment 32	180℃	150℃	2400
Embodiment 33	195℃	185℃	2400
				Comparative example 1	45℃	Room temperature	1200

The mensuration > of < optical characteristics

Measuring machine (KOBRA-WR, prince measures machines corporation system) is used to measure the front phase difference value of blooming.It should be noted that, because the glass substrate used in base material does not have birefringence, so measure the film of subsidiary glass substrate by measuring machine, the front phase difference value of the blooming that just can be made on the glass substrate.The optical detecting front phase difference value obtained measures respectively at wavelength 447.3nm, 546.9nm and 627.8nm, calculates [Re (447.3)/Re (546.9)] (as α) and [Re (627.8)/Re (546.9)] (as β).Further, laser microscope (LEXT, Olympus Corp's system) is used to measure the thickness d (μm) of blooming.Table 6 will be the results are shown in.△ n (△ n=Re (546.9)/d) is calculated divided by film thickness gauge by the value of Re (546.9).

[table 6]

	Re(546.9)	α	β	d(μm)	Δn
						Embodiment 30	84.5	0.888	1.017	1.186	0.071
Embodiment 31	95.0	0.873	1.025	1.279	0.071
						Embodiment 32	98.3	0.956	1.002	1.160	0.086
Embodiment 33	74.7	0.938	1.006	1.087	0.067
						Comparative example 1	141.0	1.075	0.978	1.001	0.141

The hot physical property > of embodiment 34 ~ 39 and comparative example 2 ~ 7< composition

The modulation > of < composition

The composition of the composition of modulometer 7.

[table 7]

Photoepolymerizationinitiater initiater: IRGACURE 819 (Ciba Japan Co., Ltd. system; Acylphosphine oxide compound)

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

The hot physical property of < observes >

The 2 quality % aqueous solution of pva coating (the fully saponified type of polyvinyl alcohol 1000, Wako Pure Chemical Industries, Ltd.'s system) on the glass substrate, after heat drying, form the film of thickness 89nm.Friction treatment is implemented to the surface of film, forms alignment films.By the composition described in spin-coating method coating table 8 on the face implementing friction treatment.Use the polarization microscope (thermal station: LTS350, Linkam Inc., polarization microscope: BX-51, Olympus Corp's system) of band thermal station, during intensification with heat-up rate 30 DEG C/min by the base plate heating after coating, the simultaneously situation of observation group's compound.Naturally cooling is adopted, the situation of observation group's compound during cooling.Show the result in table 8.

[table 8]

T _a: be nematic phase from crystalline transition, start the temperature forming one-domain structure.

T _b: at high temperature keep nematic temperature.

T _c: the temperature of crystallization.

The Production Example > of < film

The 2 quality % aqueous solution of pva coating (the fully saponified type of polyvinyl alcohol 1000, Wako Pure Chemical Industries, Ltd.'s system) on the glass substrate, heat drying, forms the film of thickness 89nm.Friction treatment is implemented to the surface of film, forms alignment films.By the composition described in spin-coating method coating table 7 on the face implementing friction treatment, with the temperature (T described in table 9 _d) dry 1 minute.Temperature (T described in table 9 _e) under place after 1 minute, irradiate integrating light quantity 2400mJ/cm ²ultraviolet, make film.At this, T _ethat reproducibility manufactures the non-crystallizable and temperature needed for film that single domain is homogeneous of liquid crystal, T well _elower, represent and more can manufacture blooming at low temperature.

[table 9]

	T _d	T _e
			Embodiment 34	100℃	70℃
Embodiment 35	130℃	70℃
			Embodiment 36	100℃	70℃
Embodiment 37	100℃	70℃
			Embodiment 38	100℃	70℃
Embodiment 39	100℃	70℃
			Comparative example 2	110℃	80℃
Comparative example 3	180℃	165℃
			Comparative example 4	110℃	80℃
Comparative example 5	120℃	90℃
			Comparative example 6	145℃	120℃
Comparative example 7	120℃	100℃

The synthesis example > of embodiment 40< compound (A71-1)

(1) synthesis example of chloro-4, the 6-dimethyl salicylic aldehydes of 5-

CDMP 100g, paraformaldehyde 47.94g, Magnesium Chloride Anhydrous 91.19g are dispersed in acetonitrile 800mL.Stir under ice bath after 30 minutes, dripped triethylamine 129.23g with 2 hours.By mixture water-bath 3 hours, 50 DEG C of reactions 18 hours.Cold 2N-hydrochloric acid is added in reaction solution, after becoming neutrality, with the extraction into ethyl acetate 2 times of 600mL, collected organic layer.After organic over anhydrous sodium sulfate, add gac 3g, after stirring, carry out diatomite filtration, with vaporizer below 40 DEG C by filtrate reduced in volume.In residue, adding heptane 1000mL, filtering insolubles by crossing.Reclaim filtrate, carry out recrystallization, obtain chloro-4, the 6-dimethyl salicylic aldehyde 20.00g of 5-as pale yellow powder thus.Take CDMP as benchmark, yield is 17%.

(2) synthesis example of chloro-4, the 6-dimethyl benzofuran-2-carboxylic acids of 5-

Make chloro-4, the 6-dimethyl salicylic aldehyde 20.00g of 5-, salt of wormwood 36.68g is dispersed in N, in N '-dimethyl ethanamide 150mL.After being heated to 80 DEG C, dripped bromo-acetic acid tert-butyl 21.13g with 10 minutes.Mixture reaction is made 3 hours in 130 DEG C.After reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then 2 cleaning of the pure water with 300mL organic layers, reclaim organic layer.After anhydrous sodium sulfate dehydration, with vaporizer distillation except desolventizing.Residue is dissolved in 60g acetic acid, adds trifluoroacetic acid 20g, stir 1 hour in 60 DEG C.Let cool to room temperature, add 1N-hydrochloric acid water 10g, the white powder that leaching is separated out.Obtained white powder is used further 1N-hydrochloric acid water, then with after washed with heptane, vacuum-drying, obtains chloro-4, the 6-dimethyl benzofuran-2-carboxylic acid 19.37g of 5-as white powder thus.With chloro-4, the 6-dimethyl salicylic aldehydes of 5-for benchmark, yield is 80%.

(3) synthesis example of compound (71-a)

Chloro-4, the 6-dimethyl benzofuran-2-carboxylic acid 19.00g of 2,5-dimethoxyaniline 19.43g, 5-are dispersed in 200g chloroform.After being cooled by obtained suspension with ice bath, added the mixture of 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 17.64g and chloroform 80g with 6 hours, in room temperature reaction 24 hours.In reaction soln, add 2,5-dimethoxyaniline 0.2g further, react 48 hours.The concentrated mixture obtained, adds mixing solutions (hydrochloric acid water 2 parts by volume, the methyl alcohol 1 parts by volume) 400g of 1N-hydrochloric acid, methyl alcohol, makes its crystallization in residue.By obtained faint yellow powder methyl alcohol, then with toluene cleaning, leaching.Vacuum-drying, obtains compound (71-a) 13.68g as pale yellow powder.With chloro-4, the 6-dimethyl benzofuran-2-carboxylic acids of 5-for benchmark, yield is 45%.

(4) synthesis example of compound (71-b)

By compound (71-a) 13.63g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.19g and toluene 150g mixes, obtained mixture is warmed up to 110 DEG C, reacts 6 hours.After cooling, add 1N-aqueous sodium hydroxide solution.Reclaim organic layer, add heptane 100mL, make its crystallization.Leaching red colored crystalline, makes it dry, obtains compound (71-b) 14.24g as orange powder.Although be mixed with the impurity deriving from lawesson reagent, be directly used in subsequent step.

(5) synthesis example of compound (71-c)

Compound (71-b) 14.24g, potassium hydroxide 11.60g and water 220g are mixed, makes obtained mixture reaction under ice-cooling.Then, add Tripotassium iron hexacyanide 34.03g under ice-cooling, next add methyl alcohol 44g, react.At room temperature reaction after 12 hours, 80 DEG C of reactions 8 hours.The pale yellow precipitate that leaching is separated out.By precipitation use water, methyl alcohol, the ethanol purge of leaching, leaching pale yellow precipitate.By obtained pale yellow powder vacuum-drying, the faint yellow solid 10.3g that to obtain with compound (71-c) be principal constituent.Yield with compound (71-a) be benchmark, in two steps for 73%.

(6) synthesis example of compound (71-d)

By compound (71-c) 10.00g and pyridinium chloride 100g mixes, and is warmed up to 190 DEG C, reacts 2 hours.Obtained mixture is added in ice, the precipitation that leaching obtains.After aqueous suspension washing, with toluene, chloroform cleaning, vacuum-drying, the yellow solid 7.20g that to obtain with compound (71-d) be principal constituent.With compound (71-c) for benchmark, yield is 78%.

(7) synthesis example of compound (A71-1)

Compound (71-d) 1.00g, compound (A) 2.54g, dimethyl aminopyridine 0.04g and chloroform 40mL are mixed.N is added under ice-cooling, N '-DIC 0.88g in obtained mixture.Obtained reaction soln is made to react a night in room temperature, after carrying out diatomite filtration, concentrating under reduced pressure.In residue, add ethanol, make its crystallization.Leaching crystallization, made it be dissolved in chloroform again, adds 0.3g gac, in stirring at room temperature 1 hour.Filtering solution, after concentrating filtrate to 1/3 with vaporizer, vigorous stirring limit, limit adds methyl alcohol, the white precipitate that leaching generates, and with washed with heptane, vacuum-drying, obtains compound (A71-1) 2.58g as cream-coloured powder.With compound (71-d) for benchmark, yield is 78%.

Compound (A71-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.83 (m, 24H), 2.35 ~ 2.85 (m, 18H), 3.93 ~ 3.98 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.80 ~ 5.84 (dd, 2H), 6.07 ~ 6.18 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.87 ~ 7.01 (m, 8H), 7.25 (s, 1H), 7.32 (s, 1H), 7.52 (d, 1H)

The phase transition temperature of the compound (A71-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A71-1), when heating up, shows the high phase of viscosity, from 154 DEG C, provides clear and definite nematic phase from 148 DEG C to 154 DEG C.And then compound (A71-1), until more than 160 DEG C all in nematic phase, when lowering the temperature, is nematic phase and crystallization till 127 DEG C.

The synthesis example > of embodiment 41< compound (A21-1)

(1) synthesis example of compound (21-a)

Make 2,5-dimethoxyaniline 12.82g, benzothiazole-2-carboxylic acid 10.00g is dispersed in chloroform 100g.After being cooled by obtained suspension with ice bath, added the mixture of 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 11.77g and chloroform 70g with 4 hours, in room temperature reaction 24 hours.In reaction soln, add 2,5-dimethoxyaniline 0.5g further react 48 hours.The concentrated mixture obtained, adds mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) 400g, the heptane 150g of 1N-hydrochloric acid, methyl alcohol, makes its crystallization in residue.The precipitation that leaching obtains, adds the mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.The aureus precipitation that leaching is separated out, cleans further with the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water-methanol.By the obtained aureus precipitation mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, methyl alcohol 2 parts by volume) of the 1N-KOH aqueous solution-methyl alcohol, then with water 150g cleaning, leaching.Vacuum-drying, obtains compound (21-a) 8.47g as yellow powder.With benzothiazole-2-carboxylic acid for benchmark, yield is 48%.

(2) synthesis example of compound (21-b)

By compound (21-a) 8.47g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 6.54g and toluene 85g mixes, obtained mixture is warming up to 110 DEG C, reacts 6 hours.After cooling, add 1N-aqueous sodium hydroxide solution.Reclaim organic layer, add heptane 100mL, make its crystallization.Leaching orange crystal, vacuum-drying, obtains the compound (21-b) as bright-yellow powder thus.Although be mixed with the impurity deriving from lawesson reagent, be directly used in subsequent step.

(3) synthesis example of compound (21-c)

Compound (21-b) 8.90g, potassium hydroxide 8.25g and water 156g are mixed, obtained mixture is reacted under ice-cooling.Then, add Tripotassium iron hexacyanide 24.19g under ice-cooling, next add methyl alcohol 30g, make it react.In room temperature reaction 12 hours, in 50 DEG C of reactions 12 hours, the pale yellow precipitate that leaching is separated out.By precipitation use water, methyl alcohol, the ethanol purge of leaching, leaching pale yellow precipitate, by the pale yellow powder vacuum-drying obtained, the faint yellow solid 7.40g that to obtain with compound (21-c) be principal constituent.With compound (21-a) for benchmark, yield is 84%.

(4) synthesis example of compound (21-d)

By compound (21-c) 7.00g and pyridinium chloride 105g mixes, and is warmed up to 190 DEG C, reacts 3 hours.Obtained mixture is added in ice, the precipitation that leaching obtains.After aqueous suspension washing, with toluene cleaning, vacuum-drying, the yellow solid 6.00g that to obtain with compound (21-d) be principal constituent.With compound (21-c) for benchmark, yield is 94%.

(5) synthesis example of compound (A21-1)

Compound (21-d) 1.00g, compound (A) 2.93g, dimethyl aminopyridine 0.04g and chloroform 50mL are mixed.N is added under ice-cooling, N '-DIC 1.01g in obtained mixture.Obtained reaction soln is at room temperature made to react a night, after carrying out diatomite filtration, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.Leaching crystallization, made it be dissolved in chloroform again, adds 0.3g gac, in stirring at room temperature 1 hour.Filtering solution, after concentrating filtrate to 1/3 with vaporizer, vigorous stirring limit, limit adds methyl alcohol, the white precipitate that leaching generates, and with washed with heptane, vacuum-drying, obtains compound (A21-1) 2.70g as cream-coloured powder.With compound (21-d) for benchmark, yield is 74%.

Compound (A21-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.83 (m, 24H), 2.32 ~ 2.50 (m, 8H), 2.62 ~ 2.84 (m, 4H), 3.93 ~ 3.98 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.80 ~ 5.84 (dd, 2H), 6.07 ~ 6.18 (m, 2H), 6.37 ~ 6.44 (m, 2H), 6.87 ~ 7.03 (m, 8H), 7.25 ~ 7.32 (2d, 2H), 7.50 ~ 7.59 (m, 2H), 7.97 ~ 8.00 (dd, 1H), 8.14 ~ 8.17 (dd, 1H)

The phase transition temperature of the compound (A21-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A21-1), when heating up, shows the high phase of viscosity, from 155 DEG C, provides clear and definite nematic phase from 137 DEG C to 155 DEG C.And then compound (A21-1) all in nematic phase, is nematic phase and crystallization when lowering the temperature more than 170 DEG C till 121 DEG C.

Embodiment 42 ~ 43, comparative example 1

The Production Example > of < blooming

The 2 quality % aqueous solution of pva coating (the fully saponified type of polyvinyl alcohol 1000, Wako Pure Chemical Industries, Ltd.'s system) on the glass substrate, after drying, form the film of thickness 89nm.Then, friction treatment is implemented to the surface of obtained film, by the composition of the composition of spin-coating method coating table 10 on the face implementing friction treatment, drying 1 minute under the drying temperature that table 11 is recorded.Next, be heated to the temperature during rayed described in table 11, the ultraviolet of the integrating light quantity of exposure chart 11 record simultaneously, forms the blooming of the thickness described in table 12.

[table 10]

LC242: the same

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

[table 11]

	Drying temperature after coating	Temperature during rayed	Integrating light quantity (mJ/cm ²)
				Embodiment 42	160℃	140℃	7200
Embodiment 43	165℃	135℃	7200
				Comparative example 1	45℃	Room temperature	1200

The mensuration > of < optical characteristics

Measuring machine (KOBRA-WR, prince measures machines corporation system) is used to measure the front phase difference value of blooming.It should be noted that, because the glass substrate used in base material does not have birefringence, so measure the film of subsidiary glass substrate by measuring machine, the front phase difference value of the blooming that just can be made on the glass substrate.The optical detecting front phase difference value obtained measures respectively at wavelength 450.9nm, 549.4nm and 627.8nm, calculates [Re (450.9)/Re (549.4)] (as α) and [Re (627.8)/Re (549.4)] (as β).Further, laser microscope (LEXT, Olympus Corp's system) is used to measure the thickness d (μm) of blooming.Show the result in table 12.△ n (△ n=Re (549.4)/d) is calculated divided by film thickness gauge by the value of Re (549.4).

[table 12]

	Re(549.4)	α	β	d(μm)	Δn
						Embodiment 42	75.0	0.811	1.039	1.150	0.060
Embodiment 43	112.0	0.858	1.030	1.546	0.072
						Comparative example 1	141.0	1.075	0.978	1.001	0.141

The blooming of embodiment 12 ~ 24, embodiment 30 ~ 33 and embodiment 42 ~ 43, the value of [Re (447.3)/Re (546.9)] (in table α) is less than 1.Further, the value of [Re (627.8)/Re (546.9)] (in table β) is more than 1.That is, the wavelength dependency of specific refractory power shows so-called inverse wave length dispersiveness, so can carry out same polarized light conversion in the wavelength region of broadness.

The film of embodiment is used for liquid crystal panel, then there is the characteristic of optical compensation excellence.And then, from embodiment 20 ~ 24 and embodiment 32 ~ 33, only compound of the present invention is mixed with liquid crystalline cpd, just can disperse from positive wavelength dispersion to inverse wave length freely to control wavelength dispersibility.

In addition, embodiment 34 ~ 39 and comparative example 2 ~ 7 are compared, known, by being mixed with liquid crystalline cpd by compound of the present invention, the temperature movement of display one-domain structure, to low temperature side, can manufacture blooming in lower temperature.

Embodiment 44 ~ 45

The Production Example > of < blooming

Same with embodiment 42 ~ 43, comparative example 1, by the composition of the composition described in spin-coating method coating table 13,140 DEG C of dryings after 1 minute, while 80 DEG C of heating, irradiate integrating light quantity 2400mJ/cm ²ultraviolet, formed blooming.Show the result in table 14.

[table 13]

Polymerization starter: IRGACURE 369 (Ciba Japan Co., Ltd. system; Acetophenone compound)

IRGACURE 819 (Ciba Japan Co., Ltd. system; Acylphosphine oxide)

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

[table 14]

	Re(549.4)	α	β	d(μm)	Δn
						Embodiment 44	147.0	0.891	1.016	2.380	0.062
Embodiment 45	143.6	0.876	1.021	2.251	0.064

The thermal test > of < blooming

The blooming obtained in embodiment 44 and embodiment 45 is kept 1000 hours in the baking oven of temperature 85 DEG C of humidity 0%, carries out thermal test.Optical characteristics before and after determination test, and then, from the α value after test, deduct the α value of initial value, using the value that obtains as variable quantity △ α.If △ α more than-0.2 below+0.2, then can judge that the change of optical characteristics is little.Table 15 will be the results are shown in.

[table 15]

The humidity resistance test > of < blooming

The blooming obtained in embodiment 44 and embodiment 45 is kept 1000 hours in the baking oven of temperature 60 C humidity 90%, carries out humidity resistance test.Optical characteristics before and after determination test, and then, from the α value after test, deduct the α value of initial value, using the value that obtains as variable quantity △ α.If △ α more than-0.2 below+0.2, then can judge that the change of optical characteristics is little.Table 16 will be the results are shown in.

[table 16]

As shown in Table 15 and Table 16, blooming of the present invention in thermal test and humidity resistance test △ α more than-0.2 below+0.2, it can thus be appreciated that blooming of the present invention shows good thermotolerance and humidity resistance simultaneously.In addition, shown in table 16, the blooming of embodiment 44 shows less △ α in humidity resistance, it can thus be appreciated that, if use acetophenone compound as polymerization starter, then blooming display is better humidity resistance, namely good weather resistance.

The synthesis example > of embodiment 46< compound (A72-1)

The synthesis example of (1) 4,5,6-trimethylammonium salicylic aldehyde

3,4,5-pseudocuminol 10.00g, paraformaldehyde 5.51g, Magnesium Chloride Anhydrous 10.49g are dispersed in acetonitrile 60mL.Stir in ice bath after 30 minutes, dripped triethylamine 14.86g with 2 hours.By mixture in 50 DEG C of reactions 8 hours, in room temperature reaction 24 hours.Add the ethyl acetate of 400mL, pure water 100mL in reaction solution after, add 1N-hydrochloric acid, after becoming acidity, collected organic layer.After organic over anhydrous sodium sulfate, with vaporizer concentrating under reduced pressure below 40 DEG C.Residue column chromatography refined, wherein said column chromatography uses ethyl acetate-heptane (1:3 volume ratio) as elutriant, obtains 4,5, the 6-trimethylammonium salicylic aldehyde 8.10g as yellow powder.With 3,4,5-pseudocuminol for benchmark, yield is 67%.

The synthesis example of (2) 4,5,6-trimethylammonium cumarone-2-carboxylic acids

Make 4,5,6-trimethylammonium salicylic aldehyde 8.10g, salt of wormwood 16.36g is dispersed in N, in N '-dimethyl ethanamide 50mL.After being heated to 80 DEG C, dripped bromo-acetic acid tert-butyl 9.62g with 30 minutes.Make mixture 135 DEG C of reactions 2 hours.After reaction solution is cooled to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, filter.Reclaim filtrate, with pure water 1000mL separatory.And then 2 cleaning of the pure water with 500mL organic layers, reclaim organic layer.After anhydrous sodium sulfate dehydration, with vaporizer distillation except desolventizing.Residue is dissolved in 150g acetic acid, adds hydrobromic acid aqueous solution 45g, stir 1 hour in 40 DEG C.Let cool to room temperature, add 1N-hydrochloric acid 150g, the incarnadine powder that leaching is separated out.The incarnadine powder obtained is used further 1N-hydrochloric acid, then with after toluene cleaning, vacuum-drying, obtains 4,5, the 6-trimethylammonium cumarone-2-carboxylic acid 6.34g as incarnadine powder thus.With 4,5,6-trimethylammonium salicylic aldehyde for benchmark, yield is 63%.

(3) synthesis example of compound (72-a)

Make 2,5-dimethoxyaniline 7.13g, 4,5,6-trimethylammonium cumarone-2-carboxylic acid 6.34g are dispersed in chloroform 30g.After being cooled by obtained suspension with ice bath, added the mixture of 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 6.55g and chloroform 100g with 4 hours, in room temperature reaction 48 hours.By obtained mixture concentrating under reduced pressure, in residue, add mixing solutions (hydrochloric acid water 2 parts by volume, the methyl alcohol 1 parts by volume) 400g of 1N-hydrochloric acid, methyl alcohol, make its crystallization.The precipitation that leaching obtains, is added in the mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.The greenish orange look precipitation of leaching, cleans with the mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, methyl alcohol 2 parts by volume) of the 1N-KOH aqueous solution-methyl alcohol, leaching.Vacuum-drying, obtains compound (72-a) 9.39g as pale yellow powder.With 4,5,6-trimethylammonium cumarone-2-carboxylic acid for benchmark, yield is 89%.

(4) synthesis example of compound (72-b)

By two to compound (72-a) 9.39g, 2.4-(4-p-methoxy-phenyl)-1,3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 6.71g and toluene 95g mixes, obtained mixture is warmed up to 110 DEG C, reacts 4 hours.After cooling, in toluene solution, add 2N-aqueous sodium hydroxide solution 500mL, heptane 100g, the yellow mercury oxide that leaching is separated out.The precipitation obtained cleaned with heptane, 2N-aqueous sodium hydroxide solution further, vacuum-drying, obtains compound (72-b) 9.83g as bright-yellow powder thus.Compound (72-b), although contain the resolvent of the lawesson reagent of 3%, is directly used in subsequent step.

(5) synthesis example of compound (72-c)

Compound (72-b) 9.83g, potassium hydroxide 8.47g and water 400g are mixed, makes obtained mixture reaction under ice-cooling.Then, Tripotassium iron hexacyanide 24.84g is added, the dispersion liquid of modulation containing compound (72-b).Methyl alcohol 70g is added in dispersion liquid, in 60 DEG C of reactions 48 hours, the yellow mercury oxide that leaching is separated out.By the precipitation water filtered, then use washed with methanol.And then, yellow powder hot toluene is carried out recrystallization.The pale yellow crystals that leaching generates, vacuum-drying, the faint yellow solid 4.60g that to obtain with compound (72-c) be principal constituent.With compound (72-a) for benchmark, yield is 47%.

(6) synthesis example of compound (72-d)

By compound (72-c) 4.60g and pyridinium chloride 64.4g mixing, is warmed up to 180 DEG C, reacts 3 hours.The mixture obtained is added in ice, the precipitation that leaching obtains.After aqueous suspension washing, with toluene cleaning, vacuum-drying, the greenish yellow solid 4.10g that to obtain with compound (72-d) be principal constituent.With compound (72-c) for benchmark, yield is 97%.

(7) synthesis example of compound (A72-1)

Compound (72-d) 1.10g, compound (A) 2.97g, dimethyl aminopyridine 0.04g and chloroform 20mL, toluene 20mL are mixed.N is added under ice-cooling, N '-DIC 1.02g in the mixture obtained.Make obtained reaction soln react a night in room temperature, in reaction solution, add silica gel 4g, gac 200mg, in stirring at room temperature after 1 hour, carry out diatomite filtration.Concentrating under reduced pressure filtrate, after removing chloroform, adds methyl alcohol in the solution, crystal is separated out.Leaching cream-coloured powder, and then with after ethanol purge 2 times, with washed with heptane, vacuum-drying, obtain compound (A72-1) 2.95g as cream-coloured powder.With compound (72-d) for benchmark, yield is 78%.

Compound (A72-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.84 (m, 24H), 2.27 ~ 2.50 (m, 17H), 2.62 ~ 2.84 (m, 4H), 3.93 ~ 3.97 (t, 4H), 4.16 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.45 (m, 2H), 6.87 ~ 7.02 (m, 8H), 7.22 ~ 7.23 (2s, 3H), 7.54 (s, 1H)

The phase transition temperature of the compound (A72-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A72-1), when heating up, shows the high phase of viscosity, from 148 DEG C, provides clear and definite nematic phase from 136 DEG C to 148 DEG C.And then compound (A72-1), until more than 170 DEG C all in nematic phase, is nematic phase and crystallization when lowering the temperature till 120 DEG C.

The synthesis example > of embodiment 47< compound (A73-1)

(1) synthesis example of 6-methyl benzofuran-2-carboxylic acid

Make 4-Methyl Salicylaldehyde 20.0g, salt of wormwood 48.73g is dispersed in N, in N '-dimethyl ethanamide 100mL.After being heated to 70 DEG C, dripped bromo-acetic acid tert-butyl 28.65g with 30 minutes.Make mixture 135 DEG C of reactions 2 hours.After reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then 2 cleaning of the pure water with 500mL organic layers, reclaim organic layer.After anhydrous sodium sulfate dehydration, with vaporizer distillation except desolventizing.Residue is dissolved in 150g acetic acid, adds 45g hydrobromic acid aqueous solution, stir 1 hour in 40 DEG C.Let cool to room temperature, add 1N-hydrochloric acid 150g, the white powder that leaching is separated out.Obtained white powder is used further 1N-hydrochloric acid, then with after heptane, toluene cleaning, vacuum-drying, obtains the 6-methyl benzofuran-2-carboxylic acid 20.58g as white powder thus.Take 4-Methyl Salicylaldehyde as benchmark, yield is 80%.

(2) synthesis example of compound (73-a)

2,5-dimethoxyaniline 26.09g, 6-methyl benzofuran-2-carboxylic acid 20.00g is dispersed in chloroform 100g.After being cooled by obtained suspension with ice bath, added the mixture of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 23.94g and chloroform 120g with 4 hours, in room temperature reaction 48 hours.Obtained mixture is concentrated, in residue, adds mixture (hydrochloric acid water 2 parts by volume, the methyl alcohol 1 parts by volume) 400g of 1N-hydrochloric acid, methyl alcohol, make its crystallization.The precipitation that leaching obtains, is added in the mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.Leaching pistac precipitates, and cleans with the mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, methyl alcohol 2 parts by volume) of the 1N-KOH aqueous solution-methyl alcohol, filters.Vacuum-drying, obtains compound (73-a) 31.26g as pale yellow powder.With 6-methyl benzofuran-2-carboxylic acid for benchmark, yield is 89%.

(3) synthesis example of compound (73-b)

By compound (73-a) 31.26g, 2, two (4-p-methoxy-phenyl)-1.3-two sulphur-2 of 4-, 4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 24.73g and toluene 300g mixes, obtained mixture is warmed up to 110 DEG C, reacts 6 hours.After cooling, after toluene solution 2N-aqueous sodium hydroxide solution 500mL is cleaned 3 times, after reclaiming organic layer, add normal heptane, make its crystallization.The aureus crystallization that leaching obtains, vacuum-drying, obtains the compound (73-b) as bright-yellow powder thus.Obtained compound (73-b) is all directly used in subsequent step.

(4) synthesis example of compound (73-c)

Compound (73-b) 35.69g, potassium hydroxide 33.37g and water 630g are mixed.Then, Tripotassium iron hexacyanide 97.91g is added, the dispersion liquid of modulation containing compound (73-b).Methyl alcohol 126g is added in dispersion liquid, in 40 DEG C of reactions 2 hours, in room temperature reaction 24 hours, the pale yellow precipitate that leaching is separated out.By the precipitation water of leaching, then use washed with methanol.And then, yellow powder hot methanol is cleaned, leaching.By obtained faint yellow material vacuum-drying, the faint yellow solid 23.31g that to obtain with compound (73-c) be principal constituent.With compound (73-a) for benchmark, yield is 66%.

(5) synthesis example of compound (73-d)

By compound (73-c) 23.31g and pyridinium chloride 233.1g mixes, and is warmed up to 180 DEG C, reacts 3 hours.Obtained mixture is added in ice, the precipitation that leaching obtains.After aqueous suspension washing, with toluene cleaning, then, be dispersed in saturated SODIUM HYDROSULPHITE sodium water solution, chloroform, in stirring at room temperature 2 hours.Filter dispersion liquid, and then make its vacuum-drying with after pure water washing and precipitating, the yellow solid 21.2g that to obtain with compound (73-d) be principal constituent.With compound (73-c) for benchmark, yield is 100%.

(6) synthesis example of compound (A73-1)

Compound (73-d) 1.00g, compound (A) 2.96g, dimethyl aminopyridine 0.04g and chloroform 20mL, toluene 20mL are mixed.N is added under ice-cooling, N '-DIC 1.02g in obtained mixture.Obtained reaction soln is made to react a night in room temperature.In reaction solution, add silica gel 4g, gac 200mg, in stirring at room temperature after 1 hour, carry out diatomite filtration.By filtrate reduced in volume, after removing chloroform, add methyl alcohol in the solution, crystal is separated out.The cream-coloured powder of leaching, and then, after ethanol purge 2 times, with washed with heptane, vacuum-drying, obtain compound (A73-1) 2.11g as cream-coloured powder.With compound (73-d) for benchmark, yield is 57%.

Compound (A73-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.45 ~ 1.85 (m, 24H), 2.36 ~ 2.87 (m, 15H), 3.93 ~ 3.97 (t, 4H), 4.15 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.45 (m, 2H), 6.87 ~ 6.99 (m, 8H), 7.13 ~ 7.16 (d, 1H), 7.23 (s, 2H), 7.38 (s, 1H), 7.51 (s, 1H), 7.57 (d, 1H).

The phase transition temperature of the compound (A73-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A73-1), when heating up, shows the high phase of viscosity, from 141 DEG C, provides clear and definite nematic phase from 82 DEG C to 141 DEG C.And then compound (A73-1), until more than 180 DEG C all in nematic phase, when lowering the temperature, is nematic phase and crystallization lentamente till 84 DEG C.

The synthesis example > of embodiment 48< compound (A63-1)

The synthesis example of (1) 3,4,6-trimethylammonium salicylic aldehyde

2,3,5-TEP 20.00g, paraformaldehyde 11.03g, Magnesium Chloride Anhydrous 20.97g are dispersed in 120g acetonitrile.In stirring at room temperature after 30 minutes, dripped triethylamine 29.72g with 2 hours.Mixture is reacted 8 hours in a water bath, room temperature reaction 96 hours.Reaction solution is injected the mixed solvent formed by the ethyl acetate of 200mL and the heptane of 400mL, add pure water 400mL.Add cold 2N-hydrochloric acid, after becoming acidity, reclaim organic layer.By anhydrous sodium sulphate by after organic layer, add silica gel 20g, gac 2g, leniently stir 30 minutes, dispersion liquid is carried out diatomite filtration.With vaporizer below 40 DEG C by filtrate reduced in volume, obtain 3,4, the 6-trimethylammonium salicylic aldehyde 24.69g as light yellow viscous liquid.Take 2,3,5-TEP as benchmark, yield is 102%.

(2) [the synthesis example of 4,6,7-trimethylammonium cumarone-2-carboxylic acid

Make 3,4,6-trimethylammonium salicylic aldehyde 24.11g, salt of wormwood 48.71g is dispersed in N, in N '-dimethyl ethanamide 130mL.After being heated to 80 DEG C, dripped bromo-acetic acid tert-butyl 28.64g with 30 minutes.By mixture in 140 DEG C of reactions 2 hours.After reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then, clean organic layer with 1N-hydrochloric acid water 500mL 2 times, reclaim organic layer.After anhydrous sodium sulfate dehydration, with vaporizer distillation except desolventizing.Residue is dissolved in 150g acetic acid, adds hydrobromic acid aqueous solution 45g, stir 1 hour in 40 DEG C.Let cool to room temperature, add 1N-hydrochloric acid 150g, the white powder that leaching is separated out.Obtained white powder used further 1N-hydrochloric acid, then use heptane, with after toluene cleaning, vacuum-drying, obtains 4,6, the 7-trimethylammonium cumarone-2-carboxylic acid 14.89g as cream-coloured powder thus.With 3,4,6-trimethylammonium salicylic aldehyde for benchmark, yield is 50%.

(3) synthesis example of compound (63-a)

Make 2,5-dimethoxyaniline 16.75g, 4,6,7-trimethylammonium cumarone-2-carboxylic acid 14.89g are dispersed in chloroform 75mL.Be cooled with an ice bath after obtained suspension, added the mixed solution of 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 15.37g and chloroform 100g with 4 hours, in room temperature reaction 72 hours.Obtained mixed solution is concentrated, in residue, adds mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) 400g, the heptane 150g of 1N-hydrochloric acid, methyl alcohol, make its crystallization.The precipitation that leaching obtains, adds in the mixing solutions (hydrochloric acid water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.Leaching pistac precipitates, and cleans with the mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, methyl alcohol 2 parts by volume) of the 1N-KOH aqueous solution-methyl alcohol, filters.Vacuum-drying, obtains compound (63-a) 22.71g as pale yellow powder.With 6-methyl benzofuran-2-carboxylic acid for benchmark, yield is 92%.

(4) synthesis example of compound (63-b)

By compound (63-a) 22.71g, 2, two (the 4-p-methoxy-phenyl)-1 of 4-, 3-bis-sulphur-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 16.24g and toluene 228g mixes, obtained mixture is warmed up to 110 DEG C, reacts 6 hours.After cooling, after toluene solution 2N-aqueous sodium hydroxide solution 500mL is cleaned 3 times, after reclaiming organic layer, concentrated, added heptane, made its crystallization.The light orange crystal that leaching obtains, vacuum-drying, obtains compound (63-b) 23.78g as bright-yellow powder thus.Its whole amount, although contain the resolvent of lawesson reagent, is directly used in subsequent step by compound (63-b).

(5) synthesis example of compound (63-c)

Compound (63-b) 23.78g, potassium hydroxide 20.48g and water 389g are mixed.Then, Tripotassium iron hexacyanide 60.09g is added, the dispersion liquid of modulation containing compound (63-b).Methyl alcohol 77.83g is added in dispersion liquid, in 50 DEG C of reactions 4 hours, in room temperature reaction 24 hours, the yellow mercury oxide that leaching is separated out.By the precipitation water filtered, then use washed with methanol.And then, yellow powder hot ethanol is cleaned, leaching.By obtained yellow substance vacuum-drying, the faint yellow solid 20.14g that to obtain with compound (63-c) be principal constituent.With compound (63-a) for benchmark, yield is 86%.

(6) synthesis example of compound (63-d)

By compound (63-c) 20.14g and pyridinium chloride 200.1g mixes, and is warmed up to 180 DEG C of reactions 3 hours.Obtained mixture is added in ice, the precipitation that leaching obtains.After aqueous suspension washing, with toluene cleaning, then, be dispersed in saturated SODIUM HYDROSULPHITE sodium water solution, chloroform, in stirring at room temperature 2 hours.Filter dispersion liquid, and then make its vacuum-drying with after pure water washing and precipitating, the orange solids 18.9g that to obtain with compound (73-d) be principal constituent.With compound (63-c) for benchmark, yield is 102%.

(7) synthesis example of compound (A63-1)

Compound (63-d) 1.10g, compound (A) 2.97g, dimethyl aminopyridine 0.04g and chloroform 20mL, toluene 20mL are mixed.N is added under ice-cooling, N '-DIC 1.02g in obtained mixture.Obtained reaction soln is made to react a night in room temperature.In reaction solution, add silica gel 4g, gac 200mg, in stirring at room temperature after 1 hour, carry out diatomite filtration.By filtrate reduced in volume, after removing chloroform, add methyl alcohol in the solution, crystal is separated out.The cream-coloured powder of leaching, and then, after ethanol purge 2 times, with washed with heptane, vacuum-drying, obtain compound (A63-1) 2.65g as cream-coloured powder.With compound (63-d) for benchmark, yield is 70%.

Compound (A63-1) ¹h-NMR (CDCl ₃): δ (ppm) 1.47 ~ 1.82 (m, 24H), 2.36 ~ 2.52 (m, 17H), 2.52 ~ 2.85 (m, 4H), 3.93 ~ 3.97 (t, 4H), 4.16 ~ 4.20 (t, 4H), 5.79 ~ 5.84 (dd, 2H), 6.07 ~ 6.17 (m, 2H), 6.37 ~ 6.45 (m, 2H), 6.87 ~ 7.05 (m, 9H), 7.23 (s, 2H), 7.53 (s, 1H).

The phase transition temperature of the compound (A63-1) obtained confirms by adopting polarized light microscope observing structure.Compound (A63-1), when heating up, shows the high phase of viscosity, from 139 DEG C, provides clear and definite nematic phase from 136 DEG C to 139 DEG C.And then compound (A63-1), until more than 180 DEG C all in nematic phase, is nematic phase and crystallization when lowering the temperature till 125 DEG C.

Embodiment 49 ~ 51 and comparative example 1

The Production Example > of < blooming

At the 2 quality % aqueous solution of glass substrate pva coating (the fully saponified type of polyvinyl alcohol 1000, Wako Pure Chemical Industries, Ltd.'s system), after drying, form the film of thickness 89nm.Then, friction treatment is implemented to the surface of obtained film, by the composition of the composition of spin-coating method coating table 17 on the face implementing friction treatment, drying 1 minute under the drying temperature described in table 18.Next, be heated to the temperature during rayed described in table 18, the ultraviolet of the integrating light quantity of exposure chart 18 record simultaneously, forms the blooming of the thickness described in table 19.

[table 17]

LC242: the same

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

[table 18]

	Drying temperature after coating	Temperature during rayed	Integrating light quantity (mJ/cm ²)
				Embodiment 49	155℃	120℃	2400
Embodiment 50	110℃	90℃	2400
				Embodiment 51	155℃	120℃	2400
Comparative example 1	45℃	Room temperature	1200

The mensuration > of < optical characteristics

Measuring machine (KOBRA-WR, prince measures machines corporation system) is used to measure the front phase difference value of blooming.It should be noted that, because the glass substrate used in base material does not have birefringence, so measure the film of subsidiary glass substrate by measuring machine, the front phase difference value of the blooming that just can be made on the glass substrate.The optical detecting front phase difference value obtained measures respectively at wavelength 447.3nm, 546.9nm and 627.8nm, calculates [Re (447.3)/Re (546.9)] (as α) and [Re (627.8)/Re (546.9)] (as β).In addition, laser microscope (LEXT, Olympus Corp's system) is used to measure the thickness d (μm) of blooming.Table 19 will be the results are shown in.△ n (△ n=Re (546.9)/d) is calculated divided by thickness by the value of Re (546.9).

[table 19]

	Re(546.9)	α	β	d(μm)	⊿n
						Embodiment 49	126.4	0.791	1.039	2.573	0.049
Embodiment 50	142.4	0.898	1.016	2.091	0.068
						Embodiment 51	126.8	0.853	1.026	2.528	0.050
Comparative example 1	141.0	1.075	0.978	1.001	0.141

Blooming of the present invention can carry out same polarized light conversion in the wavelength region of broadness.

Claims

1. with the compound that formula (3-1) represents,

In formula (3-1), Z ¹and Z ²represent hydrogen atom independently of one another,

Q ¹represent-S-or-O-,

D ¹and D ²represent-CO-O-or-O-CO-independently of one another,

G ¹and G ²represent Isosorbide-5-Nitrae-hexanaphthene two base,

E ¹and E ²represent-CO-O-or-O-CO-independently of one another,

B ¹and B ²expression-O-,

A ¹and A ²represent Isosorbide-5-Nitrae-phenylene,

K and l represents 1 independently of one another,

F ¹and F ²represent the alkane 2 basis of carbonatoms 1 ~ 12 independently of one another,

P ¹and P ²represent acryloxy or methacryloxy independently of one another,

Y ¹with formula (Y ¹-2) group represented,

Formula (Y ¹-2) in, Z ³represent the alkylthio of the alkoxyl group of the fluoroalkyl of the alkyl sulphinyl of the alkyl sulphonyl of the alkyl of halogen atom, carbonatoms 1 ~ 6, cyano group, nitro, nitroso-group, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, carbonatoms 1 ~ 6, the N of carbonatoms 2 ~ 8 independently of one another; the N-alkylamino of N-dialkyl amido, carbonatoms 1 ~ 4, sulfamyl, the N-alkylsulfamoyl group of carbonatoms 1 ~ 6, the N of carbonatoms 2 ~ 12; N-dialkyl sulfamine or-COOH

V ¹and V ²represent-CO-,-S-,-NR independently of one another ³-,-O-,-Se-or-SO ₂-,

W ¹and W ²expression-CR independently of one another ³=or-N=, wherein R ³represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4 independently of one another,

B represents the integer of 0 ~ 2 independently of one another.

2. compound as claimed in claim 1, wherein, V ¹for-S-,-NR ³-or-O-.

3. a composition, it contains compound according to claim 1, and liquid crystalline cpd, this liquid crystalline cpd is different from compound according to claim 1, this liquid crystalline cpd is the compound shown in formula (I-1) ~ formula (I-5), compound shown in formula (B1-1) ~ formula (B20-8), compound shown in formula (C1-1) ~ formula (C4-8), compound shown in formula (II-1) ~ formula (II-6), compound shown in formula (III-1) ~ formula (III-19), compound shown in formula (IV-1) ~ formula (IV-14), or the compound shown in formula (V-1) ~ formula (V-5),

4. composition as claimed in claim 3, wherein, also containing polymerization starter.

5. composition as claimed in claim 4, wherein, polymerization starter contains acetophenone compound.

6. a blooming, by obtaining compound polymerization according to claim 1.

7. a blooming, by obtaining the composition polymerization according to any one of claim 3 ~ 5.

8. blooming as claimed in claims 6 or 7, the phase difference value Re (550) for wavelength 550nm place is λ/4 plate of 113 ~ 163nm.

9. blooming as claimed in claims 6 or 7, the phase difference value Re (550) for wavelength 550nm place is λ/2 plate of 250 ~ 300nm.

10. a polaroid, wherein, containing the blooming according to any one of claim 6 ~ 9 and polarizing coating.

11. 1 kinds of colour filters, wherein, are coating the blooming alignment films on filter substrate is formed with according to any one of claim 6 ~ 9.

12. 1 kinds of liquid crystal indicators, wherein, containing colour filter according to claim 11.

13. 1 kinds of panel display apparatus, wherein, possess the liquid crystal panel containing polaroid according to claim 10.

14. 1 kinds of organic EL displays, wherein, possess the organic electroluminescence panel containing polaroid according to claim 10.

The manufacture method of 15. 1 kinds of non-polymeric membrane, is characterized in that, by the solution coat containing compound described in claim 1 on supporting substrate or be coated in the alignment films that is formed on supporting substrate, and makes it dry.

The manufacture method of 16. 1 kinds of bloomings, is characterized in that, makes the non-polymeric membrane solidification obtained by manufacture method according to claim 15.