CN101838264A

CN101838264A - The manufacture method of compound, blooming and blooming

Info

Publication number: CN101838264A
Application number: CN201010133280A
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: 2010-09-22
Anticipated expiration: 2030-03-12
Also published as: CN104592219B; KR20100105411A; CN101838264B; CN104592219A; TWI482769B; KR101641385B1; TW201100410A

Abstract

The present invention relates to the manufacture method of compound, blooming and blooming.Specifically, relate to the compound of the divalent group shown in (1-1) or the formula (1-2) that has formula and make this compound polymerization and the blooming that obtains.

In the formula, Z ¹And Z ²Represent hydrogen atom etc. independently of one another; Q ¹And Q ²Expression-S-etc. independently of one another; Y ¹Expression replaces or unsubstituted polycycle aromatic hydrocarbyl or replacement 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.

Description

The manufacture method of compound, blooming and blooming

Technical field

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

Background technology

Contain the parts that polaroid, polarizer etc. have used blooming in the panel display apparatus (FPD).As blooming, can enumerate solvent polymerization compound in solvent and solution coat behind supporting substrate, carry out polymerization and the blooming that obtains.As such polymerizable compound, at SID Symposium Digest of Technical Papers, 2006,37 volumes disclosed the compound shown in the following formula (LC242) in p.1673.

Summary of the invention

The invention provides following scheme etc.

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

(in the formula, Z ¹And Z ²The alkyl, cyano group, nitro, 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 1～6, the N of carbonatoms 2～12 of representing hydrogen atom, halogen atom, carbonatoms 1～6 independently of one another; the N-alkylsulfamoyl group of N-dialkyl amido, carbonatoms 1～6, the N of carbonatoms 2～12, the 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 ²The alkyl of representing hydrogen atom or carbonatoms 1～4 independently of one another.

Y ¹Expression replaces or unsubstituted polycycle aromatic hydrocarbyl or replacement 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 the alkyl of halogen atom, carbonatoms 1～4, the fluoroalkyl of carbonatoms 1～4, alkoxyl group, cyano group or the nitro of carbonatoms 1～4, this ester ring type alkyl-CH ₂-can with-O-,-S-or-the NH-displacement.)

[2], wherein, has the divalent group of formula (2-1) or formula (2-2) expression as [1] described compound.

(in the formula, Z ¹, Z ², Q ¹, Q ², Y ¹, D ¹, D ², G ¹And G ²The expression and the identical meaning of [1] middle definition respectively.

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

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

[3] as [1] described compound, with formula (3-1) or formula (3-2) expression.

(in the 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 respectively and [1] and [2] in the identical meaning of definition.

F ¹And F ²The alkane 2 basis of representing 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, this alkane 2 basis-CH ₂-can with-O-or-the CO-displacement.

P ¹And P ²Represent hydrogen atom or polymerizable group independently of one another.)

[4] as each described compound in [1]～[3], wherein, Y ¹Be formula (Y ¹-1) or formula (Y ¹-4) Biao Shi group.

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

V ¹Expression-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 ³The alkyl of representing 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 0～3 integer independently of one another.)

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

(in the formula, Z ³, a, V ¹And W ²The expression and the identical meaning of [4] middle definition respectively.)

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

[7] as each described compound in [1]～[6], wherein, G ¹And G ²For instead-1,4-hexanaphthene two bases.

[8] as each described compound in [2]～[7], wherein, A ¹And A ² Represent 1 independently of one another, 4-phenylene or 1,4-hexanaphthene two bases, this 1,4-phenylene and 1,4-hexanaphthene two bases can have alkyl, trifluoromethyl, cyano group or the nitro of halogen atom, carbonatoms 1～4.

[9] as each described compound in [3]～[8], wherein, only with A ¹Bonded B ¹Only with A ²Bonded B ²Be independently of one another-CH ₂-CH ₂-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-O-CH ₂-,-CH ₂-O-or singly-bound,

With F ¹Bonded B ¹With with F ²Bonded B ²Be independently of one another-O-,-CO-O-,-O-CO-,-O-CO-O-,-CO-NH-,-NH-CO-or singly-bound.

[10] as each described compound in [3]～[9], wherein, P ¹And P ²Be hydrogen atom, acryloxy or methacryloxy independently of one another, and P ¹And P ²Be not hydrogen atom simultaneously.

[11] a kind of composition, wherein, contain [1]～[10] in each described compound and liquid crystalline cpd (but being different from above-claimed cpd).

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

(in the formula, A ¹¹Represent divalence aromatic hydrocarbyl, 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 the alkyl of halogen atom, 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)-and CH=CH-or singly-bound, R ¹⁴And R ¹⁵The alkyl of representing hydrogen atom, fluorine atom or carbonatoms 1～4 independently of one another, perhaps R ¹⁴And R ¹⁵In conjunction with and the expression carbonatoms 4～7 alkane 2 basis.R ¹⁶The alkyl of expression hydrogen atom or carbonatoms 1～4.

E ¹¹The alkane 2 basis of expression 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 ¹¹The expression polymerizable group.

G represents the alkyl of hydrogen atom, halogen atom, 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, perhaps expression has the alkyl of the carbonatoms 1～18 of polymerizable group, and this alkyl can have the alkoxy or halogen atom of carbonatoms 1～6.

T represents 1～5 integer.)

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

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

[15] a kind of blooming is by obtaining each described compound polymerization in [1]～[10].

[16] a kind of blooming is by obtaining each described composition polymerization in [11]～[14].

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

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

[19] a kind of polaroid, wherein, contain [15]～[18] in each described blooming and polarizing coating.

[20] a kind of colour filter, wherein, be formed with on the alignment films on coating filter substrate [15]～[18] in each described blooming.

[21] a kind of liquid crystal indicator wherein, contains [20] described colour filter.

[22] a kind of panel display apparatus wherein, possesses the liquid crystal panel that contains [19] described polaroid.

[23] a kind of organic EL display wherein, possesses the organic electroluminescence panel that contains [19] described polaroid.

[24] a kind of manufacture method of not polymeric membrane is characterized in that, will contain [1]～[10] in the solution coat of each described compound on the supporting substrate or be coated on the alignment films that is formed on the supporting substrate, and make it dry.

[25] a kind of manufacture method of blooming is characterized in that, the not polymeric membrane that obtains by [24] described manufacture method is solidified.

Description of drawings

Fig. 1 is the synoptic diagram of expression colour filter 1 of the present invention.

Fig. 2 is the synoptic diagram of expression liquid crystal indicator 5 of the present invention.

Fig. 3 is the synoptic diagram of expression polaroid 30 of the present invention.

Fig. 4 is the synoptic diagram of the applying product 21 of expression liquid crystal panel 20 of liquid crystal indicator of the present invention and polaroid 30.

Fig. 5 is the synoptic diagram of organic EL plate 23 of expression 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 applying product

23 organic EL plates

24 luminescent layers

Embodiment

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

In formula (1-1) and the formula (1-2), Z ¹And Z ²The alkyl, amino, nitro, 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 1～6, the N of carbonatoms 2～12 of representing hydrogen atom, halogen atom, carbonatoms 1～6 independently of one another; the N-alkylsulfamoyl group of N-dialkyl amido, carbonatoms 1～6, the N of carbonatoms 2～12, the N-dialkyl sulfamine or-COOH.

As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms and iodine atom, preferred fluorine atom, chlorine atom and bromine atoms.

Alkyl as carbonatoms 1～6, can enumerate methyl, ethyl, propyl group, sec.-propyl, sound of chopping wood base, isobutyl-, sec-butyl, the tertiary butyl, amyl group and hexyl, the alkyl of preferred carbonatoms 1～4, the more preferably alkyl of carbonatoms 1～2, preferable methyl especially.

Alkyl sulphinyl as carbonatoms 1～6; can enumerate methylsulfinyl, ethyl sulfinyl, propyl group sulfinyl, sec.-propyl sulfinyl, butyl sulfinyl, isobutyl-sulfinyl, sec-butyl sulfinyl, tertiary butyl sulfinyl, amyl group sulfinyl and hexyl sulfinyl; the alkyl sulphinyl of preferred carbonatoms 1～4; the more preferably alkyl sulphinyl of carbonatoms 1～2, special preferable methyl sulfinyl.

Alkyl sulphonyl as carbonatoms 1～6; can enumerate methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, sec.-propyl alkylsulfonyl, butyl alkylsulfonyl, isobutyl-alkylsulfonyl, sec-butyl alkylsulfonyl, tertiary butyl alkylsulfonyl, amyl group alkylsulfonyl and hexyl alkylsulfonyl; the alkyl sulphonyl of preferred carbonatoms 1～4; the more preferably alkyl sulphonyl of carbonatoms 1～2, special preferable methyl alkylsulfonyl.

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

Alkoxyl group as carbonatoms 1～6, can enumerate methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy and hexyloxy, the alkoxyl group of preferred carbonatoms 1～4, the more preferably alkoxyl group of carbonatoms 1～2, preferred especially methoxyl group.

Alkylthio as carbonatoms 1～6, can enumerate methylthio group, ethylmercapto group, rosickyite base, iprotiazem base, butylthio, isobutyl sulfenyl, secondary butylthio, uncle's butylthio, penta sulfenyl and own sulfenyl, the alkylthio of preferred carbonatoms 1～4, the more preferably alkylthio of carbonatoms 1～2, preferred especially methylthio group.

N-alkylamino as carbonatoms 1～6, can enumerate N-methylamino, N-ethylamino, N-propyl group amino, N-sec.-propyl amino, N-butyl amino, N-isobutylamino, N-sec-butyl amino, N-tertiary butyl amino, N-amyl group amino and N-hexyl amino, the N-alkylamino of preferred carbonatoms 1～4, the more preferably N-alkylamino of carbonatoms 1～2, preferred especially N-methylamino.

As the N of carbonatoms 2～12, the N-dialkyl amido can be enumerated N, N-dimethylamino, N-methyl-N-ethylamino, N, N-diethylamino, N, N-dipropyl amino, N, N-diisopropylaminoethyl, N, N-dibutylamino, N, N-diisobutyl amino, N, N-diamyl amino and N, N-dihexyl amino, the N of preferred carbonatoms 2～8, the N-dialkyl amido, the more preferably N of carbonatoms 2～4, N-dialkyl amido, preferred especially N, the N-dimethylamino.

N-alkylsulfamoyl group as carbonatoms 1～6; can enumerate N-methyl sulfamyl, N-ethyl sulfamyl, N-propyl group sulfamyl, N-sec.-propyl sulfamyl, N-butyl sulfamyl, N-isobutyl-sulfamyl, N-sec-butyl sulfamyl, N-tertiary butyl sulfamyl, N-amyl group sulfamyl and N-hexyl sulfamyl; the N-alkylsulfamoyl group of preferred carbonatoms 1～4; the more preferably N-alkylsulfamoyl group of carbonatoms 1～2, preferred especially N-methyl sulfamyl.

N as carbonatoms 2～12; the N-dialkyl sulfamine; can enumerate N; N-dimethylamino alkylsulfonyl, 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; the N-dialkyl sulfamine, the more preferably N of carbonatoms 2～4, N-dialkyl sulfamine; preferred especially N, N-dimethylamino alkylsulfonyl.

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-methyl sulfamyl, N, N-dimethylamino alkylsulfonyl 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 ²The alkyl of representing hydrogen atom or carbonatoms 1～4 independently of one another.As R ¹And R ²The alkyl of carbonatoms 1～4, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-and the tertiary butyl, the alkyl of preferred carbonatoms 1～2, more preferably methyl.

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

As the group of the expression of the formula (1-1-A) in the divalent group shown in the formula (1-1), can enumerate the group shown in following formula (1-1-1)～formula (1-1-18).

As the group of the expression of the formula (1-2-A) in the divalent group shown in the formula (1-2), can enumerate the group shown in following formula (1-2-1)～formula (1-2-5).

In formula (1-1) and the formula (1-2), Y ¹Expression replaces or unsubstituted polycycle aromatic hydrocarbyl or replacement or unsubstituted polycycle aromatic heterocycle." polycycle aromatic hydrocarbyl " means the aromatic hydrocarbyl with at least 2 aromatic nucleus, can enumerate 2 above aromatic nucleus condense and form condense the above aromatic nucleus of aromatic hydrocarbyl and 2 in conjunction with and the aromatic hydrocarbyl that forms." polycycle aromatic heterocycle " means to have at least 1 aromatic heterocycle and have the aromatic heterocycle that is selected from least 1 ring in aromatic nucleus and the aromatic heterocycle, can enumerate 1 above heteroaromatic with being selected from that ring more than 1 in aromatic nucleus and the aromatic heterocycle condenses the aromatic heterocycle that forms and at least 1 aromatic heterocycle with being selected from that at least 1 loops in aromatic nucleus and the aromatic heterocycle closes the aromatic heterocycle that forms.

Polycycle aromatic hydrocarbyl and polycycle aromatic heterocycle both can be not have to replace, and also can have substituting group.As substituting group; can enumerate the alkyl, 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 of halogen atom, carbonatoms 1～6; the N-alkylsulfamoyl group of N-dialkyl amido, sulfamyl, carbonatoms 1～6, the N of carbonatoms 2-12, the N-dialkyl sulfamine and-COOH.

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

V ¹And V ²Independently of one another expression-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 ³The alkyl of representing 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 0～3 integer independently of one another, and b represents 0～2 integer independently of one another.)

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

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

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

(in the 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; the N-dialkyl sulfamine can be enumerated 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; more preferably halogen atom, methyl, ethyl, sec.-propyl, sec-butyl, amyl group, hexyl, cyano group, nitro or trifluoromethyl are preferably methyl, ethyl, sec.-propyl, sec-butyl, amyl group or hexyl especially.

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

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

V ¹, V ²And W ¹～W ⁵In at least one preferably contain S, N or O.

A is preferably 0 or 1, and b is preferably 0.

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

In formula (1-1) and the 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 ⁷The alkyl (for example methyl, ethyl, propyl group, sec.-propyl, butyl etc.) of representing hydrogen atom, fluorine atom or carbonatoms 1～4 independently of one another, R ⁸The alkyl (for example methyl, ethyl, propyl group, sec.-propyl, butyl etc.) of expression 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-, more preferably *-O-CO-, *-O-C (=S)-or *-NR ⁸-CO-.Herein, * represents and the group shown in the formula (1-1-A) or the combining site of the group shown in the 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, more preferably hydrogen atom, methyl or ethyl.R ⁸Be preferably hydrogen atom, methyl or ethyl.

In formula (1-1) and the 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 be used the alkyl of halogen atom, carbonatoms 1～4, the fluoroalkyl of carbonatoms 1～4, alkoxyl group, cyano group or the nitration of carbonatoms 1～4, this ester ring type alkyl-CH ₂-can with-O-,-S-or-the NH-displacement.

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

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

G ¹And G ²Be preferably the group shown in the formula (g-1), more preferably 1,4-hexanaphthene two bases, be preferably especially anti--1,4-hexanaphthene two bases.

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

(in the 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 represent 0～3 integer independently of one another.)

As E ¹And E ²Divalent linker, can enumerate-CR 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 ¹⁰The alkyl of representing hydrogen atom, fluorine atom or carbonatoms 1～4 independently of one another, R ¹¹The alkyl of expression hydrogen atom or carbonatoms 1～4.

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

As B ¹And B ²Divalent linker, can enumerate-CR 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-.

From the easy viewpoint of making of compound of the present invention, only with A ¹Bonded B ¹Only with A ²Bonded B ²Be preferably independently of one another-CH ₂-CH ₂-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-O-CH ₂-,-CH ₂-O-or singly-bound, the viewpoint from the high liquid crystal liquid crystal property of compound exhibits of the present invention, be preferably-CO-O-or-O-CO-.

From the viewpoint of the easier manufacturing of compound of the present invention, preferred B ¹With B ²Identical.

As A ¹And A ²Divalence ester ring type alkyl or divalence aromatic hydrocarbyl, can enumerate the divalence aromatic hydrocarbyl of the carbonatoms 6～20 shown in the group shown in above-mentioned formula (g-1)～formula (g-10), following formula (the a-1)～formula (a-8).

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

Wherein, A ¹And A ²Be preferably 1 independently of one another, 4-phenylene or 1,4-hexanaphthene two bases, the viewpoint of making easily from compound of the present invention, more preferably 1,4-phenylene.

From the viewpoint of the easier manufacturing of compound of the present invention, preferred A ¹With A ²Identical.

From the viewpoint of the liquid crystal liquid crystal property of compound of the present invention, preferred k and l are 0～2.Preferred k and l's and be below 5 is more preferably below 4.

The compound of compound of the present invention formula (3-1) or formula (3-2) expression more preferably.

(in the 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, preferred-(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 ¹Bonded B ¹With with F ²Bonded B ²Be preferably independently of one another-O-,-CO-O-,-O-CO-,-O-CO-O-,-CO-NH-,-NH-CO-or singly-bound.

Preferred P ¹And P ²In at least one be polymerizable group, have the viewpoint of excellent tendency, more preferably P from the film hardness of the blooming that obtains by compound of the present invention ¹And P ²Be polymerizable group.

Polymerizable group be so long as can participate in the group of the polyreaction of The compounds of this invention and get final product, and specifically can enumerate N-alkylamino, amino, epoxy group(ing), oxetanyl (oxetanyl group), formyl radical, isocyanate base and the isothiocyanic acid foundation of vinyl, vinyloxy group, styryl, right-(2-phenyl vinyl) phenyl, acryl, methacryloyl, acryloxy, methacryloxy, carboxyl, ethanoyl, hydroxyl, formamyl, carbonatoms 1～4.Wherein, from being suitable for photopolymerisable viewpoint, preferred free-radical polymerised group or cationically polymerizable group, the viewpoint of also making easily from processing ease, compound of the present invention, more preferably acryloxy or methacryloxy, preferred especially acryloxy.

Polymerizable group can be directly and F ¹And F ²In conjunction with, but preferably by divalent linker (for example described B more than 1 ¹And B ²Divalent linker etc.) combination.

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, can enumerate the group of formula (R-1)～formula (R-134) expression.Should illustrate that in the following formula, * represents and the combining site of the group shown in formula (1-1-A) or the formula (1-2-A) that n represents 2～12 integer.

As compound of the present invention, can enumerate the compound shown in formula (A1-1)～formula (A73-8).Should illustrate that in the following formula, * represents combining site, for example the compound of formula (A1-1) expression is following compound.

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

Compound of the present invention can be according to its structure, by with Methoden derOrganischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, known organic synthesis (for example condensation reaction of record in the new experimental chemistry lecture etc., esterification, Williamson's reaction, ullmann reaction, witig reaction, the schiff bases formation reaction, the reaction of benzyl reaction Yuan head, Suzuki-Pu, palace reaction, the reaction of root bank, the reaction of bear field, Hui Shan reacts (Hiyama reaction), the Buchwald-Hartwig reaction, Friedel-Crafts reaction, the He Ke reaction, Aldol reaction etc.) appropriate combination and making.

D for example ¹And D ²For the formula (3-1) of *-O-CO-or the compound shown in the formula (3-2) can be made by the following method: by making the compound reaction shown in compound shown in the formula (11-1) and the formula (11-2), obtain the compound shown in the formula (11-3), make the compound reaction shown in compound shown in the resulting formula (11-3) and the formula (11-4) then.

HO-Ar-OH????(11-1)

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

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

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

(in the formula, G ², E ², A ², B ², F ², P ²Represent implication same as described above 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 under the identical situation, can react by making above formula (11-2) compound of the compound shown in the formula (11-1) and 2 equivalents, with a step manufacturing objective compound.

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

As condensing agent, can enumerate 1-cyclohexyl-3-(2-morpholino ethyl) carbodiimide tosilate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, two (2, the 6-diisopropyl phenyl) carbodiimide, two (trimethyl silyl) carbodiimide, N, N '-carbodiimide compounds 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-oil of mirbane alkylsulfonyl)-1H-1; 2; the 4-triazole; 1H-benzotriazole-1-base oxygen base tripyrrole Wan Ji Phosphonium hexafluorophosphate; 1H-benzotriazole-1-base oxygen base three (dimethylamino) Phosphonium hexafluorophosphates; N; N; N '; N '-tetramethyl--O-(N-succinimido) urea a tetrafluoro borate; N-(1; 2; 2; 2-tetrachloro ethoxy carbonyl oxygen base) succinimide; N-benzene methoxy carbonyl acyl succinimide; O-(6-chlorinated benzotriazole-1-yl)-N; N; N '; N '-tetramethyl-urea a tetrafluoro borate; O-(6-chlorinated benzotriazole-1-yl)-N; N; N '; N '-tetramethyl-urea hexafluorophosphate; 2-bromo-1-ethylpyridine a tetrafluoro borate; 2-chloro-1; 3-methylimidazole muriate; 2-chloro-1,3-methylimidazole hexafluorophosphate; 2-chloro-1-picoline iodide; 2-chloro-1-picoline tosilate; 2-fluoro-1-picoline tosilate; trichoroacetic acid(TCA) five chlorophenyl ester etc.Select many viewpoints from reactive, the 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, the 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.

Concrete example as liquid crystalline cpd, can enumerate the compound that has polymerizable group in the compound that " liquid crystal brief guide (the liquid crystal brief guide council that compiles compiles, and ball kind (strain) is put down into distribution on October 30th, 12), 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 " put down in writing.

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

Contain the composition of The compounds of this invention and liquid crystalline cpd by use, optical characteristics, hot rerum naturas such as the wavelength dispersion value of the blooming that makes the said composition polymerization and obtain, phasic difference value can be adjusted to desirable value.

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

(in the formula, A ¹¹Represent divalence aromatic hydrocarbyl, 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 the alkyl of halogen atom, 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)-and CH=CH-or singly-bound, R ¹⁴And R ¹⁵The alkyl of representing hydrogen atom, fluorine atom or carbonatoms 1～4 independently of one another, perhaps R ¹⁴And R ¹⁵In conjunction with and the expression carbonatoms 4～7 alkane 2 basis.R ¹⁶The alkyl of expression hydrogen atom or carbonatoms 1～4.E ¹¹The alkane 2 basis of expression 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 ¹¹The expression polymerizable group.

T represents 1～5 integer.)

Particularly as P ¹¹With the polymerizable group among the G; so long as can get final product with the group of compound polymerization of the present invention, can enumerate vinyl, vinyl oxygen base, styryl, right-(2-phenyl vinyl) phenyl, acryl, acryloxy, methacryloyl, methacryloxy, carboxyl, ethanoyl, hydroxyl, formamyl, amino, carbonatoms 1～4 N-alkylamino, epoxy group(ing), oxetanyl, formyl radical ,-N=C=O or-N=C=S etc.Wherein, from the high viewpoint of photopolymerisable reactivity, preferred free-radical polymerised group or cationically polymerizable group are from the also easy viewpoint of manufacturing of processing ease and liquid crystalline cpd, preferred acryloxy, methacryloxy or vinyloxy group.

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

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

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 the formula, P ¹¹, E ¹¹, B ¹¹, A ¹¹, B ¹²Represent the meaning same as described above.

F ¹¹Expression 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 ¹²The alkane 2 basis of expression 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 ¹²The expression polymerizable group.

t ¹And t ²The integer of expression 1～5.)

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

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 the formula, A ¹²～A ¹⁵Expression and A ¹¹Identical implication, B ¹³～B ¹⁶Expression and B ¹¹Identical implication.)

In the compound shown in formula (20-1), formula (20-2), formula (I), formula (II), formula (III), formula (IV) and the 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, can enumerate the compound shown in the compound equation (I) shown in following formula (I-1)～formula (I-5), formula (B1-1)～formula (B20-8) and formula (the C1-1)～formula (C4-8); Compound shown in the compound equation (II) shown in formula (II-1)～formula (II-6); Compound shown in the compound equation (III) shown in formula (III-1)～formula (III-19); Compound shown in the compound equation (IV) shown in formula (IV-1)～formula (IV-14); Compound shown in the formula V such as compound shown in formula (V-1)～formula (V-5) etc.Should illustrate that in the following formula, k represents 1～11 integer, * represents combining site.These liquid crystalline cpds are synthetic easily or have commercially available and viewpoint easy acquisition is preferred liquid crystalline cpd from it.

Use under the situation of the composition that contains liquid crystalline cpd for the hot rerum natura of controlling resulting blooming, viewpoint from the reliability excellence 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 viewpoint to the intermiscibility excellence of The compounds of this invention, preferred formula (I-1)～formula (I-5), formula (B1-1)～formula (B20-8), liquid crystalline cpd shown in formula (C1-1)-Shi (C4-8) and formula (III-1)～formula (III-19).From obtaining to show the viewpoint of the long dispersive blooming of head sea, the liquid crystalline cpd shown in preferred formula (B1-1)-Shi (B20-8) and formula (C1-1)～formula (C4-8).

With respect to total 100 weight parts 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 preferably also contains polymerization starter.Polymerization starter preferably contains Photoepolymerizationinitiater initiater, as Photoepolymerizationinitiater initiater, preferably produces the Photoepolymerizationinitiater initiater of free radical by rayed.

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

As the bitter almond oil camphor compound, can enumerate bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether and bitter almond oil camphor ethyl isobutyl ether.

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

As acetophenone compound, can enumerate α, α-diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-methylthio group phenyl) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) 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, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligopolymer of propane-1-ketone.

As the acylphosphine oxide compound, can enumerate 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide.

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

As Photoepolymerizationinitiater initiater, also can use IRGACURE907 (Ciba Japan Co., Ltd. system), 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 corporate system), ADEKA OPTOMER SP-152 (ADEKA Co., Ltd. system), ADEKA OPTOMER SP-170 (ADEKA Co., Ltd. system), TAZ-A (Japanese Siber Hegner corporate system), TAZ-PP (Japanese Siber Hegner corporate system), commercially available products such as TAZ-104 (three and chemical company's system).

From the viewpoint that the thermotolerance and the humidity resistance of gained blooming has the tendency that increases, as Photoepolymerizationinitiater initiater, preferably use acetophenone compound, more preferably 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone.

With respect to total 100 weight parts of liquid crystalline cpd and The compounds of this invention, the content of polymerization starter is generally 0.1～30 weight part in the composition of the present invention, is preferably 0.5～10 weight part.As long as in above-mentioned scope, just can under the situation of the orientation of not upsetting liquid crystalline cpd, make compound polymerization of the present invention.

Composition of the present invention can contain photosensitizers.As photosensitizers, can enumerate xanthone compounds such as xanthone, thioxanthone (for example 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone etc.), anthracene, have substituent anthracene compounds such as alkoxyl group (for example dibutoxy anthracene etc.), thiodiphenylamine and rubrene.

By using photosensitizers, can carry out the polyreaction of The compounds of this invention with highly sensitive, the ageing stability of resulting blooming is improved.With respect to total 100 weight parts 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 can under the situation of the orientation of not upsetting liquid crystalline cpd, make compound polymerization of the present invention.

Composition of the present invention can contain polymerization retarder.As polymerization retarder, can enumerate Resorcinol, have substituent Resorcinol compound, butyl-catechols etc. such as alkoxyl group and have substituent pyrocatechol compound, pyrogallol compounds, 2 such as alkyl, 2,6,6-tetramethyl piperidine-radical scavengers such as 1-oxyradical, thiophenol compound, beta-naphthylamine compound, 2-Naphthol compound etc.

By using polymerization retarder, the control of the polyreaction of liquid crystalline cpd, The compounds of this invention becomes easily, can improve the stability of resulting blooming.With respect to total 100 weight parts 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 can under the situation of the orientation of not upsetting liquid crystalline cpd, make compound polymerization of the present invention.

Composition of the present invention can contain flow agent.As flow agent, can enumerate radiation-curing coating additive (BYK-Chemie Japan system: BYK-352, 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 be additive (Dainippon Ink Chemicals's system: F-445, F-470, F-479) etc.

By using flow agent, can access more level and smooth blooming.In addition, in the manufacturing processed of blooming, also can control the flowability of composition of the present invention, perhaps adjust the cross-linking density in the resulting blooming.With respect to total 100 weight parts 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 can under the situation of the orientation of not upsetting liquid crystalline cpd, make compound polymerization of the present invention.

Composition of the present invention is considered from its mobile aspect, is preferably contained organic solvent.As organic solvent, so long as can dissolve the organic solvent of The compounds of this invention, liquid crystalline cpd etc. and polyreaction is got final product for the inert solvent, specifically can enumerate alcoholic solvents such as methyl alcohol, ethanol, ethylene glycol, Virahol, propylene glycol, ethylene glycol monomethyl ether, butyl glycol ether; Ester solvents such as ethyl acetate, butylacetate, ethylene glycol monomethyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, pimelinketone, 2-heptanone, methyl iso-butyl ketone (MIBK); Non-chlorinated aliphatichydrocarbon solvents such as pentane, hexane, heptane; Non-chlorinated aromatic hydrocarbons solvents such as toluene, dimethylbenzene, phenol; Nitrile solvents such as acetonitrile; Ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran (THF), glycol dimethyl ether; Chlorinated hydrocarbon solvent such as chloroform, chlorobenzene; Phenol etc.These organic solvents can use separately, also can be used in combination of two or more.Compound particularly of the present invention and composition intermiscibility excellence of the present invention, can be dissolved in alcoholic solvent, ester solvent, ketone solvent, non-chlorinated aliphatichydrocarbon solvent and non-chlorinated aromatic hydrocarbons solvent, so can under the situation of not using chlorinated hydrocarbon solvents such as chloroform, carry out film forming.

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

Composition of the present invention contains under the situation of organic solvent, has the tendency of difficult generation from the thickness inequality of blooming, and its viscosity is generally 0.1～10Pas, is preferably 0.1～7Pas.

In addition, the concentration of solids component is generally 2～50 weight % in the composition of the present invention, is preferably 5～50 weight %.The concentration of solids component is 2 weight % when above, and blooming can be not thin excessively, has the tendency of the blooming of the necessary degree of birefringence of optical compensation that obtains to have liquid crystal panel easily.In addition, the concentration of solids component is 50 weight % when following, and the viscosity of composition can be not too small, has the tendency of the thickness inequality that is difficult for producing blooming.Herein, so-called " solids component " is meant the composition of removing behind the organic solvent from composition of the present invention.

Then, blooming of the present invention is described.

In the present invention, so-called " blooming " is meant film transmissive light, that have optical function.So-called optical function is meant refraction, double refraction etc.A kind of phase retardation film as blooming is used for rectilinearly polarized light is converted to circularly polarized light, elliptically polarized light, perhaps 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 that derives from The compounds of this invention, can adjust the wavelength dispersion characteristic of blooming by the content of adjusting this structural unit.Increase if derive from the content of the structural unit of The compounds of this invention in the blooming, then show more flat wavelength dispersion characteristic, and then show the long dispersing characteristic of head sea.

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

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

(b) to synthetic each composition, make the different blooming of content of structural unit identical thickness, that derive from The compounds of this invention,

(c) obtain the phase difference value of the blooming that in (b), obtains,

(d) based on the phase difference value that in (c), obtains, obtain the correlationship of the phase difference value of the content of the structural unit that derives from The compounds of this invention and blooming,

(e), determine the content of necessary for the desired phase difference value of the blooming of giving above-mentioned thickness, as to derive from The compounds of this invention structural unit by the correlationship that in (d), obtains.

Usually, in the long dispersed wavelength region of demonstration head sea of wavelength region, [Re (450)/Re (550)]＜1 and [Re (650)/Re (550)]＞1 of value (Re (λ)/Re (550)) near 1 that the phase difference value Re of certain af at wavelength lambda (λ) obtains divided by the phase difference value Re (550) at 550nm place, same polarisation conversion is possible.

Blooming of the present invention is by obtaining compound polymerization of the present invention.Can be with a kind of compound polymerization of the present invention, also can be with two or more compound polymerizations of the present invention.In addition, make composition polymerization of the present invention, also can make blooming of the present invention.

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

By on supporting substrate, being coated with the solution of compound of the present invention and carrying out drying, can obtain not polymeric membrane.When polymeric membrane did not show mesomorphic phase such as nematic phase, the blooming that obtains showed by the birefringence due to the single domain orientation.

By content, the glue spread of this solution on supporting substrate of the The compounds of this invention in the suitable adjustment The compounds of this invention solution, can adjust the thickness of blooming.The amount of compound of the present invention is under certain situation, and the phase difference value of the blooming that obtains (length of delay, Re (λ)) is by formula (7) decision, so in order to obtain desirable Re (λ), adjust thickness d and Δ n (λ) and get final product.

Re(λ)＝d×Δn(λ)????(7)

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

As the solution of The compounds of this invention coating process, can enumerate extrusion coated method, directly intaglio plate coating method, counter-rotating intaglio plate coating method, CAP coating method and mouthful mould coating method to supporting substrate.Can also enumerate the method that coating machines such as using dip coater, metering bar coater, spin coater is coated with.

As supporting substrate, can enumerate glass, plastic sheet, plastic film and light transmissive film.As light transmissive film, can enumerate polyolefin films such as polyethylene, polypropylene, norbornene-based polymer; Polyvinyl alcohol film; The polyethylene terephthalate film; The polymethacrylate film; The polyacrylic ester film; Cellulose ester membrane; Poly (ethylene naphthalate) film; Polycarbonate membrane; Polysulfone membrane; Poly (ether sulfone) film; The polyetherketone film; Polyphenylene sulfide film; Polyphenylene oxide film etc.

Even in the bonding process of blooming, transportation operation, preserve operation etc. and require in the operation of blooming intensity,, also can easily operate not making under the situation of blooming breakage etc. by using supporting substrate.

Preferably after forming alignment films on the supporting substrate, on this alignment films, be coated with the solution of compound of the present invention.Alignment films preferably has the solvent resistance that is insoluble to this solution when the solution of coating The compounds of this invention.In addition, alignment films preferably has being used for removing the thermotolerance of the heat treated of desolvating, make liquid crystal molecular orientation.And then, preferably the time can not produce the alignment films that waits peeling off of causing etc. because of friction in friction.As this alignment films, preferably form by orientation polymkeric substance or the composition that contains the orientation polymkeric substance.

As above-mentioned orientation polymkeric substance, can enumerate at intramolecularly and have the polymeric amide of amido linkage or gelatinization compound, have the polyimide of imide bond and as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, Ju oxazole, polymine, polystyrene, Polyvinylpyrolidone (PVP), polyacrylic acid and the polyacrylic ester of its hydrolyzate at intramolecularly.These orientation polymkeric substance can use separately, also can mix two or more uses.In addition, can also be the multipolymer of these orientation polymkeric substance.These orientation polymkeric substance can be by the dehydration polycondensation, take off chain polymerizations such as polycondensation, radical polymerization, anionoid polymerization, cationoid polymerisation, polycoordination, ring-opening polymerization etc. such as amine polycondensation and easily obtain.

These orientation polymkeric substance are dissolved in usually in the solvent and use as solution.To solvent without limits.Specifically, can enumerate water; Alcoholic solvents such as methyl alcohol, ethanol, ethylene glycol, Virahol, propylene glycol, ethylene glycol monomethyl ether, butyl glycol ether; Ester solvents such as ethyl acetate, butylacetate, ethylene glycol monomethyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, pimelinketone, 2-heptanone, methyl iso-butyl ketone (MIBK); Non-chlorinated aliphatichydrocarbon solvents such as pentane, hexane, heptane; Non-chlorinated aromatic hydrocarbons solvent such as toluene, dimethylbenzene; Nitrile solvents such as acetonitrile; Ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran (THF), glycol dimethyl ether; 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, can enumerate SUNEVER (registered trademark, Nissan Chemical Ind Ltd's system), OPTOMER (registered trademark, JSR Corp.'s system) etc.

When using such alignment films, owing to need not to carry out based on the control of tensile specific refractory power, so inequality reduces in birefringent, can provide and can tackle the big blooming that supporting substrate upper flat plate display unit (FPD) maximizes.

As the method that on supporting substrate, forms alignment films, can enumerate being coated on the supporting substrate after making solvent with commercially available aligning film material, as the compound of aligning film material, carry out the annealed method then.

The thickness of alignment films is generally 10～10000nm, is preferably 10～1000nm.When above-mentioned scope, can make The compounds of this invention etc. on this alignment films, be orientated to desirable angle.As required, can carry out friction treatment, also can carry out polarized light UV irradiation, can make The compounds of this invention etc. be orientated to desirable direction by described processing to alignment films to alignment films.That is, can adjust shape, the slope of indicatrix of demonstration double refraction state of the blooming of manufacturing.

As the method for alignment films being carried out friction treatment, the method that can be listed below: the alignment films of carrying on the friction roller and the platform that are wound with friction cloth of rotation and transporting is contacted.

The method of stacked not polymeric membrane on the alignment films that is laminated on the described supporting substrate is compared with the method for making liquid crystal cells and injecting liquid crystalline cpd in this liquid crystal cells, can reduce production cost, and can adopt the film production of roller film.

Removing of solvent can be carried out abreast with polyreaction, but from the viewpoint of film-forming properties, preferably removes most solvent before carrying out polyreaction.

As the method for removing of solvent, can enumerate methods such as seasoning, air seasoning, drying under reduced pressure.The temperature that heats and remove when desolvating is generally 0～250 ℃, is preferably 50～220 ℃, more preferably 80～170 ℃.Be preferably 10 seconds heat-up time～60 minutes, more preferably 30 seconds～30 minutes.Heating temperature and heat-up time be in above-mentioned scope the time, as supporting substrate, can use not necessarily supporting substrate fully of thermotolerance.

By making the polymerization of not polymeric membrane, the curing that obtains, can obtain The compounds of this invention the immobilized film of orientation, be polymeric membrane.Can be vulnerable to the film of heat to birefringent influence.

Make the polymeric membrane polymeric method not can be according to the kind of liquid crystalline cpd and The compounds of this invention and suitably decision.Use light polymerization method when the polymerizable group in The compounds of this invention and the liquid crystalline cpd is the optical polymerism group, use hot polymerization legal when this polymerizable group is the thermopolymerization group.Adopt light polymerization method, can make not polymeric membrane polymerization at low temperatures, from the stable on heating range of choice of supporting substrate wide viewpoint and industrial viewpoint easy to manufacture, preferred The compounds of this invention and the liquid crystalline cpd that use with optical polymerism polymerizable group.In addition, from the viewpoint of film-forming properties also preferred light polymerization.Photopolymerization reaction is not by carrying out the irradiation of polymeric membrane visible light, UV-light or laser.In operating aspect, preferred especially UV-light.Rayed can be carried out under The compounds of this invention becomes the temperature of mesomorphic phase.At this moment, can also utilize mask etc. with the polymeric membrane patterning.

Can exposure, Heating temperature, heat-up time when suitably adjusting polymerization degree of birefringence Δ n (λ) be adjusted, so that give desired phase differential.

Compare with the stretched film of giving phase differential by strained polymer, the thickness of blooming of the present invention is thinner.

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

The blooming transparency that obtains like this is excellent, can be used as various indicating meters and uses with film.The thickness of blooming as mentioned above, because of the difference of the phase difference value of blooming is different, but thickness is preferably 0.1～10 μ m, from reducing stress optic viewpoint, more preferably 0.2～5 μ m is preferably 0.5～3 μ m especially.

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

For such film and can carry out the blooming of same polarization conversion, can in FPD such as all liquid crystal panels, organic EL, use as optical compensation films in wideer wavelength region.

Blooming of the present invention can be used as broadband λ/4 plates or λ/2 plates use.When using, can suitably select to derive from the blooming content of structural unit of The compounds of this invention and the thickness of blooming as broadband λ/4 plates or λ/2 plates.When using, can adjust thickness, so that the Re of the blooming that obtains (550) is generally 113～163nm, is preferably 135～140nm, is preferably especially about about 137.5nm as λ/4 plates.When using, can adjust thickness, so that the Re of the blooming that obtains (550) is generally 250～300nm, is preferably 273～277nm, is preferably especially about about 275nm as λ/2 plates.

Blooming of the present invention can also use with blooming as VA (Vertical Alingment) pattern.When using with blooming, can suitably select to derive from the blooming content of the structural unit of The compounds of this invention as the VA pattern.Can adjust thickness, so that the Re of the blooming that obtains (550) is preferably 40～100nm, more preferably about 60～80nm.

Only use a spot of The compounds of this invention, the wavelength dispersion characteristic displacement that just can make blooming can be by the easy desired wavelength dispersion characteristic of method adjustment near 1 value.

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

Even 1 of blooming of the present invention also shows excellent optical, but also can stacked multi-disc use.In addition, can be used in combination with other film.As with the concrete example of other film combination, can be set forth in ellipsoidal polarizing plate that the blooming of the present invention of fitting on the polarizing coating forms, on this ellipsoidal polarizing plate further with blooming of the present invention as broadband λ/4 plates broadband circular polarizing disk of forming etc. of fitting.

Blooming of the present invention can by in coating on the supporting substrate or on the alignment films, make it polymerization and form, therefore as shown in Figure 1, can on colour filter, form the blooming of broadband, for example λ/4, λ/2 more easily.

Colour filter 1 has stacked gradually color-filter layer 4, alignment films 3 and blooming of the present invention 2.

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

Then, the solution of the The compounds of this invention of The compounds of this invention content has been adjusted in modulation in order to make the blooming that obtains have desirable wavelength dispersion characteristic, the mode that reaches the thickness of desirable phase difference value with formation is coated with this solution on the alignment films 3 that obtains, form blooming 2.

By using this colour filter 1, can make more slim liquid crystal indicator.As the one example, with illustrating of expression liquid crystal indicator 5 of the present invention in Fig. 2.

In liquid crystal indicator shown in Figure 25, on polaroid 6, being situated between has glass substrate etc. and backlight opposing substrates 7 by adhesive.On the color-filter layer of making on the substrate 74 ', being situated between is formed with blooming 2 ' by alignment films 3 '.And then, on blooming 2 ', be formed with comparative electrode 8, on comparative electrode 8, be formed with mesomorphic phase 9.In the backlight side, Jie is had substrates 11 such as glass substrate by adhesive on polaroid 10.And then, on substrate 11, be formed with the thin film transistor (TFT) and the insulation layer 12 that are used to make the active driving of liquid crystal layer, and then on TFT, be formed with transparency electrode 13 and/or the reflecting electrode 13 ' that uses Ag, Al or ITO (Indium Tin Oxide, tin indium oxide).Compare with liquid crystal indicator in the past, the formation of liquid crystal indicator 5 shown in Figure 2 is few formations of sheet number of blooming, can make more slim liquid crystal indicator.

Below record colour filter 1 ' is formed at the example of method for making of liquid crystal indicator 5 of the liquid crystal layer side of side's substrate.Can followingly carry out: on the substrate of backlight side, on pyrex, pile up grid, gate insulating film and amorphous silicon and the patterning that forms by Mo, MoW etc., then thereby amorphous silicon is annealed crystallization and formed semiconductor film with excimer laser, then, region doping P, B etc. in the grid both sides, the TFT of formation n type passage, p type passage.And then, by forming by SiO ₂The insulation layer 12 that forms, thus the substrate of backlight side obtained.And then, by sputtering ITO on backlight side group plate 11, thus the transparency electrode 13 that stacked total transmissivity type display unit is used on backlight side group plate.In addition, similarly, replace ITO, can obtain the reflecting electrode 13 ' that the fully-reflected type display unit is used by using Ag, Al etc.And then, by appropriate combination reflecting electrode, transparency electrode, also can obtain the electrode of the backlight side that transflective liquid crystal display device uses.

On the other hand, on opposing substrates 7, form color-filter layer 4 '.With R, G, B colour filter, can also obtain color liquid crystal display arrangement by also.Then, go up coating orientation polymkeric substance, rub, thereby form alignment films 3 ' at color-filter layer 4 '.Go up the solution of coating compound of the present invention in this alignment films 3 ', Yi Bian be heated to the temperature range that obtains mesomorphic phase, Yi Bian the polymerization by uviolizing forms blooming 2 '.After forming blooming,, can form comparative electrode 8 by sputtering ITO.And then on this comparative electrode, form alignment films, and form mesomorphic phase 9, assemble with the substrate of above-mentioned backlight side at last, thereby can make liquid crystal indicator 5.

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 for example liquid crystal indicator (LCD), organic EL.

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

Polaroid of the present invention contains blooming of the present invention and has the film (polarizing coating) of polarization function, obtains by stacked blooming of the present invention and polarizing coating usually.Specifically, by directly or use the tackiness agent blooming of the present invention of fitting to obtain on the single face of polarizing coating or two sides.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 synoptic diagram of expression polaroid 1 of the present invention.

Among the polaroid 30a shown in Fig. 3 (a), duplexer 14 and polarizing coating 15 are directly fitted, and duplexer 14 is made of supporting substrate 16, alignment films 17 and blooming 18.Polaroid 30a presses the sequential cascade of supporting substrate 16, alignment films 17, blooming 18, polarizing coating 15.

Among the polaroid 30b shown in Fig. 3 (b), duplexer 14 and polarizing coating 15 are situated between and are fitted by binder layer 19.

Among the 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.

Among the polaroid 30d shown in Fig. 3 (d), duplexer 14 and duplexer 14 ' are situated between and are fitted by binder layer 19, and then, directly be fitted with polarizing coating 15 on the duplexer 14 '.

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

Can use from duplexer 14 peeled off supporting substrate 16 and alignment films 17 and blooming 18 replace duplexer 14, also can use from duplexer 14 peeled off supporting substrate 16 and the film that constitutes by alignment films 17 and blooming 18 replace duplexer 14.Can use from duplexer 14 ' peeled off supporting substrate 16 ' and alignment films 17 ' and blooming 18 ' replace duplexer 14 ', also can use from duplexer 14 ' peeled off supporting substrate 16 ' and the film that constitutes by alignment films 17 ' and blooming 18 ' replace duplexer 14 '.

Polaroid of the present invention can stacked a plurality of duplexers, and these a plurality of duplexers can be all identical, also can be different.

Polarizing coating 15 is so long as have the film of polarization function and get final product, specifically can be set forth in adsorb iodine, the back draft of dichroism pigment in the polyvinyl alcohol mesentery and film; With the polyvinyl alcohol mesentery stretch back absorption iodine, dichroism pigment and film etc.

The tackiness agent that uses in binder layer 19 and the binder layer 19 ' is the tackiness agent of transparency height, excellent heat resistance preferably.As this tackiness agent, can enumerate acrylic adhesive, epoxy is tackiness agent, polyurethane series tackiness agent etc.

Panel display apparatus of the present invention possesses blooming of the present invention, specifically, can enumerate possess with polaroid of the present invention and liquid crystal panel fit the applying product that form liquid crystal indicator, possess the organic EL display of organic EL plate that polaroid of the present invention and luminescent layer applying are formed.

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

Fig. 4 is the synoptic diagram of the applying product 21 of expression liquid crystal panel 20 of liquid crystal indicator of the present invention and polaroid 30.The product 21 of fitting are formed polaroid 30 of the present invention and liquid crystal panel 20 Jie by bonding coat 22 applyings.By using not shown electrode, liquid crystal panel 20 is applied voltage, can drive liquid crystal molecule, carry out white and black displays.

Fig. 5 is the synoptic diagram of organic EL plate 23 of expression organic EL display of the present invention.Organic EL plate 23 is formed polarizing coating 30 of the present invention and luminescent layer 24 Jie by bonding coat 25 applyings.

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

Embodiment

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

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

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

With 2,5-dimethoxyaniline 21.5g, thionaphthene-2-carboxylic acid 25.0g and anhydrous chloroform 125.3g mix, and make it reaction.In the mixture that obtains, add N, N-dimethyl aminopyridine 1.71g.Resulting mixture is cooled off with ice bath, add N, N '-dicyclohexylcarbodiimide 31.8g reacted 1 hour., mixture returned to room temperature, resulting mixture is filtered by silica gel, remove post precipitation, concentrating under reduced pressure thereafter.In residue, add 1/2 (v/v) solution of ethyl acetate-heptane, make its crystallization.Filter the crystallization of being separated out, vacuum-drying obtains compound (1-a) 33.4g as pale yellow powder.With 2, the 5-dimethoxyaniline is a benchmark, and yield is 76%.

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

With compound (1-a) 33.35g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two 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 mix, resulting mixture is warmed up to 80 ℃, makes it reaction.The cooling back concentrates, and obtaining with the resolvent of compound (1-b) and lawesson reagent is the red sticky solid of principal constituent.

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

The mixture that contains compound (1-b), sodium hydroxide 25.5g and the water 580g that obtain in the preceding paragraph are mixed, under ice-cooled, make resulting mixture reaction.Then, add in the mixture, in room temperature reaction 12 hours at the ice-cooled aqueous solution that will contain down the 95.6g Tripotassium iron hexacyanide.The yellow mercury oxide that leaching is separated out.With the precipitation water of leaching, then clean, and clean with ethanol with hexane, vacuum-drying, obtaining with compound (1-c) is the faint yellow solid 19.5g of principal constituent.With compound (1-a) is benchmark, and yield is 56%.

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

Compound (1-c) 19.5g and pyridinium chloride 97.5g are mixed, be warmed up to 180 ℃, reacted 2 hours.After the cooling of resulting mixture, add water, the resulting precipitation of leaching, is then cleaned with hexane water, and obtaining with compound (1-d) is the solid 18g of principal constituent.With compound (1-c) is benchmark, and 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.In the ice-cooled mixture that is obtaining down, add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 7.68g.Stir resulting reaction soln, after filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol and carry out the crystallization processing.The leaching crystallization makes it be dissolved in chloroform again.Add methyl alcohol while stirring resulting solution, the white precipitate that leaching generates after the vacuum-drying, obtains compound (A1-1) 10.9g as white powder.With compound (1-d) is benchmark, and 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 that obtains (A1-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A1-1) is smectic phase from 147 ℃ to 155 ℃ when heating up, from 155 ℃ to being nematic phase more than 180 ℃, when cooling, till 93 ℃, be nematic phase and crystallization.

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

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

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

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

With compound (5-a) 13.0g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 100g mix, and resulting mixture is warmed up to 80 ℃, react 5 hours.The cooling back concentrates, and obtaining with the resolvent of compound (5-b) and lawesson reagent is the red sticky solid of principal constituent.

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

The mixture that contains compound (5-b), sodium hydroxide 10.5g and the water 250g that obtain in the preceding paragraph are mixed, under ice-cooled, make resulting mixture reaction.Then, at the ice-cooled aqueous solution that contains the 39.3g Tripotassium iron hexacyanide that adds down, make it reaction.In room temperature reaction after 12 hours, the yellow mercury oxide that leaching is separated out.With the precipitation water of leaching, then clean, and clean with ethanol with hexane, vacuum-drying, obtaining with compound (5-c) is the faint yellow solid 9.3g of principal constituent.With compound (5-a) is benchmark, and yield is 69%.

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

Compound (5-c) 7.0g and pyridinium chloride 35.0g are mixed, be warmed up to 180 ℃, reacted 2 hours.After resulting mixture cooling, add water, the resulting precipitation of leaching, water, hexane clean, and obtaining with compound (5-d) is the solid 6.5g of principal constituent.With compound (5-c) is benchmark, and 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.In the ice-cooled mixture that is obtaining down, add N, N '-DIC 1.71g.Make resulting reaction soln react a night in room temperature, after the filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol and make its crystallization.The leaching crystallization makes it be dissolved in chloroform again.Add methyl alcohol while stirring resulting solution, the white precipitate that leaching generates cleans with ethanol, obtains compound (A5-1) 4.73g as white powder after the vacuum-drying.With compound (5-d) is benchmark, and 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 that obtains (A5-1) can be confirmed by adopting the polarized light microscope observing structure.Compound (A5-1) when heating up, from 139 ℃ to being nematic phase more than 180 ℃, when cooling, till 93 ℃, be nematic phase and crystallization.

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

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

5-cresotinic acid aldehyde 50g, salt of wormwood 101.51g, Tetrabutylammonium bromide 11.84g, potassiumiodide 30.48g and toluene are mixed, be heated to 80 ℃.In resulting dispersion liquid, drip bromo diethyl malonate 114.1g, in 110 ℃ (backflow of toluene boiling point) reaction 24 hours.In the brown solution that obtains, add the solution that 3mL is dissolved with 3g potassium hydroxide, further reacted 24 hours.Behind resulting reaction solution cool to room temperature, use the vaporizer concentrating under reduced pressure.In residue, add potassium hydroxide 40g, ethanol 400mL, stirred 1 hour in 80 ℃.Behind the cool to room temperature, remove ethanol with the vaporizer distillation.Residue is dissolved among pure water 500mL, the ice 500g, pH is adjusted into 3 with 2N sulfuric acid.Adopt to filter and collect the yellow mercury oxide of being separated out, and then clean with pure water 1000mL, vacuum-drying obtains the 5-methyl cumarone-2 carboxylic acid 43.7g as pale yellow powder.With the 4-Methyl Salicylaldehyde is benchmark, and yield is 68%.

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

With 2,5-dimethoxyaniline 30.4g, 5-methyl-cumarone-2-carboxylic acid 35.0g, triethylamine 20.1g, N, N '-dimethyl aminopyridine 4.85g and dehydration N, N '-N,N-DIMETHYLACETAMIDE 175.0g mixes.With ice bath with the cooling of resulting solution after, (dimethylamino) Phosphonium hexafluorophosphate (hereinafter referred to as bop reagent) 92.28g was in room temperature reaction 24 hours to add 1H-benzotriazole-1-base oxygen base three.In resulting mixture, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of entry and methyl alcohol, make and separate out crystallization.The resulting precipitation of leaching, the mixing solutions of water and methyl alcohol (water 1 parts by volume, methyl alcohol 1 parts by volume) cleans, and carries out vacuum-drying, obtains compound (6-a) 23.8g as pale yellow powder.With 2, the 5-dimethoxyaniline is a benchmark, and yield is 39%.

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

With compound (6-a) 23.8g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 16.1g and toluene 80g mix, and resulting mixture is warmed up to 80 ℃, react 8 hours.The cooling back concentrates, and obtaining with the resolvent of compound (6-b) and lawesson reagent is the red sticky solid of principal constituent.

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

The mixture that contains compound (6-b), sodium hydroxide 18.4g and the water 400g that obtain in the preceding paragraph are mixed, at the resulting mixture of ice-cooled stirring down.Then, at the ice-cooled aqueous solution that contains the 68.7g Tripotassium iron hexacyanide that adds down, make it reaction.In room temperature reaction 24 hours, the yellow mercury oxide that leaching is separated out.With the precipitation water of leaching, then with the hexane cleaning, clean with ethanol, carry out vacuum-drying, obtaining with compound (6-c) is the faint yellow solid 14.8g of principal constituent.With compound (6-a) is benchmark, and yield is 59%.

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

Compound (6-c) 14.8g and pyridinium chloride 74.0g (5 times of quality) are mixed, be warmed up to 180 ℃, reacted 2 hours.After resulting mixture cooling, add water, the resulting precipitation of leaching, water, toluene clean, and obtaining with compound (6-d) is the solid 10.4g of principal constituent.With compound (6-c) is benchmark, and 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.At the ice-cooled N, N '-di-isopropyl carbon imide 1.73g of in resulting mixture, adding down.At room temperature make resulting reaction soln react a night, carry out concentrating under reduced pressure after the filtered through silica gel.In residue, add methyl alcohol and make its crystallization.The leaching crystallization makes it be dissolved in chloroform again.Add methyl alcohol while stirring resulting solution, the white precipitate that leaching generates is used washed with heptane, and vacuum-drying obtains compound (A6-1) 4.72g as white powder.With compound (6-d) is benchmark, and 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 (d d, 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 that obtains (A6-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A6-1) when heating up, from 146 ℃ to being nematic phase more than 190 ℃, when cooling, till 100 ℃, be nematic phase and crystallization.

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

(1) synthesis example of 5-isobutyl-benzo furans

Make 4-isopropyl-phenol 40g be dissolved in N, among N '-N,N-DIMETHYLACETAMIDE 240.0g.After utilizing ice bath with the solution cooling, divide 10 times and add sodium hydroxide 10.9g.In stirring at room 1 hour, after the phenomenon that produces hydrogen finishes, drip monochloroacetaldehyde dimethyl acetal 33.17g.In 80 ℃ of stirrings 5 hours, behind the affirmation reaction terminating, reaction solution is added among entry 1000mL, the methyl iso-butyl ketone (MIBK) 400mL, carry out separatory.Reclaim organic layer, and then 2 times the pure water with 800mL cleans organic layer.After reclaiming organic layer, use anhydrous sodium sulfate dehydration, use the vaporizer concentrating under reduced pressure, obtain red thick liquid.On the other hand, toluene and ortho-phosphoric acid 2.61g mixing with 400g are heated to 110 ℃.In this solution, drip by red thick liquid being dissolved in the solution that obtains in the 100mL toluene.After 3 hours, be cooled to room temperature in 110 ℃ of stirrings.With 1N-sodium bicarbonate aqueous solution cleaning reaction liquid 2 times, clean with pure water 500mL at last.Reclaim organic layer, behind anhydrous sodium sulfate dehydration, use the vaporizer concentrating under reduced pressure, vacuum-drying obtains the 5-isobutyl-benzo furans 41.9g as the incarnadine thick liquid.With the 4-isopropyl-phenol is benchmark, and yield is 90%.

(2) synthesis example of 2-formyl radical-5-isobutyl-benzo furans

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

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

2-formyl radical-5-isobutyl-benzo furans 16.40g, thionamic acid 9.43g mixed with the pure water of 60mL.With the ice bath cooling, drip the aqueous solution (water is 50mL) of Textone 8.78g.Reaction is 36 hours under water-bath.In reaction soln, add toluene 100mL, potassium hydroxide 5g, pH is adjusted into 12.Carry out separatory, reclaim water layer, and then clean water layer with the toluene of 300mL.Reclaim water layer, with 2N-hydrochloric acid pH regulator is 2 after, adding toluene 300mL carries out separatory.Reclaim organic layer, behind anhydrous sodium sulfate dehydration, use the vaporizer concentrating under reduced pressure, vacuum-drying obtains the 5-isobutyl-benzo furans-2-carboxylic acid 6.7g as the incarnadine thick liquid.With 2-formyl radical-5-isobutyl-benzo furans is benchmark, and yield is 38%.

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

With 2,5-dimethoxyaniline 4.71g, 5-isobutyl-benzo furans-2-carboxylic acid 8.71g, triethylamine 3.11g, N, N '-dimethyl aminopyridine 0.75g and dehydration N, N '-N,N-DIMETHYLACETAMIDE 35.0g mixes.After cooling off resulting solution with ice bath, add bop reagent 14.28g, in room temperature reaction 24 hours.In resulting mixture, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of entry and methyl alcohol, make and separate out crystallization.The resulting precipitation of leaching, the mixing solutions of water and methyl alcohol (water 1 parts by volume, methyl alcohol 1 parts by volume) cleans, and vacuum-drying obtains compound (10-a) 5.7g as pale yellow powder.With 2, the 5-dimethoxyaniline is a benchmark, and yield is 53%.

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

With compound (10-a) 4.7g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 100g mix, and resulting mixture is warmed up to 80 ℃, react 5 hours.The cooling back concentrates, and obtaining with the resolvent of compound (10-b) and lawesson reagent is the red sticky solid of principal constituent.

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

The mixture that contains compound (10-b), sodium hydroxide 3.1g and the water 50g that obtain in the preceding paragraph are mixed, at the resulting mixture of ice-cooled stirring down.Then, at the ice-cooled aqueous solution that contains the 11.94g Tripotassium iron hexacyanide that adds down, make its reaction.In room temperature reaction 24 hours, the yellow mercury oxide that leaching is separated out.With the precipitation water of leaching, then with the hexane cleaning, use washed with methanol.Solvent to yellow powder adding heptane-ethyl acetate 1: 1 (volume ratio), leaves standstill a night under ice bath after 1 hour in stirring at room.The resulting pale yellow powder of leaching, vacuum-drying, obtaining with compound (10-c) is the faint yellow solid 2.5g of principal constituent.With compound (10-a) is benchmark, and yield is 51%.

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

Compound (10-c) 2.5g and pyridinium chloride 12.5g are mixed, be warmed up to 180 ℃, reacted 2 hours.After resulting mixture cooling, add water, the resulting precipitation of leaching, water, toluene, hexane clean, and obtaining with compound (10-d) is the solid 1.8g of principal constituent.With compound (10-c) is benchmark, and 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.At the ice-cooled N, N '-DIC 1.70g of in resulting mixture, adding down.At room temperature make resulting reaction soln react a night, after the filtered through silica gel, carry out concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.The leaching crystallization makes it be dissolved in chloroform again.Add methyl alcohol while stirring resulting solution, the white precipitate that leaching generates cleans with ethanol, carry out the silica gel column chromatography analysis, reclaim first composition, behind the vaporizer concentrating under reduced pressure, make its crystallization with cold methanol with chloroform 80vol%-acetone 20vol% wash-out.The pale yellow powder that leaching generates, vacuum-drying obtains compound (A10-1) 4.60g as white powder.With compound (10-d) is benchmark, and 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 (d d, 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 that obtains (A10-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A10-1) since 144 ℃ of phases that show that viscosity is high, shows transparency a little at 169 ℃ when heating up.In when cooling, have clear and definite nematic phase since 167 ℃, till 105 ℃, be nematic phase and crystallization.

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

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

Make 3,5-xylenol 25g is dissolved in N, among N '-N,N-DIMETHYLACETAMIDE 150.0g.After utilizing ice bath with the solution cooling, add sodium hydroxide 9.82.In stirring at room 1 hour, drip monochloroacetaldehyde dimethyl acetal 25.49g.In 100 ℃ of stirrings 15 hours, reaction solution is added among entry 1000mL, the methyl iso-butyl ketone (MIBK) 400mL, carry out separatory.Reclaim organic layer, 2 times the 1N-aqueous sodium hydroxide solution with 500mL cleans organic layer, and then 2 pure water with 800mL clean organic layer.After reclaiming organic layer, use anhydrous sodium sulfate dehydration, use the vaporizer concentrating under reduced pressure, obtain the incarnadine thick liquid.On the other hand, toluene and the mixing of 3.01g ortho-phosphoric acid with 400g are heated to 110 ℃.In this solution, drip by the incarnadine thick liquid being dissolved in the solution that obtains in the 100mL toluene.After 3 hours, be cooled to room temperature in 110 ℃ of stirrings.With 1N-sodium bicarbonate aqueous solution cleaning reaction liquid 2 times, clean with pure water 500mL at last.Reclaim organic layer, behind anhydrous sodium sulfate dehydration, use the vaporizer concentrating under reduced pressure, vacuum-drying obtains as 4 of incarnadine thick liquid, 6-dimethyl benzofuran 16.5g.With 3, the 5-xylenol is a benchmark, and yield is 55%.

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

With 4,6-dimethyl benzofuran 21.62g is dissolved in N, among N '-dimethyl formamide 28.4g.After utilizing water-bath with the solution cooling, drip phosphoryl chloride 25g.Pink solution, was stirred 10 hours in 100 ℃ after 1 hour in stirring at room.Reaction solution put be chilled to room temperature, add pure water 100mL, stirs after 1 hour, neutralize with the 1N sodium bicarbonate.After pH regulator is 8, with the toluene separatory.Reclaim organic layer, add gac 2.6g, filter.Use the vaporizer concentrating under reduced pressure, residue is dissolved in the chloroform, make its crystallization with heptane.The leaching crystallization obtains the 2-formyl radical-4 as pale yellow powder after the vacuum-drying, 6-dimethyl benzofuran 19.5g.With 4, the 6-dimethyl benzofuran is a benchmark, and yield is 76%.

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

With 2-formyl radical-4,6-dimethyl benzofuran 19.50g, thionamic acid 13.04g mix with the pure water of 100mL.With the ice bath cooling, drip the aqueous solution (water is 100mL) of Textone 12.15g.Reaction is 36 hours under water-bath.In reaction soln, add toluene 100mL, potassium hydroxide 25g, pH is adjusted into 12.Carry out separatory, reclaim water layer, and then clean water layer with the toluene of 200mL.Reclaim water layer, with 2N-hydrochloric acid pH regulator is 2 after, adding toluene 400mL carries out separatory.Reclaim organic layer, behind anhydrous sodium sulfate dehydration, use the vaporizer concentrating under reduced pressure, vacuum-drying obtains as 4 of yellow powder, 6-dimethyl benzofuran-2-carboxylic acid 14.27g.With 2-formyl radical-4, the 6-dimethyl benzofuran is a benchmark, and yield is 67%.

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

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

Make 4,6-dimethyl salicylic aldehyde 45.0g, salt of wormwood 101.g are dispersed in N, among N '-N,N-DIMETHYLACETAMIDE 360mL.After being heated to 80 ℃, with 1 hour dripping bromine ethyl acetate 50.0g.Made mixture reaction 4 hours in 80 ℃.Behind the reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 400mL, be adjusted to acidity with cold 1N-hydrochloric acid 1000mL after, carry out separatory.3 times the pure water with 1000mL cleans organic layer, reclaims organic layer.Behind anhydrous sodium sulfate dehydration, distill except that desolvating with vaporizer.In residue, add potassium hydroxide 40g, ethanol 400mL, stirred 1 hour in 80 ℃.Put be chilled to room temperature after, remove with vaporizer distillation and to desolvate, add pure water 1000mL.Confirm pH be 12 or more after, water layer is cleaned 2 times usefulness washed with heptane 1 time with toluene.Reclaiming water layer, with the neutralization of 4N-sulfuric acid, is 3 with pH regulator.The yellow mercury oxide that leaching is separated out, after pure water suspension washing, vacuum-drying obtains thus as 4 of yellow powder, 6-dimethyl benzofuran-2-carboxylic acid 48.1g.With 4,6-dimethyl salicylic aldehyde is a benchmark, and yield is 83%.(5) synthesis example of compound (11-a)

With 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 '-N,N-DIMETHYLACETAMIDE 100.0g mixes.With ice bath with the cooling of the solution that obtains after, add bop reagent 34.85g, in room temperature reaction 24 hours.In resulting mixture, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of entry and methyl alcohol, make and separate out crystallization.The resulting precipitation of leaching, the mixing solutions of water and methyl alcohol (water 3 parts by volume, methyl alcohol 2 parts by volume) cleans, and vacuum-drying obtains compound (11-a) 16.2g as pale yellow powder.With 2, the 5-dimethoxyaniline is a benchmark, and yield is 66%.

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

With compound (11-a) 16.0g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 100g mix, and resulting mixture is warmed up to 80 ℃, react 12 hours.The cooling back concentrates, and obtaining with the resolvent of compound (11-b) and lawesson reagent is the red sticky solid of principal constituent.

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

The mixture that contains compound (11-b), sodium hydroxide 11.8g and the water 250g that obtain in the preceding paragraph are mixed, at the ice-cooled mixture reaction that obtains that makes down.Then, at the ice-cooled aqueous solution that contains the 44.17g Tripotassium iron hexacyanide that adds down, make its reaction.In 60 ℃ of reactions 12 hours, the yellow mercury oxide that leaching is separated out.With the precipitation water of leaching, then with the hexane cleaning, make its crystallization with toluene.With the yellow substance vacuum-drying that obtains, obtaining with compound (11-c) is the khaki color solid 4.1g of principal constituent.With compound (11-a) is benchmark, and yield is 25%.

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

Compound (11-c) 4.0g and pyridinium chloride 40.0g are mixed, be warmed up to 180 ℃, reacted 3 hours.The mixture that obtains is added in the ice the resulting precipitation of leaching.After the aqueous suspension washing, clean with toluene, vacuum-drying, obtaining with compound (11-d) is the khaki color solid 3.4g of principal constituent.With compound (11-c) is benchmark, and 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-cooled, in resulting mixture, add N, N '-DIC 2.92g.At room temperature make resulting reaction soln react a night, after the filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.The leaching crystallization was dissolved in the chloroform it again, adds the 0.3g gac, in stirring at room 1 hour.Filtering solution, with vaporizer filtrate decompression is concentrated into 1/3 after, add methyl alcohol while stir, the white precipitate that leaching generates is used washed with heptane, vacuum-drying obtains compound (A11-1) 7.60g as white powder.With compound (11-d) is benchmark, and 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 (d d, 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 that obtains (A11-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A11-1) shows the high intermediate phase of viscosity from 105 ℃ to 137 ℃ when heating up.Though be difficult to distinguish mesomorphic phase, be clear and definite nematic liquid crystal phase more than 137 ℃.Nematic liquid crystal is maintained to more than 180 ℃ mutually, is nematic phase and crystallization when cooling till 61 ℃.

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

(1) synthesis example of 5-fluorobenzene and furans-2 carboxylic acids

5-fluorine salicylic aldehyde 25g, salt of wormwood 49.32g and 2-butanone 200g are mixed, be heated to 80 ℃.In resulting dispersion liquid, drip bromo diethyl malonate 55.5g, in 100 ℃ of reactions 24 hours.With resulting red tan solution put be chilled to room temperature after, clean with pure water, 1mol/L wet chemical.Reclaim organic layer, use anhydrous sodium sulfate dehydration, use the vaporizer concentrating under reduced pressure.In residue, add potassium hydroxide 25g, ethanol 250mL, stirred 2 hours in 80 ℃.After being cooled to the room temperature cooling, remove ethanol with the vaporizer distillation.Residue is dissolved among pure water 500mL, the ice 500g, pH is adjusted into 3 with 2N sulfuric acid.Adopt to filter and collect the pale purple precipitation of being separated out, and then, to clean with pure water 1000mL, vacuum-drying obtains 5-fluorobenzene and furans-2 carboxylic acid 23.4g as pale yellow powder.With 4-fluorine salicylic aldehyde is benchmark, and yield is 73%.

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

With 2,5-dimethoxyaniline 17.01g, 5-fluorobenzene and furans-2 carboxylic acid 20.0g, triethylamine 11.24g, N, N '-dimethyl aminopyridine 2.71g and dehydration N, N '-N,N-DIMETHYLACETAMIDE 100.0g mixes.With ice bath with the cooling of resulting solution after, add bop reagent 51.57g, in room temperature reaction 24 hours.In the mixture that obtains, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of entry, methyl alcohol, crystallization is separated out.The resulting precipitation of leaching, with mixing solutions (water 1 parts by volume, the methyl alcohol 1 parts by volume) cleaning of water-methanol, vacuum-drying obtains compound (15-a) 32.1g as pale yellow powder.With 2, the 5-dimethoxyaniline is a benchmark, and yield is 92%.

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

With compound (15-a) 32.0g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 24.6g and toluene 320g mix, and the mixture that obtains is warmed up to 80 ℃, react 24 hours.The cooling back concentrates, and the resolvent that obtains with compound (15-b) and lawesson reagent is the yellow solid of principal constituent.

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

The mixture that contains compound (15-b), sodium hydroxide 21.7g and the water 500g that obtain in the preceding paragraph are mixed, at the resulting mixture of ice-cooled stirring down.Then, add Tripotassium iron hexacyanide 81.3g, make its reaction.In room temperature reaction 2 hours, the yellow mercury oxide that leaching is separated out.With the precipitation water of leaching, then with the hexane cleaning, clean with toluene, vacuum-drying, obtaining with compound (15-c) is the khaki color solid 27.1g of principal constituent.With compound (15-a) is benchmark, and yield is 91%.

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

Compound (15-c) 10.0g and pyridinium chloride 50.0g are mixed, be warmed up to 180 ℃, reacted 2 hours.After resulting mixture cooling, add water, the resulting precipitation of leaching, water, hexane, toluene clean, and obtaining with compound (15-d) is the solid 6.0g of principal constituent.With compound (15-c) is benchmark, and 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.At the ice-cooled N, N '-DIC 3.02g of in resulting mixture, adding down.At room temperature make resulting reaction soln react a night, after the filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol and make its crystallization.The leaching crystallization makes it be dissolved in chloroform again.Add gac 0.3g, stir after 1 hour, filter.Behind the vaporizer concentrated filtrate, add methyl alcohol while stir, the white precipitate that leaching generates.To precipitate and use washed with heptane, vacuum-drying obtains compound (A15-1) 8.20g as white powder.With compound (15-d) is benchmark, and 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 (d d, 2H), 6.07～6.17 (m, 2H), 6.37～6.44 (m, 2H), 6.87～7.02 (m, 8H), 7.14～7.19 (d t, 1H), 7.28 (s, 2H), 7.33～7.37 (dd, 1H), 7.50～7.55 (m, 2H)

The phase transition temperature of the compound that obtains (A15-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A15-1) is when heating up, and the high phase of demonstration viscosity is difficult to distinguish mesomorphic phase from 143 ℃ to 178 ℃.But, showing clear and definite nematic phase more than 178 ℃, until being the nematic liquid crystal phase more than 200 ℃.When cooling, till 110 ℃, be nematic phase and crystallization.

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

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

4-propyl group salicylic aldehyde 27.8g, salt of wormwood 46.81g, Tetrabutylammonium bromide 11.84g, potassiumiodide 30.48g and toluene are mixed, be heated to 80 ℃.The hexaoxacyclooctadecane-6-6 of Dropwise 5 2.6g bromo diethyl malonate, 2.8g in the dispersion liquid that obtains was in 110 ℃ (backflow of toluene boiling point) reaction 24 hours.After resulting sorrel reaction solution is cooled to room temperature, use the vaporizer concentrating under reduced pressure.In residue, add potassium hydroxide 27.8g, ethanol 278mL, stirred 1 hour in 80 ℃.Behind the cool to room temperature, remove ethanol with the vaporizer distillation.Residue is dissolved among pure water 500mL, the ice 500g, pH is adjusted into 3 with 2N sulfuric acid.Adopt to filter and collect the yellow mercury oxide of being separated out, and then clean with pure water 1000mL, vacuum-drying obtains the 5-propyl group cumarone-2 carboxylic acid 5.8g as pale yellow powder.With 4-propyl group salicylic aldehyde is benchmark, and yield is 17%.

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

With 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 '-N,N-DIMETHYLACETAMIDE 30.0g mixes.With ice bath with the cooling of resulting solution after, add bop reagent 12.96g, in room temperature reaction 24 hours.In resulting mixture, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of entry and methyl alcohol, crystal is separated out.The resulting precipitation of leaching, the mixing solutions of water and methyl alcohol (water 1 parts by volume, methyl alcohol 1 parts by volume) cleans, and vacuum-drying obtains compound (57-a) 6.33g as pale yellow powder.With 2, the 5-dimethoxyaniline is a benchmark, and yield is 67%.

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

With compound (57-a) 6.0g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 100g mix, and resulting mixture is warmed up to 80 ℃, react 5 hours.The cooling back concentrates, and obtaining with the resolvent of compound (57-b) and lawesson reagent is the red sticky solid of principal constituent.

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

The mixture that contains compound (57-b), sodium hydroxide 4.5g and the water 50g that obtain in the preceding paragraph are mixed, at the resulting mixture of ice-cooled stirring down.Then, at the ice-cooled Tripotassium iron hexacyanide 16.8g that adds down, make its reaction.In room temperature reaction 48 hours, the yellow mercury oxide that leaching is separated out.With the precipitation water of leaching, then with the hexane cleaning, clean with ethanol, vacuum-drying, obtaining with compound (57-c) is the faint yellow solid 2.8g of principal constituent.With compound (57-a) is benchmark, and yield is 42%.

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

Compound (57-c) 2.70g and pyridinium chloride 13.5g are mixed, be warmed up to 180 ℃, reacted 2 hours.After resulting mixture cooling, add water, the resulting precipitation of leaching, water, hexane clean, and obtaining with compound (57-d) is the solid 2.4g of principal constituent.With compound (57-c) is benchmark, and 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.At the ice-cooled N, N '-DIC 1.72g of in resulting mixture, adding down.At room temperature make resulting reaction soln react a night, after the filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.The leaching crystallization makes it be dissolved in chloroform again.Add methyl alcohol while stirring resulting solution, the white precipitate that leaching generates cleans with ethanol, and vacuum-drying obtains compound (A57-1) 3.85g as white powder.With compound (57-d) is benchmark, and 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 (d d, 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 that obtains (A57-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A57-1) is when heating up, and the high phase of demonstration viscosity presents clear and definite nematic phase since 143 ℃ from 131 ℃ to 143 ℃.And then compound (A57-1) when cooling, is nematic phase and crystallization until being nematic phase more than 180 ℃ till 100 ℃.

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

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

With 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 '-N,N-DIMETHYLACETAMIDE 95.0g mixes.With ice bath with the cooling of the solution that obtains after, add bop reagent 47.9g, in room temperature reaction 24 hours.In resulting mixture, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of entry and methyl alcohol, crystal is separated out.The resulting precipitation of leaching, the mixing solutions of water and methyl alcohol (water 1 parts by volume, methyl alcohol 1 parts by volume) cleans, and vacuum-drying obtains compound (25-a) 21.0g as yellow powder.With 2, the 5-dimethoxyaniline is a benchmark, and yield is 64%.

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

With compound (25-a) 27.0g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 17.8g and toluene 122g mix, and resulting mixture is warmed up to 80 ℃, react 5 hours.The precipitation of separating out after the leaching cooling, the resolvent that obtains with compound (25-b) and lawesson reagent is the brown solid of principal constituent.

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

The mixture 26.4g that contains compound (25-b), the sodium hydroxide 18.9g and the water 450g that obtain in the preceding paragraph are mixed, under ice-cooled, make resulting mixture reaction.Then, at the ice-cold aqueous solution that contains the 70.7g Tripotassium iron hexacyanide that adds down, make its reaction.In room temperature reaction 12 hours, the yellow mercury oxide that leaching is separated out.With the precipitation water of leaching, then with the hexane cleaning, clean with ethanol, vacuum-drying, obtaining with compound (25-c) is the yellow solid 15g of principal constituent.With compound (25-a) is benchmark, and yield is 58%.

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

Compound (25-c) 15.0g and pyridinium chloride 75.0g are mixed, be warmed up to 180 ℃, reacted 3 hours.After resulting mixture cooling, add water, the resulting precipitation of leaching, water, hot toluene, hexane clean, and obtaining with compound (25-d) is the solid 6.6g of principal constituent.With compound (25-c) is benchmark, and 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.At the ice-cold N, N '-DIC 1.98g of in resulting mixture, adding down.At room temperature make resulting reaction soln react a night, add the 0.8g gac, leave standstill a night after, filtered through silica gel, concentrating under reduced pressure then.In residue, add methyl alcohol, make its crystallization.The leaching crystallization makes it be dissolved in chloroform again.Add methyl alcohol while stirring resulting solution, the brown precipitation that leaching generates is cleaned with ethanol, and vacuum-drying obtains compound (A25-1) 4.30g as filbert powder.With compound (25-d) is benchmark, and 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 (d d, 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 that obtains (A25-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A25-1) is smectic phase from 175 ℃ to 180 ℃ when heating up, from 180 ℃ to being nematic phase more than 238 ℃, show transparency a little at 238 ℃.When cooling, till 168 ℃, be nematic phase and crystallization.

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

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

With 2,5-dimethoxyaniline 35.4g, triethylamine 46.7g and anhydrous chloroform 400g mix in container, drop into 4-phenyl Benzoyl chloride 50.0g when making its reaction.This mixing solutions is warmed up to 60 ℃, and slaking was cooled to room temperature after 3 hours, put in the water.The organic layer that separation is obtained takes out, and water, then cleans with hydrochloric acid.Concentrate resulting organic layer, obtain the solid 76.6g of compound (41-a).With 2, the 5-dimethoxyaniline is a benchmark, and yield is 98%.

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

Similarly operate with the synthesis example of compound (1-b), the resolvent that obtains with compound (41-b) and lawesson reagent is the solid of principal constituent.

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

Similarly operate with the synthesis example of compound (1-c), obtaining with compound (41-c) is the solid of principal constituent.

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

Similarly operate with the synthesis example of compound (1-d), obtaining with compound (41-d) is the solid of principal constituent.

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

Similarly operate with the synthesis example of compound (A1-1), obtain compound (A41-1).With compound (41-d) is benchmark, and 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 crystalline phase transition temperature of compound (A41-1) is confirmed by adopting the polarized light microscope observing structure.If elevated temperature then changes smectic phase near 214 ℃.Further elevated temperature then becomes nematic phase near 234 ℃.Further elevated temperature then becomes isotropic phase near 275 ℃.Reduce temperature by this temperature, then become nematic phase near 269 ℃, become smectic phase near 227 ℃, returning near 204 ℃ is crystallization.That is, compound (A41-1) is smectic phase from 214 ℃ to 234 ℃ when heating up as can be known, is nematic phase from 234 ℃ to 275 ℃.And as can be known, when cooling, be nematic phase, be smectic phase from 227 ℃ to 204 ℃ from 269 ℃ to 227 ℃.

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 4-phenyl Benzoyl chloride of 4-(4-n-propyl phenyl) Benzoyl chloride replacement as 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)

Except that the starting compound in the synthesis example of compound (1-1) (1-d) being changed into compound (43-d), using the same method obtains compound (A43-1).With compound (43-d) is benchmark, and 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 crystalline phase transition temperature of compound (A43-1) is confirmed by adopting the polarized light microscope observing structure.Elevated temperature then becomes isotropic phase near 143 ℃.Reduce temperature by this temperature, then near 118 ℃, be returned as crystallization.That is, compound (A43-1) does not show mesomorphic phase as can be known.

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

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

With 2,3-dicyano Resorcinol 10.0g, potassium hydroxide 35.0g and water 70.0g mix, with mixture while stirring 100 ℃ of heating.Resulting mixture is cooled to room temperature, adds sulfuric acid 40.0g, further stir.In resulting mixture, add ethyl acetate, take out organic layer.With resulting organic layer concentrating under reduced pressure, except that after desolvating, vacuum-drying obtains compound (66-a) 8.5g.With 2,3-dicyano Resorcinol is a benchmark, and yield is 68%.

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

Compound (66-a) 10.0g, 2-amino-6-methoxyl group benzo thiazole 19.1g and tetrahydrofuran (THF) 200.0g are mixed, with mixture while stirring 70 ℃ of heating.Resulting mixture is cooled to room temperature, makes N, N '-dicyclohexylcarbodiimide 12.5g is dissolved among the tetrahydrofuran (THF) 37.5g, after room temperature drips, while stirring 80 ℃ of heated and stirred 36 hours.Resulting mixture put is chilled to room temperature, adopt remove by filter white precipitate after, resulting filtrate decompression is concentrated, remove desolvate after, make the residue crystallization with chloroform.Filter the light green powder that generates, clean with chloroform.The light green powder that obtains is dissolved in the tetrahydrofuran (THF) once more, adds methyl alcohol, crystal is separated out.After filtering the green precipitate that generates, vacuum-drying obtains compound (66-b) 2.8g.With compound (66-a) is benchmark, and 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 resulting mixture in room temperature and to make N, N '-dicyclohexylcarbodiimide 4.56g is dissolved among the chloroform 10.7g and the liquid that obtains stirs.After filtering resulting mixture, add 2N hydrochloric acid 62g, stir,, take out organic layer the liquid separatory.After above separatory operation repetition 2 times, the organic layer that separatory is obtained reclaims, and uses anhydrous sodium sulfate drying, except that after desolvating, adds methyl alcohol with the vaporizer distillation, stirs.Filter the post precipitation that generates, vacuum-drying obtains compound (A66-1) 4.1g.With compound (66-b) is benchmark, and 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 (d d, 2H), 6.07～6.17 (m, 2H), 6.37～6.44 (m, 2H), 6.86～7.01 (m, 8H), 7.08～7.13 (d d, 1H), 7.32 (d, 1H), 7.50～7.52 (m, 2H), 8.00 (d, 1H)

The phase transition temperature of the compound that obtains (A66-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A66-1) is when heating up, and the high phase of demonstration viscosity is difficult to distinguish mesomorphic phase from 125 ℃ to 140 ℃.But, showing clear and definite mesomorphic phase more than 140 ℃.

Embodiment 12～24 and comparative example 1

The Production Example of＜blooming 〉

The 2 quality % aqueous solution of pva coating on glass substrate (polyvinyl alcohol 1000 fully saponified types, Wako Pure Chemical Industries, Ltd.'s system) after the drying, form the film of thickness 89nm.Then, friction treatment is implemented on the surface of resulting film, the composition of composition, dry 1 minute of the drying temperature of being put down in writing with table 2 by spin-coating method coating table 1 on the face of having implemented friction treatment.Next, the temperature when being heated to the rayed that table 2 puts down in writing, the ultraviolet ray of the integrating light quantity put down in writing of exposure chart 2 simultaneously, the blooming of the thickness that formation table 3 is put down in writing.

[table 1]

	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)
	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)	Embodiment 12	??A1-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00
Embodiment 13	??A5-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00	Embodiment 12	??A1-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00
Embodiment 13	??A5-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00	Embodiment 14	??A6-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00
Embodiment 15	??A10-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00	Embodiment 14	??A6-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00

	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)
	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)	Embodiment 16	??A11-1??(29.10)	??-	??IRGACURE?819??(0.87)	??BYK361N??(0.03)	??70.00
Embodiment 17	??A15-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00	Embodiment 16	??A11-1??(29.10)	??-	??IRGACURE?819??(0.87)	??BYK361N??(0.03)	??70.00
Embodiment 17	??A15-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00	Embodiment 18	??A57-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00
Embodiment 19	??A25-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00	Embodiment 18	??A57-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00
Embodiment 19	??A25-1??(14.55)	??-	??IRGACURE?819??(0.44)	??BYK361N??(0.01)	??85.00	Embodiment 20	??A11-1??(9.70)	??LC242??(9.70)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00
Embodiment 21	??A11-1??(11.64)	??LC242??(7.76)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00	Embodiment 20	??A11-1??(9.70)	??LC242??(9.70)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00
Embodiment 21	??A11-1??(11.64)	??LC242??(7.76)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00	Embodiment 22	??A11-1??(13.58)	??LC242??(5.82)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00
Embodiment 23	??A11-1??(15.52)	??LC242??(3.88)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00	Embodiment 22	??A11-1??(13.58)	??LC242??(5.82)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00
Embodiment 23	??A11-1??(15.52)	??LC242??(3.88)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00	Embodiment 24	??A11-1??(17.46)	??LC242??(1.94)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00
Comparative example 1	??-	??LC242??(29.04)	??IRGACURE?819??(0.89)	??BYK361N??(0.09)	??69.15	Embodiment 24	??A11-1??(17.46)	??LC242??(1.94)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00

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

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

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

[table 2]

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

The mensuration of＜optical characteristics 〉

Use mensuration machine (KOBRA-WR, prince's instrumentation machines corporation system) to measure the front phase difference value of blooming.Need to prove,,, just can access the front phase difference value of the blooming of on glass substrate, making so measure the film that attaches glass substrate with the mensuration machine because the glass substrate that uses in the base material does not have birefringence.The optical detecting front phase difference value that obtains is measured 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).And, use laser microscope (LEXT, Olympus Corp's system) to measure the thickness d (μ m) of blooming.Show the result in table 3.Value with Re (546.9) is calculated Δ n (Δ n=Re (546.9)/d) divided by thickness.

[table 3]

	??Re(546.9)	??α	??β	??d(μm)	??Δn
	??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 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 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 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 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 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 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	Embodiment 24	??80.1	??0.887	??1.018	??1.189	??0.067

The synthesis example-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 are dispersed in N, among N '-N,N-DIMETHYLACETAMIDE 700mL.After being heated to 80 ℃, with 30 minutes dripping bromine tert.-butyl acetate 190.5g.Made mixture reaction 2 hours in 130 ℃.Behind the reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 600mL, carry out separatory with pure water 1200mL.And then 2 pure water with 1000mL clean organic layer, the recovery organic layer.Behind anhydrous sodium sulfate dehydration, distill except that desolvating with vaporizer.Residue is dissolved among the acetate 240g, adds hydrobromic acid aqueous solution 72g, stirred 1 hour in 40 ℃.Put be chilled to room temperature after, add 1N-hydrochloric acid 150g, the white powder that leaching is separated out.Further with after the cleaning of 1N-hydrochloric acid, vacuum-drying obtains thus as 4 of yellow powder, 6-dimethyl benzofuran-2-carboxylic acid 81.7g with resulting white powder.With 4,6-dimethyl salicylic aldehyde is a benchmark, and yield is 44%.

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

With 2,5-dimethoxyaniline 96.6g, 4,6-dimethyl benzofuran-2-carboxylic acid 80.0g and chloroform 400.0g mix.With resulting suspension with after the ice bath cooling, with the mixture of 4 hours adding 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 88.7g and chloroform 300g, in room temperature reaction 48 hours.Resulting mixture is concentrated, add 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 resulting precipitation of leaching adds the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of entry and methyl alcohol.The faint yellow precipitation that leaching is separated out, with mixing solutions (water 2 parts by volume, the methyl alcohol 1 parts by volume) cleaning of water-methanol, vacuum-drying obtains compound (11-a) 124.2g as pale yellow powder.With 4,6-dimethyl benzofuran-2-carboxylic acid is a benchmark, and yield is 91%.

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

With compound (11-a) 123.0g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 1200g mix, and resulting mixture is warmed up to 110 ℃, react 8 hours.Behind the 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 is used washed with heptane, vacuum-drying, and obtaining thus with compound (11-b) is the aureus powder 109.2g of principal constituent.With compound (11-a) is benchmark, and yield is 85%.

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

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

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

Compound (11-c) 40.0g and pyridinium chloride 400.0g are mixed, be warmed up to 180 ℃, reacted 3 hours.In the mixture that obtains, add ice, the resulting precipitation of leaching.After the aqueous suspension washing, clean with toluene, vacuum-drying, obtaining with compound (11-d) is the yellow solid 36.6g of principal constituent.With compound (11-c) is benchmark, and 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.At the ice-cooled N, N '-dicyclohexylcarbodiimide 55.6g of in resulting mixture, adding down.At room temperature make resulting reaction soln react a night, after the filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.The leaching crystallization made it be dissolved in chloroform again, adds the 2.3g gac, in stirring at room 1 hour.Filtering solution, with vaporizer filtrate decompression is concentrated into 1/3 after, add methyl alcohol while stir, the white precipitate that leaching generates is used washed with heptane, vacuum-drying obtains compound (A11-1) 74.5g as white powder.With compound (11-d) is benchmark, and yield is 60%.

The synthesis example-3 of embodiment 26＜compound (A11-1) 〉

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

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

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

With 2,5-xylenol 50g, paraformaldehyde 30.7g, Magnesium Chloride Anhydrous 58.4g are dispersed among the tetrahydrofuran (THF) 500mL.In ice bath, stir after 30 minutes, with 2 hours dropping triethylamine 82.83g.Mixture was reacted in water-bath 8 hours, room temperature reaction 120 hours.In reaction solution, add cold 5N-hydrochloric acid 1500mL, after the formation acidity, the ethyl acetate extraction of usefulness 400mL 2 times, collected organic layer.With after the organic layer dehydration, carry out diatomite filtration with anhydrous sodium sulphate, below 40 ℃ filtrate decompression is being concentrated with vaporizer.Residue is dissolved in the 100mL toluene, in solution, adds the heptane of 600mL.In solution, add silica gel 30g, stir after 1 hour, filter.Filtrate decompression is concentrated, and then the adding heptane extracts in residue, the heptane distillation is removed, obtain as 3 of yellow liquid 6-dimethyl salicylic aldehyde 10.5g.With 2, the 5-xylenol is a benchmark, and yield is 17%.

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

Make 3,6-dimethyl salicylic aldehyde 10.48g, salt of wormwood 23.63g are dispersed in N, among N '-N,N-DIMETHYLACETAMIDE 70mL.After being heated to 80 ℃, with 10 minutes dripping bromine tert.-butyl acetate 13.61g.Made mixture reaction 3 hours in 130 ℃.After reaction solution is cooled to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then 2 times the pure water with 300mL cleans organic layer, reclaims organic layer.Behind anhydrous sodium sulfate dehydration, distill except that desolvating with vaporizer.Residue is dissolved in the 40g acetate, adds hydrobromic acid aqueous solution 8g, stirred 1 hour in 40 ℃.Put be chilled to room temperature after, add 1N-salt sour water 10g, the white powder that leaching is separated out.Resulting white powder is further used 1N-salt sour water, followed with after the washed with heptane, and vacuum-drying obtains thus as 4 of white powder, 7-dimethyl benzofuran-2-carboxylic acid 7.31g.With 3,6-dimethyl salicylic aldehyde is a benchmark, and 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 is dispersed among the chloroform 38g.With ice bath with the cooling of resulting suspension after, with the mixture of 4 hours adding 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 8.09g and chloroform 50g, in room temperature reaction 24 hours.Further add 2 in reaction soln, 5-dimethoxyaniline 1.18g reacted 48 hours.Resulting mixture is concentrated, in residue, add mixing solutions (salt sour 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 resulting precipitation of leaching, the mixing solutions (salt sour water 2 parts by volume, methyl alcohol 1 parts by volume) of adding hydrochloric acid water-methanol.Pistac that leaching is separated out precipitation is further cleaned with the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water-methanol.With the resulting 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 water 150g cleaning back leaching.Vacuum-drying obtains compound (61-a) 8.82g as pale yellow powder.With 4,7-dimethyl benzofuran-2-carboxylic acid is a benchmark, and yield is 71%.

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

With compound (61-a) 8.82g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 6.58g and toluene 88g mix, and resulting mixture is warmed up to 110 ℃, react 12 hours.After the cooling, adopt and remove by filter the orange solids of being separated out, in filtrate, add heptane, make its crystallization.The yellow mercury oxide that leaching is separated out, vacuum-drying obtains compound (61-b) 4.7g as the aureus powder thus.With compound (61-a) is benchmark, and yield is 51%.

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

Compound (61-b) 4.27g, potassium hydroxide 3.83g and water 73g are mixed, under ice-cooled, make resulting mixture reaction.Then,, then add methyl alcohol 15g, make its reaction at the ice-cold Tripotassium iron hexacyanide 11.23g that adds down.In room temperature reaction 12 hours, the yellow mercury oxide that leaching is separated out.Precipitation water, methyl alcohol, the ethanol of leaching are cleaned the faint yellow precipitation of leaching.With the yellow powder vacuum-drying that obtains, obtaining with compound (61-c) is the faint yellow solid 3.08g of principal constituent.Compound (61-a) is a benchmark, and yield is 73%.

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

Compound (61-c) 3.08g and pyridinium chloride 15.4g are mixed, be warmed up to 190 ℃, reacted 7 hours.In resulting mixture, add ice, the resulting precipitation of leaching.After the aqueous suspension washing, clean with toluene, vacuum-drying, obtaining with compound (61-d) is the khaki color solid 2.41g of principal constituent.With compound (61-c) is benchmark, and 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.At the ice-cooled N, N '-DIC 2.34g of in resulting mixture, adding down.Make resulting reaction soln at one night of room temperature reaction, after the filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.The leaching crystallization made it be dissolved in chloroform again, adds the 0.3g gac, in stirring at room 1 hour.Filtering solution, with vaporizer filtrate decompression is concentrated into 1/3 after, vigorous stirring limit, limit adds methyl alcohol, the white precipitate that leaching generates is used washed with heptane, vacuum-drying obtains compound (A61-1) 4.52g as cream-coloured powder.With compound (61-d) is benchmark, and 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 (d d, 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 that obtains (A61-1) moves temperature and confirms by adopting the polarized light microscope observing structure.Compound (A61-1) is when heating up, and the high phase of demonstration viscosity provides clear and definite nematic phase since 138 ℃ from 136 ℃ to 138 ℃.And then compound (A61-1) when cooling, is nematic phase and crystallization until being nematic phase more than 150 ℃ till 90 ℃.

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

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

2-cyclohexyl-5-methylphenol 100g, paraformaldehyde 39.5g, Magnesium Chloride Anhydrous 75.0g are dispersed among the tetrahydrofuran (THF) 900mL.Under ice bath, stir after 30 minutes, with 2 hours dropping triethylamine 106.4g.Mixture was reacted 8 hours under water-bath, room temperature reaction 96 hours.In reaction solution, add cold 5N-hydrochloric acid 1500mL, become acidity after, with the ethyl acetate extraction of 400mL 2 times, collected organic layer.With organic layer with anhydrous sodium sulfate dehydration after, with vaporizer at concentrating under reduced pressure below 40 ℃.Residue is dissolved in the 100mL toluene, in solution, adds the heptane of 600mL.In solution, add silica gel 38g, remove with vaporizer and desolvate.Add heptane and extract in residue, heptane is removed in distillation then, obtains slow crystalline yellow crystal 4 thus, 6-dimethyl salicylic aldehyde 35.2g.With 2-cyclohexyl-5-methylphenol is benchmark, and yield is 31%.

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

Make 3-cyclohexyl-6-cresotinic acid aldehyde 35.0g, salt of wormwood 72.2g be dispersed in N, among N '-N,N-DIMETHYLACETAMIDE 300mL.After being heated to 80 ℃, with 30 minutes dripping bromine tert.-butyl acetate 41.6g.Made mixture reaction 3 hours at 130 ℃.Behind the reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then 2 times the pure water with 500mL cleans organic layer, reclaims organic layer.Behind anhydrous sodium sulfate dehydration, distill except that desolvating with vaporizer.Residue is dissolved in the 240g acetate, adds hydrobromic acid aqueous solution 72g, stirred 1 hour in 40 ℃.Put be chilled to room temperature after, add 1N-hydrochloric acid 150g, the white powder that leaching is separated out.And then with resulting white powder 1N-hydrochloric acid, then with after the washed with heptane, vacuum-drying obtains the 4-methyl-7-cyclohexyl benzo furans-2-carboxylic acid 25.8g as white powder thus.With 3-cyclohexyl-6-cresotinic acid aldehyde is benchmark, and yield is 59%.

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

Make 2,5-dimethoxyaniline 22.2g, 4-methyl-7-cyclohexyl benzo furans-2-carboxylic acid 25.00g, triethylamine 9.79g are dispersed among the chloroform 125g.With resulting suspension with after the ice bath cooling, with the mixture of 4 hours adding 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 20.4g and chloroform 100g, in room temperature reaction 72 hours.Resulting mixture is concentrated, in residue, add mixing solutions (salt sour 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 resulting precipitation of leaching, the mixing solutions (salt sour water 2 parts by volume, methyl alcohol 1 parts by volume) of adding hydrochloric acid water-methanol.Pistac that leaching is separated out precipitation is further cleaned with the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water-methanol.With the pistac that obtains precipitation 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, then clean leaching with methyl alcohol 150g.Vacuum-drying obtains compound (69-a) 12.3g as pale yellow powder.With 4-methyl-7-cyclohexyl benzo furans-2-carboxylic acid is benchmark, and yield is 32%.

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

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

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

Compound (69-b) 11.5g, the potassium hydroxide 9.58g and the water 182g that obtain in the preceding paragraph are mixed, under ice-cooled, make resulting mixture reaction.Then, add Tripotassium iron hexacyanide 28.09g, modulation contains the dispersion liquid of compound (69-b).In dispersion liquid, add methyl alcohol 40g, in 40 ℃ of reactions 2 hours, in room temperature reaction 24 hours, the yellow mercury oxide that leaching is separated out.With the precipitation water of leaching, then clean with hexane.And then, it is dispersed among mixed solvent (toluene 1 parts by volume, the heptane 2 parts by volume) 400ml of toluene-heptane, reclaim flaxen insoluble composition.With resulting faint yellow vacuum-drying, obtaining with compound (69-c) is the faint yellow solid 4.5g of principal constituent.With compound (69-a) is benchmark, and yield is 36%.

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

Compound (69-c) 4.54g and pyridinium chloride 45.4g are mixed, be warmed up to 180 ℃, reacted 3 hours.In resulting mixture, add ice, the resulting precipitation of leaching.After the aqueous suspension washing, clean with toluene, vacuum-drying, obtaining with compound (69-d) is the khaki color solid 3.4g of principal constituent.With compound (69-c) is benchmark, and 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.At the ice-cooled N, N '-DIC 2.71g of in resulting mixture, adding down.At room temperature make resulting reaction soln react a night, after the filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.The leaching crystallization made it be dissolved in chloroform again, adds the 0.3g gac, in stirring at room 1 hour.Solution is filtered, with vaporizer filtrate decompression is concentrated into 1/3 after, add methyl alcohol while stir, the white precipitate of leaching generation is used washed with heptane, vacuum-drying obtains compound (A69-1) 4.84g as cream-coloured powder.With compound (69-d) is benchmark, and 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 (d d, 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 that obtains (A69-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A69-1) since 207 ℃ of phases that show that viscosity is high, carries out thermopolymerization at 220 ℃ when heating up.

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 among the tetrahydrofuran (THF) 900mL.Under ice bath, stir after 30 minutes, with 2 hours dropping triethylamine 111.5g.Mixture was reacted 8 hours under water-bath, in room temperature reaction 96 hours.In reaction solution, add cold 5N-hydrochloric acid 1500mL, become acidity after, with the ethyl acetate extraction of 400mL 2 times, collected organic layer.With organic layer with anhydrous sodium sulfate dehydration after, with vaporizer at concentrating under reduced pressure below 40 ℃.Residue is dissolved in the 100mL toluene, in solution, adds the heptane of 600mL.In solution, add silica gel 90g, remove with vaporizer and desolvate.Add heptane and extract in residue, heptane is removed in distillation then, obtains the 3-propyl group salicylic aldehyde 28.8g as yellow liquid thus.With the 2-propylphenol is benchmark, and 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 be dispersed in N, among N '-N,N-DIMETHYLACETAMIDE 200mL.After being heated to 80 ℃, with 30 minutes dripping bromine tert.-butyl acetate 34.2g.Mixture was reacted 2 hours in 130 ℃.Behind the reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then 2 times the pure water with 500mL cleans organic layer, reclaims organic layer.Behind anhydrous sodium sulfate dehydration, distill except that desolvating with vaporizer.Residue is dissolved in the 150g acetate, adds hydrobromic acid aqueous solution 45g, stirred 1 hour in 40 ℃.Put be chilled to room temperature after, add 1N-hydrochloric acid 150g, the white powder that leaching is separated out.And then with resulting white powder 1N-hydrochloric acid, then with after the 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 is benchmark, and 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 are dispersed among the chloroform 90g.With ice bath with the cooling of resulting suspension after, with the mixture of 4 hours adding 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 18.6g and chloroform 100g, in room temperature reaction 72 hours.Concentrate resulting mixture, in residue, add mixing solutions (salt sour 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 resulting precipitation of leaching adds in the mixing solutions (salt sour water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.Leaching pistac precipitation is with mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, the methyl alcohol 2 parts by volume) cleaning of the 1N-KOH aqueous solution-methyl alcohol, leaching.Vacuum-drying obtains compound (70-a) 19.8g as pale yellow powder.With 7-propyl group cumarone-2-carboxylic acid is benchmark, and yield is 66%.

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

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

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

Compound (70-b) 18.6g, potassium hydroxide 17.86g and water 320g are mixed, at the ice-cooled mixture reaction that obtains that makes down.Then, add Tripotassium iron hexacyanide 52.41g, modulation contains the dispersion liquid of compound (70-b).In dispersion liquid, add methyl alcohol 70g, in 40 ℃ of reactions 2 hours, in room temperature reaction 24 hours, the yellow mercury oxide that leaching is separated out.With the precipitation water of leaching, then use washed with methanol.And then, yellow powder is cleaned leaching with hot ethanol.With resulting yellow powder vacuum-drying, obtaining with compound (70-c) is the faint yellow solid 15.8g of principal constituent.With compound (70-a) is benchmark, and yield is 76%.

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

Compound (70-c) 15.8g and pyridinium chloride 158g are mixed, be warmed up to 180 ℃, reacted 3 hours.Resulting mixture is added in the ice the resulting precipitation of leaching.After the aqueous suspension washing, clean with toluene, make its vacuum-drying, obtaining with compound (70-d) is the khaki color solid 13.6g of principal constituent.With compound (70-c) is benchmark, and 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.At the ice-cooled N, N '-DIC 4.65g of in resulting mixture, adding down.Make resulting reaction soln react a night in room temperature, after the filtered through silica gel, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.The leaching crystallization made it be dissolved in chloroform again, adds the 0.3g gac, in stirring at room 1 hour.Solution is filtered, with vaporizer filtrate decompression is concentrated into 1/3 after, add methyl alcohol while stir, the white precipitate of leaching generation is used washed with heptane, vacuum-drying obtains compound (A70-1) 8.38g as cream-coloured powder.With compound (70-d) is benchmark, and 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 (d d, 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 that obtains (A70-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A70-1) is when heating up, and the high phase of demonstration viscosity provides clear and definite nematic phase since 142 ℃ from 137 ℃ to 142 ℃.And then compound (A70-1) is nematic phase and crystallization until all being nematic phase more than 220 ℃ till 125 ℃ when cooling.Embodiment 30～33 and comparative example 1

The Production Example of＜blooming 〉

The 2 quality % aqueous solution of pva coating on glass substrate (polyvinyl alcohol 1000 fully saponified types, Wako Pure Chemical Industries, Ltd.'s system) after the drying, form the film of thickness 89nm.Then, friction treatment is implemented on the surface of resulting film, the composition of composition, dry 1 minute of the drying temperature of being put down in writing with table 5 by spin-coating method coating table 4 on the face of having implemented friction treatment.Next, the temperature when being heated to the rayed that table 5 puts down in writing, the ultraviolet ray of the integrating light quantity put down in writing of exposure chart 5 simultaneously, the blooming of the thickness that formation table 6 is put down in writing.

[table 4]

	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)
	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)	Embodiment 30	??A61-1??(19.40)	??-	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00
Embodiment 31	??A70-1??(19.40)	??-	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00	Embodiment 30	??A61-1??(19.40)	??-	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00
Embodiment 31	??A70-1??(19.40)	??-	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00	Embodiment 32	??A69-1??(4.85)	??B1-1??(14.55)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00
Embodiment 33	??A69-1??(9.70)	??B1-1??(9.70)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00	Embodiment 32	??A69-1??(4.85)	??B1-1??(14.55)	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00

	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)
	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)	Comparative example 1	??-	??LC242??(29.04)	??IRGACURE?819??(0.89)	??BYK361N??(0.09)	??69.15

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

LC242: the same

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

[table 5]

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

The mensuration of＜optical characteristics 〉

Use mensuration machine (KOBRA-WR, prince's instrumentation machines corporation system) to measure the front phase difference value of blooming.Need to prove,,, just can access the front phase difference value of the blooming of on glass substrate, making so measure the film that attaches glass substrate with the mensuration machine because the glass substrate that uses in the base material does not have birefringence.The optical detecting front phase difference value that obtains is measured 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).And, use laser microscope (LEXT, Olympus Corp's system) to measure the thickness d (μ m) of blooming.To the results are shown in table 6.Value with Re (546.9) is calculated Δ n (Δ n=Re (546.9)/d) divided by film thickness gauge.

[table 6]

	??Re(546.9)	??α	??β	??d(μm)	??Δn
	??Re(546.9)	??α	??β	??d(μm)	??Δn	Embodiment
30	??84.5	??0.888	??1.017	??1.186	??0.071	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 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	Embodiment 33	??74.7	??0.938	??1.006	??1.087	??0.067

The hot rerum natura of embodiment 34～39 and comparative example 2～7＜composition 〉

The modulation of＜composition 〉

The composition of the composition of modulometer 7.

[table 7]

	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)
	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)	Embodiment 34	??A11-1??(14.6)	??B5-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88
Embodiment 35	??A11-1??(14.6)	??B11-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88	Embodiment 34	??A11-1??(14.6)	??B5-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88
Embodiment 35	??A11-1??(14.6)	??B11-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88	Embodiment 36	??A11-1??(14.6)	??B1-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88
Embodiment 37	??A11-1??(14.6)	??B2-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88	Embodiment 36	??A11-1??(14.6)	??B1-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88
Embodiment 37	??A11-1??(14.6)	??B2-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88	Embodiment 38	??A11-1??(14.6)	??B9-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88
Embodiment 39	??A11-1??(14.6)	??C1-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88	Embodiment 38	??A11-1??(14.6)	??B9-1??(4.9)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88

	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)
	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)	Comparative example 2	??-	??B5-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88
Comparative example 3	??-	??B11-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88	Comparative example 2	??-	??B5-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88
Comparative example 3	??-	??B11-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88	Comparative example 4	??-	??B1-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88
Comparative example 5	??-	??B2-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88	Comparative example 4	??-	??B1-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88
Comparative example 5	??-	??B2-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88	Comparative example 6	??-	??B9-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88
Comparative example 7	??-	??C1-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88	Comparative example 6	??-	??B9-1??(19.5)	??IRGACURE?819??(0.6)	??BYK361N??(0.02)	??79.88

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

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

＜hot rerum natura is observed 〉

The 2 quality % aqueous solution of pva coating on glass substrate (polyvinyl alcohol 1000 fully saponified types, Wako Pure Chemical Industries, Ltd.'s system) behind the heat drying, form the film of thickness 89nm.Friction treatment is implemented on surface to film, forms alignment films.The composition of on the face of having implemented friction treatment, being put down in writing by spin-coating method coating table 8.Use is with the polarization microscope (hot platform: LTS350, Linkam corporate system, polarization microscope: BX-51, Olympus Corp's system) of hot platform, the substrate heating after will being coated with 30 ℃/minute of heat-up rates during intensification, the situation of observation group's compound simultaneously.Adopt naturally cooling, the situation of observation group's compound during cooling.Show the result in table 8.

[table 8]

T _a: from crystalline transition is nematic phase, begins to form the temperature of 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 on glass substrate (polyvinyl alcohol 1000 fully saponified types, Wako Pure Chemical Industries, Ltd.'s system), heat drying, the film of formation thickness 89nm.Friction treatment is implemented on surface to film, forms alignment films.The composition of on the face of having implemented friction treatment, being put down in writing by spin-coating method coating table 7, the temperature (T that is put down in writing with table 9 _d) dry 1 minute.Temperature (the T that puts down in writing at table 9 _e) place after 1 minute irradiation integrating light quantity 2400mJ/cm down ²Ultraviolet ray, make film.At this, T _eBe that reproducibility is made the non-crystallizable and required temperature of the film single domain homogeneous of liquid crystal, T well _eLow more, expression can be made blooming at low temperature more.

[table 9]

	??T _d	??T _e
	??T _d	??T _e	Embodiment 34	??100℃	??70℃
Embodiment 35	??130℃	??70℃	Embodiment 34	??100℃	??70℃
Embodiment 35	??130℃	??70℃	Embodiment 36	??100℃	??70℃
Embodiment 37	??100℃	??70℃	Embodiment 36	??100℃	??70℃
Embodiment 37	??100℃	??70℃	Embodiment 38	??100℃	??70℃

	??T _d	??T _e
	??T _d	??T _e	Embodiment 39	??100℃	??70℃
Comparative example 2	??110℃	??80℃	Embodiment 39	??100℃	??70℃
Comparative example 2	??110℃	??80℃	Comparative example 3	??180℃	??165℃
Comparative example 4	??110℃	??80℃	Comparative example 3	??180℃	??165℃
Comparative example 4	??110℃	??80℃	Comparative example 5	??120℃	??90℃
Comparative example 6	??145℃	??120℃	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) the 5-chloro-4, the synthesis example of 6-dimethyl salicylic aldehyde

Make 4-chloro-3,5-xylenol 100g, paraformaldehyde 47.94g, Magnesium Chloride Anhydrous 91.19g are dispersed among the acetonitrile 800mL.Under ice bath, stir after 30 minutes, with 2 hours dropping triethylamine 129.23g.With mixture water-bath 3 hours, 50 ℃ of reactions 18 hours.In reaction solution, add cold 2N-hydrochloric acid, become neutrality after, with the ethyl acetate extraction of 600mL 2 times, collected organic layer.With organic layer with anhydrous sodium sulfate dehydration after, add gac 3g, after the stirring, carry out diatomite filtration, filtrate decompression is being concentrated below 40 ℃ with vaporizer.In residue, add heptane 1000mL, by removing by filter insolubles.Reclaim filtrate, carry out recrystallization, obtain 5-chloro-4 thus, 6-dimethyl salicylic aldehyde 20.00g as pale yellow powder.With 4-chloro-3, the 5-xylenol is a benchmark, and yield is 17%.

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

Make 5-chloro-4,6-dimethyl salicylic aldehyde 20.00g, salt of wormwood 36.68g are dispersed in N, among N '-N,N-DIMETHYLACETAMIDE 150mL.After being heated to 80 ℃, with 10 minutes dripping bromine tert.-butyl acetate 21.13g.Made mixture reaction 3 hours in 130 ℃.Behind the reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then 2 times the pure water with 300mL cleans organic layer, reclaims organic layer.Behind anhydrous sodium sulfate dehydration, distill except that desolvating with vaporizer.Residue is dissolved in the 60g acetate, adds trifluoroacetic acid 20g, stirred 1 hour in 60 ℃.Put be chilled to room temperature after, add 1N-salt sour water 10g, the white powder that leaching is separated out.Resulting white powder is further used 1N-salt sour water, followed with after the washed with heptane, and vacuum-drying obtains the 5-chloro-4 as white powder thus, 6-dimethyl benzofuran-2-carboxylic acid 19.37g.With 5-chloro-4,6-dimethyl salicylic aldehyde is a benchmark, and yield is 80%.

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

Make 2,5-dimethoxyaniline 19.43g, 5-chloro-4,6-dimethyl benzofuran-2-carboxylic acid 19.00g is dispersed in the 200g chloroform.With ice bath with the cooling of resulting suspension after, with the mixture of 6 hours adding 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 17.64g and chloroform 80g, in room temperature reaction 24 hours.Further add 2 in reaction soln, 5-dimethoxyaniline 0.2g reacted 48 hours.Concentrate resulting mixture, in residue, add mixing solutions (salt sour water 2 parts by volume, the methyl alcohol 1 parts by volume) 400g of 1N-hydrochloric acid, methyl alcohol, make its crystallization.With resulting faint yellow powder methyl alcohol, then with toluene cleaning, leaching.Vacuum-drying obtains compound (71-a) 13.68g as pale yellow powder.With 5-chloro-4,6-dimethyl benzofuran-2-carboxylic acid is a benchmark, and yield is 45%.

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

With compound (71-a) 13.63g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.19g and toluene 150g mix, and resulting mixture is warmed up to 110 ℃, react 6 hours.After the cooling, add the 1N-aqueous sodium hydroxide solution.Reclaim organic layer, add heptane 100mL, make its crystallization.The red crystallization of leaching makes its drying, obtains compound (71-b) 14.24g as orange powder.Though be mixed with the impurity that derives 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, under ice-cooled, make resulting mixture reaction.Then,, next add methyl alcohol 44g, react at the ice-cooled Tripotassium iron hexacyanide 34.03g that adds down., reacted 8 hours after 12 hours at room temperature reaction at 80 ℃.The faint yellow precipitation that leaching is separated out.Precipitation water, methyl alcohol, the ethanol of leaching are cleaned the faint yellow precipitation of leaching.With resulting pale yellow powder vacuum-drying, obtaining with compound (71-c) is the faint yellow solid 10.3g of principal constituent.Yield is benchmark, is 73% in two steps with compound (71-a).

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

Compound (71-c) 10.00g and pyridinium chloride 100g are mixed, be warmed up to 190 ℃, reacted 2 hours.Resulting mixture is added in the ice the resulting precipitation of leaching.After the aqueous suspension washing, clean with toluene, chloroform, vacuum-drying, obtaining with compound (71-d) is the yellow solid 7.20g of principal constituent.With compound (71-c) is benchmark, and 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.At the ice-cooled N, N '-DIC 0.88g of in resulting mixture, adding down.After room temperature makes resulting reaction soln react a night, carries out diatomite filtration, concentrating under reduced pressure.In residue, add ethanol, make its crystallization.The leaching crystallization made it be dissolved in chloroform again, adds the 0.3g gac, in stirring at room 1 hour.Filtering solution, with vaporizer filtrate decompression is concentrated into 1/3 after, vigorous stirring limit, limit adds methyl alcohol, the white precipitate that leaching generates is used washed with heptane, vacuum-drying obtains compound (A71-1) 2.58g as cream-coloured powder.With compound (71-d) is benchmark, and 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 (d d, 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 that obtains (A71-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A71-1) is when heating up, and the high phase of demonstration viscosity provides clear and definite nematic phase since 154 ℃ from 148 ℃ to 154 ℃.And then compound (A71-1) when cooling, is nematic phase and crystallization until all being nematic phase more than 160 ℃ till 127 ℃.

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 are dispersed among the chloroform 100g.With ice bath with the cooling of resulting suspension after, with the mixture of 4 hours adding 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 11.77g and chloroform 70g, in room temperature reaction 24 hours.In reaction soln, further add 2,5-dimethoxyaniline 0.5g reaction 48 hours.Concentrate resulting mixture, in residue, add mixing solutions (salt sour 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 resulting precipitation of leaching, the mixing solutions (salt sour water 2 parts by volume, methyl alcohol 1 parts by volume) of adding hydrochloric acid water-methanol.Aureus that leaching is separated out precipitation is further cleaned with the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water-methanol.With the resulting 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 water 150g cleaning, leaching.Vacuum-drying obtains compound (21-a) 8.47g as yellow powder.With benzothiazole-2-carboxylic acid is benchmark, and yield is 48%.

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

With compound (21-a) 8.47g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 6.54g and toluene 85g mix, and resulting mixture is warming up to 110 ℃, react 6 hours.After the cooling, add the 1N-aqueous sodium hydroxide solution.Reclaim organic layer, add heptane 100mL, make its crystallization.The orange crystallization of leaching, vacuum-drying obtains the compound (21-b) as the aureus powder thus.Though be mixed with the impurity that derives 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, make resulting mixture in ice-cooled reaction down.Then,, next add methyl alcohol 30g, make its reaction at the ice-cooled Tripotassium iron hexacyanide 24.19g that adds down.In room temperature reaction 12 hours, in 50 ℃ of reactions 12 hours, the faint yellow precipitation that leaching is separated out.Precipitation water, methyl alcohol, the ethanol of leaching are cleaned, the faint yellow precipitation of leaching, with the pale yellow powder vacuum-drying that obtains, obtaining with compound (21-c) is the faint yellow solid 7.40g of principal constituent.With compound (21-a) is benchmark, and yield is 84%.

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

Compound (21-c) 7.00g and pyridinium chloride 105g are mixed, be warmed up to 190 ℃, reacted 3 hours.Resulting mixture is added in the ice the resulting precipitation of leaching.After the aqueous suspension washing, clean with toluene, vacuum-drying, obtaining with compound (21-d) is the yellow solid 6.00g of principal constituent.With compound (21-c) be 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.At the ice-cooled N, N '-DIC 1.01g of in resulting mixture, adding down.At room temperature make resulting reaction soln react a night, carry out diatomite filtration after, concentrating under reduced pressure.In residue, add methyl alcohol, make its crystallization.The leaching crystallization was dissolved in the chloroform it again, adds the 0.3g gac, in stirring at room 1 hour.Filtering solution, with vaporizer filtrate decompression is concentrated into 1/3 after, vigorous stirring limit, limit adds methyl alcohol, the white precipitate that leaching generates is used washed with heptane, vacuum-drying obtains compound (A21-1) 2.70g as cream-coloured powder.With compound (21-d) is benchmark, and 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 that obtains (A21-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A21-1) is when heating up, and the high phase of demonstration viscosity provides clear and definite nematic phase since 155 ℃ from 137 ℃ to 155 ℃.And then compound (A21-1) all is being nematic phase more than 170 ℃, is nematic phase and crystallization when cooling till 121 ℃.

Embodiment 42～43, comparative example 1

The Production Example of＜blooming 〉

The 2 quality % aqueous solution of pva coating on glass substrate (polyvinyl alcohol 1000 fully saponified types, Wako Pure Chemical Industries, Ltd.'s system) after the drying, form the film of thickness 89nm.Then, friction treatment is implemented on the surface of resulting film, the composition of composition, under the drying temperature of table 11 record dry 1 minute by spin-coating method coating table 10 on the face of having implemented friction treatment.Next, the temperature when being heated to the rayed that table 11 puts down in writing, the ultraviolet ray of the integrating light quantity of exposure chart 11 records simultaneously, the blooming of the thickness that formation table 12 is put down in writing.

[table 10]

	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)
	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)	Embodiment 42	??A71-1??(19.40)	??-	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00
Embodiment 43	??A21-1??(19.40)	??-	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00	Embodiment 42	??A71-1??(19.40)	??-	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00
Embodiment 43	??A21-1??(19.40)	??-	??IRGACURE?819??(0.58)	??BYK361N??(0.02)	??80.00	Comparative example 1	??-	??LC242??(29.04)	??IRGACURE?819??(0.89)	??BYK361N??(0.09)	??69.15

LC242: the same

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

[table 11]

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

The mensuration of＜optical characteristics 〉

Use mensuration machine (KOBRA-WR, prince's instrumentation machines corporation system) to measure the front phase difference value of blooming.Need to prove,,, just can access the front phase difference value of the blooming of on glass substrate, making so measure the film that attaches glass substrate with the mensuration machine because the glass substrate that uses in the base material does not have birefringence.Resulting optical detecting front phase difference value is measured 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).And, use laser microscope (LEXT, Olympus Corp's system) to measure the thickness d (μ m) of blooming.Show the result in table 12.Value with Re (549.4) is calculated Δ n (Δ n=Re (549.4)/d) divided by film thickness gauge.

[table 12]

	??Re(549.4)	??α	??β	??d(μm)	??Δn
	??Re(549.4)	??α	??β	??d(μm)	??Δn	Embodiment 42	??75.0	??0.811	??1.039	??1.150	??0.060

	??Re(549.4)	??α	??β	??d(μm)	??Δn
	??Re(549.4)	??α	??β	??d(μm)	??Δn	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	Embodiment 43	??112.0	??0.858	??1.030	??1.546	??0.072

The blooming of embodiment 12～24, embodiment 30～33 and embodiment 42～43, the value of [Re (447.3)/Re (546.9)] (α in the table) is below 1.And the value of [Re (627.8)/Re (546.9)] (β in the table) is more than 1.That is, the wavelength dependency of specific refractory power shows that so-called head sea is long dispersed, 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 has the characteristic of optical compensation excellence.And then, by embodiment 20～24 and embodiment 32～33 as can be known, only compound of the present invention is mixed with liquid crystalline cpd, just can grow and disperse freely to control wavelength dispersibility from positive wavelength dispersion to head sea.

In addition, with embodiment 34～39 and comparative example 2～7 relatively, as can be known, by compound of the present invention is mixed with liquid crystalline cpd, the temperature movement of demonstration one-domain structure is to low temperature side, can be at low temperature manufacturing blooming more.

Embodiment 44～45

The Production Example of＜blooming 〉

Same with embodiment 42～43, comparative example 1, the composition of the composition of being put down in writing by spin-coating method coating table 13,140 ℃ of dryings after 1 minute, irradiation integrating light quantity 2400mJ/cm in 80 ℃ of heating ²Ultraviolet ray, form blooming.Show the result in table 14.

[table 13]

	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)
	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)	Embodiment 44	??A11-1??(21.79)	??B1-1??(5.45)	??IRGACURE?369??(1.90)	??BYK361N??(0.02)	??70.84
Embodiment 45	??A11-1??(21.79)	??B1-1??(5.45)	??IRGACURE?819??(0.89)	??BYK361N??(0.02)	??71.85	Embodiment 44	??A11-1??(21.79)	??B1-1??(5.45)	??IRGACURE?369??(1.90)	??BYK361N??(0.02)	??70.84

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
	??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	Embodiment 44	??147.0	??0.891	??1.016	??2.380	??0.062

The thermal test of＜blooming 〉

The blooming that obtains among embodiment 44 and the embodiment 45 was kept 1000 hours in the baking oven of 85 ℃ of humidity 0% of temperature, carry out thermal test.Optical characteristics before and after the determination test, and then, from the α value after the test, deduct the α value of initial value, with the value that obtains as variation delta α.If Δ α more than-0.2+below 0.2, can judge that then change of optical property is little.To the results are shown in table 15.

[table 15]

The humidity resistance test of＜blooming 〉

The blooming that obtains among embodiment 44 and the embodiment 45 was kept 1000 hours in the baking oven of 60 ℃ of humidity 90% of temperature, carry out the humidity resistance test.Optical characteristics before and after the determination test, and then, from the α value after the test, deduct the α value of initial value, with the value that obtains as variation delta α.If Δ α more than-0.2+below 0.2, can judge that then change of optical property is little.To the results are shown in table 16.

[table 16]

Shown in table 15 and table 16, blooming of the present invention in the test of thermal test and humidity resistance Δ α more than-0.2+below 0.2, hence one can see that, and blooming of the present invention shows good thermotolerance and humidity resistance simultaneously.In addition, shown in table 16, the blooming of embodiment 44 shows littler Δ α in humidity resistance, and hence one can see that, if use acetophenone compound as polymerization starter, then blooming shows better humidity resistance, is favorable durability.

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

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

Make

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

(2) 4,5, the synthesis example of 6-trimethylammonium benzo furans-2-carboxylic acid

Make

4,5,6-trimethylammonium salicylic aldehyde 8.10g, salt of wormwood 16.36g are dispersed in N, among N '-N,N-DIMETHYLACETAMIDE 50mL.After being heated to 80 ℃, with 30 minutes dripping bromine tert.-butyl acetate 9.62g.Make mixture 135 ℃ 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 times the pure water with 500mL cleans organic layer, reclaims organic layer.Behind anhydrous sodium sulfate dehydration, distill except that desolvating with vaporizer.Residue is dissolved in the 150g acetate, adds hydrobromic acid aqueous solution 45g, stirred 1 hour in 40 ℃.Put be chilled to room temperature after, add 1N-hydrochloric acid 150g, the incarnadine powder that leaching is separated out.The incarnadine powder that obtains is further used 1N-hydrochloric acid, followed with after the toluene cleaning, and vacuum-drying obtains thus as 4,5 of incarnadine powder, 6-trimethylammonium benzo furans-2-carboxylic acid 6.34g.With 4,5,6-trimethylammonium salicylic aldehyde is a benchmark, and yield is 63%.

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

Make 2,5-dimethoxyaniline 7.13g, 4,5,6-trimethylammonium benzo furans-2-carboxylic acid 6.34g is dispersed among the chloroform 30g.With ice bath with the cooling of resulting suspension after, with the mixture of 4 hours adding 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 6.55g and chloroform 100g, in room temperature reaction 48 hours.With resulting mixture concentrating under reduced pressure, in residue, add mixing solutions (salt sour water 2 parts by volume, the methyl alcohol 1 parts by volume) 400g of 1N-hydrochloric acid, methyl alcohol, make its crystallization.The resulting precipitation of leaching adds it in mixing solutions (salt sour water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.The greenish orange look precipitation of leaching is with mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, the methyl alcohol 2 parts by volume) cleaning 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 benzo furans-2-carboxylic acid is a benchmark, and yield is 89%.

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

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

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

Compound (72-b) 9.83g, potassium hydroxide 8.47g and water 400g are mixed, under ice-cooled, make resulting mixture reaction.Then, add Tripotassium iron hexacyanide 24.84g, modulation contains the dispersion liquid of compound (72-b).In dispersion liquid, add methyl alcohol 70g, in 60 ℃ of reactions 48 hours, the yellow mercury oxide that leaching is separated out.With filter the precipitation water, then use washed with methanol.And then, yellow powder is carried out recrystallization with hot toluene.The faint yellow crystallization that leaching generates, vacuum-drying, obtaining with compound (72-c) is the faint yellow solid 4.60g of principal constituent.With compound (72-a) is benchmark, and yield is 47%.

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

Compound (72-c) 4.60g and pyridinium chloride 64.4g are mixed, be warmed up to 180 ℃, reacted 3 hours.The mixture that obtains is added in the ice the resulting precipitation of leaching.After the aqueous suspension washing, clean with toluene, vacuum-drying, obtaining with compound (72-d) is the yellow-green colour solid 4.10g of principal constituent.With compound (72-c) is benchmark, and 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.In the ice-cooled mixture that is obtaining down, add N, N '-DIC 1.02g.Make resulting reaction soln react a night in room temperature, in reaction solution, add silica gel 4g, gac 200mg, after 1 hour, carry out diatomite filtration in stirring at room.Concentrating under reduced pressure filtrate, remove chloroform after, in solution, add methyl alcohol, crystal is separated out.The leaching cream-coloured powder, and then, use washed with heptane with after the ethanol cleaning 2 times, vacuum-drying obtains compound (A72-1) 2.95g as cream-coloured powder.With compound (72-d) is benchmark, and 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 that obtains (A72-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A72-1) is when heating up, and the high phase of demonstration viscosity provides clear and definite nematic phase since 148 ℃ from 136 ℃ to 148 ℃.And then compound (A72-1) is nematic phase and crystallization until all being nematic phase more than 170 ℃ till 120 ℃ when cooling.

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

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

Make 4-Methyl Salicylaldehyde 20.0g, salt of wormwood 48.73g be dispersed in N, among N '-N,N-DIMETHYLACETAMIDE 100mL.After being heated to 70 ℃, with 30 minutes dripping bromine tert.-butyl acetate 28.65g.Make mixture 135 ℃ of reactions 2 hours.Behind the reaction solution cool to room temperature, add methyl iso-butyl ketone (MIBK) 200mL, carry out separatory with pure water 1000mL.And then 2 times the pure water with 500mL cleans organic layer, reclaims organic layer.Behind anhydrous sodium sulfate dehydration, distill except that desolvating with vaporizer.Residue is dissolved in the 150g acetate, adds the 45g hydrobromic acid aqueous solution, stirred 1 hour in 40 ℃.Put be chilled to room temperature after, add 1N-hydrochloric acid 150g, the white powder that leaching is separated out.Resulting white powder is further used 1N-hydrochloric acid, followed with after heptane, the toluene cleaning, and vacuum-drying obtains the 6-methyl cumarone-2-carboxylic acid 20.58g as white powder thus.With the 4-Methyl Salicylaldehyde is benchmark, and yield is 80%.

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

Make 2,5-dimethoxyaniline 26.09g, 6-methyl cumarone-2-carboxylic acid 20.00g are dispersed among the chloroform 100g.With ice bath with the cooling of resulting suspension after, with the mixture of 4 hours adding 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 23.94g and chloroform 120g, in room temperature reaction 48 hours.Resulting mixture is concentrated, in residue, add 1N-hydrochloric acid, methanol mixture (salt sour water 2 parts by volume, methyl alcohol 1 parts by volume) 400g, make its crystallization.The resulting precipitation of leaching adds it in mixing solutions (salt sour water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.Leaching pistac precipitation with mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, the methyl alcohol 2 parts by volume) cleaning of the 1N-KOH aqueous solution-methyl alcohol, is filtered.Vacuum-drying obtains compound (73-a) 31.26g as pale yellow powder.With 6-methyl cumarone-2-carboxylic acid is benchmark, and yield is 89%.

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

With compound (73-a) 31.26g, 2, two (4-p-methoxy-phenyl)-1.3-two sulphur-2 of 4-, 4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 24.73g and toluene 300g mix, and resulting mixture is warmed up to 110 ℃, react 6 hours.After the cooling, after toluene solution usefulness 2N-aqueous sodium hydroxide solution 500mL cleaning 3 times, behind the recovery organic layer, add normal heptane, make its crystallization.The aureus crystallization that leaching obtains, vacuum-drying obtains the compound (73-b) as the aureus powder thus.(73-b) all is directly used in subsequent step with resulting compound.

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

Compound (73-b) 35.69g, potassium hydroxide 33.37g and water 630g are mixed.Then, add Tripotassium iron hexacyanide 97.91g, modulation contains the dispersion liquid of compound (73-b).In dispersion liquid, add methyl alcohol 126g, in 40 ℃ of reactions 2 hours, in room temperature reaction 24 hours, the faint yellow precipitation that leaching is separated out.With the precipitation water of leaching, then use washed with methanol.And then, yellow powder is cleaned leaching with hot methanol.With resulting faint yellow material vacuum-drying, obtaining with compound (73-c) is the faint yellow solid 23.31g of principal constituent.With compound (73-a) is benchmark, and yield is 66%.

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

Compound (73-c) 23.31g and pyridinium chloride 233.1g are mixed, be warmed up to 180 ℃, reacted 3 hours.Resulting mixture is added in the ice the resulting precipitation of leaching.With after the aqueous suspension washing, clean with toluene, then, be dispersed in saturated SODIUM HYDROSULPHITE sodium water solution, the chloroform, in stirring at room 2 hours.Filter dispersion liquid, and then with making its vacuum-drying after the pure water washing and precipitating, obtaining with compound (73-d) is the yellow solid 21.2g of principal constituent.With compound (73-c) is benchmark, and 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.At the ice-cooled N, N '-DIC 1.02g of in resulting mixture, adding down.Make resulting reaction soln react a night in room temperature.In reaction solution, add silica gel 4g, gac 200mg, after 1 hour, carry out diatomite filtration in stirring at room.Filtrate decompression is concentrated, remove chloroform after, in solution, add methyl alcohol, crystal is separated out.The cream-coloured powder of leaching, and then, after ethanol cleaning 2 times, use washed with heptane, vacuum-drying obtains compound (A73-1) 2.11g as cream-coloured powder.With compound (73-d) is benchmark, and 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 (d d, 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 that obtains (A73-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A73-1) is when heating up, and the high phase of demonstration viscosity provides clear and definite nematic phase since 141 ℃ from 82 ℃ to 141 ℃.And then compound (A73-1) when cooling, is nematic phase and crystallization lentamente until all being nematic phase more than 180 ℃ till 84 ℃.

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

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

Make

2,3,5-pseudocuminol 20.00g, paraformaldehyde 11.03g, Magnesium Chloride Anhydrous 20.97g are dispersed in the 120g acetonitrile.In stirring at room after 30 minutes, with dripping triethylamine 29.72g in 2 hours.Mixture was reacted in water-bath 8 hours, room temperature reaction 96 hours.Reaction solution is injected the mixed solvent that the heptane by the ethyl acetate of 200mL and 400mL forms, adding pure water 400mL.Add cold 2N-hydrochloric acid, become acidity after, reclaim organic layer.With after the organic layer dehydration, add silica gel 20g, gac 2g with anhydrous sodium sulphate, leniently stirred 30 minutes, dispersion liquid is carried out diatomite filtration.Below 40 ℃ filtrate decompression being concentrated, obtain as 3,4 of light yellow viscous liquid 6-trimethylammonium salicylic aldehyde 24.69g with vaporizer.With 2,3, the 5-pseudocuminol is a benchmark, and yield is 102%.

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

Make

3,4,6-trimethylammonium salicylic aldehyde 24.11g, salt of wormwood 48.71g are dispersed in N, among N '-N,N-DIMETHYLACETAMIDE 130mL.After being heated to 80 ℃, with 30 minutes dripping bromine tert.-butyl acetate 28.64g.Mixture was reacted 2 hours in 140 ℃.Behind the 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-salt sour water 500mL, reclaim organic layer for 2 times.Behind anhydrous sodium sulfate dehydration, distill except that desolvating with vaporizer.Residue is dissolved in the 150g acetate, adds hydrobromic acid aqueous solution 45g, stirred 1 hour in 40 ℃.Put be chilled to room temperature after, add 1N-hydrochloric acid 150g, the white powder that leaching is separated out.Resulting white powder is further used 1N-hydrochloric acid, followed with heptane, with after the toluene cleaning, and vacuum-drying obtains thus as 4,6 of cream-coloured powder, 7-trimethylammonium benzo furans-2-carboxylic acid 14.89g.With 3,4,6-trimethylammonium salicylic aldehyde is a benchmark, and yield is 50%.

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

Make 2,5-dimethoxyaniline 16.75g, 4,6,7-trimethylammonium benzo furans-2-carboxylic acid 14.89g is dispersed among the chloroform 75mL.After cooling off resulting suspension with ice bath, with the mixed solution that added 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride 15.37g and chloroform 100g in 4 hours, in room temperature reaction 72 hours.Resulting mixed solution is concentrated, in residue, add mixing solutions (salt sour 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 resulting precipitation of leaching adds in the mixing solutions (salt sour water 2 parts by volume, methyl alcohol 1 parts by volume) of hydrochloric acid water-methanol.Leaching pistac precipitation with mixing solutions (potassium hydroxide aqueous solution 1 parts by volume, the methyl alcohol 2 parts by volume) cleaning of the 1N-KOH aqueous solution-methyl alcohol, is filtered.Vacuum-drying obtains compound (63-a) 22.71g as pale yellow powder.With 6-methyl cumarone-2-carboxylic acid is benchmark, and yield is 92%.

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

With compound (63-a) 22.71g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-two sulphur-2,4-two phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 16.24g and toluene 228g mix, and resulting mixture is warmed up to 110 ℃, react 6 hours.After the cooling, toluene solution cleaned 3 times with 2N-aqueous sodium hydroxide solution 500mL after, reclaim organic layer after, it is concentrated, add heptane, make its crystallization.The resulting greenish orange look crystallization of leaching, vacuum-drying obtains compound (63-b) 23.78g as the aureus powder thus.Compound (63-b) is all measured it and is directly used in subsequent step though contain the resolvent of lawesson reagent.

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

Compound (63-b) 23.78g, potassium hydroxide 20.48g and water 389g are mixed.Then, add Tripotassium iron hexacyanide 60.09g, modulation contains the dispersion liquid of compound (63-b).In dispersion liquid, add methyl alcohol 77.83g, in 50 ℃ of reactions 4 hours, in room temperature reaction 24 hours, the yellow mercury oxide that leaching is separated out.With filter the precipitation water, then use washed with methanol.And then, yellow powder is cleaned leaching with hot ethanol.With resulting yellow substance vacuum-drying, obtaining with compound (63-c) is the faint yellow solid 20.14g of principal constituent.With compound (63-a) is benchmark, and yield is 86%.

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

Compound (63-c) 20.14g and pyridinium chloride 200.1g are mixed, be warmed up to 180 ℃ of reactions 3 hours.Resulting mixture is added in the ice the resulting precipitation of leaching.With after the aqueous suspension washing, clean with toluene, then, be dispersed in saturated SODIUM HYDROSULPHITE sodium water solution, the chloroform, in stirring at room 2 hours.Filter dispersion liquid, and then with making its vacuum-drying after the pure water washing and precipitating, obtaining with compound (73-d) is the orange solids 18.9g of principal constituent.With compound (63-c) is benchmark, and 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.At the ice-cooled N, N '-DIC 1.02g of in resulting mixture, adding down.Make resulting reaction soln react a night in room temperature.In reaction solution, add silica gel 4g, gac 200mg, after 1 hour, carry out diatomite filtration in stirring at room.Filtrate decompression is concentrated, remove chloroform after, in solution, add methyl alcohol, crystal is separated out.The cream-coloured powder of leaching, and then, after ethanol cleaning 2 times, use washed with heptane, vacuum-drying obtains compound (A63-1) 2.65g as cream-coloured powder.With compound (63-d) is benchmark, and 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 (d d, 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 that obtains (A63-1) is confirmed by adopting the polarized light microscope observing structure.Compound (A63-1) is when heating up, and the high phase of demonstration viscosity provides clear and definite nematic phase since 139 ℃ from 136 ℃ to 139 ℃.And then compound (A63-1) is nematic phase and crystallization until all being nematic phase more than 180 ℃ till 125 ℃ when cooling.

Embodiment 49～51 and comparative example 1

The Production Example of＜blooming 〉

At the 2 quality % aqueous solution of glass substrate pva coating (polyvinyl alcohol 1000 fully saponified types, Wako Pure Chemical Industries, Ltd.'s system), after the drying, form the film of thickness 89nm.Then, friction treatment is implemented on the surface of resulting film, the composition of composition, under the drying temperature that table 18 is put down in writing dry 1 minute by spin-coating method coating table 17 on the face of having implemented friction treatment.Next, the temperature when being heated to the rayed that table 18 puts down in writing, the ultraviolet ray of the integrating light quantity of exposure chart 18 records simultaneously forms the blooming of the described thickness of table 19.

[table 17]

	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)
	Compound of the present invention (%)	Liquid crystalline cpd (%)	Polymerization starter (%)	Flow agent (%)	Solvent (%)	Embodiment 49	??A72-1??(28.04)	??-	??IRGACURE?369??(1.97)	??BYK361N??(0.03)	??69.97
Embodiment 50	??A73-1??(28.03)	??-	??IRGACURE?819??(1.96)	??BYK361N??(0.03)	??69.97	Embodiment 49	??A72-1??(28.04)	??-	??IRGACURE?369??(1.97)	??BYK361N??(0.03)	??69.97
Embodiment 50	??A73-1??(28.03)	??-	??IRGACURE?819??(1.96)	??BYK361N??(0.03)	??69.97	Embodiment 50	??A63-1??(28.03)	??-	??IRGACURE?819??(1.96)	??BYK361N??(0.03)	??69.98
Comparative example 1	??-	??LC242??(29.04)	??IRGACURE?819??(0.89)	??BYK361N??(0.02)	??69.15	Embodiment 50	??A63-1??(28.03)	??-	??IRGACURE?819??(1.96)	??BYK361N??(0.03)	??69.98

LC242: the same

Flow agent: BYK361N (BYK-Chemie Japan system)

Solvent: cyclopentanone

[table 18]

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

The mensuration of＜optical characteristics 〉

Use mensuration machine (KOBRA-WR, prince's instrumentation machines corporation system) to measure the front phase difference value of blooming.Need to prove,,, just can access the front phase difference value of the blooming of on glass substrate, making so measure the film that attaches glass substrate with the mensuration machine because the glass substrate that uses in the base material does not have birefringence.Resulting optical detecting front phase difference value is measured 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, use laser microscope (LEXT, Olympus Corp's system) to measure the thickness d (μ m) of blooming.To the results are shown in table 19.Value with Re (546.9) is calculated Δ n (Δ n=Re (546.9)/d) divided by thickness.

[table 19]

	??Re(546.9)	??α	??β	??d(μm)	??Δn
	??Re(546.9)	??α	??β	??d(μm)	??Δn	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 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	Embodiment 51	??126.8	??0.853	??1.026	??2.528	??0.050

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

Claims

1. the compound that has divalent group shown in formula (1-1) or the formula (1-2),

In the formula, Z ¹And Z ²Represent hydrogen atom independently of one another; halogen atom; the alkyl of carbonatoms 1～6; cyano group; nitro; 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 1～6; the N of carbonatoms 2～12; the N-dialkyl amido; the N-alkylsulfamoyl group of carbonatoms 1～6; the N of carbonatoms 2～12; the 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 ²The alkyl of representing hydrogen atom or carbonatoms 1～4 independently of one another,

Y ¹Expression replaces or unsubstituted polycycle aromatic hydrocarbyl or replacement 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 the alkyl of halogen atom, carbonatoms 1～4, the fluoroalkyl of carbonatoms 1～4, alkoxyl group, cyano group or the nitro of carbonatoms 1～4, this ester ring type alkyl-CH ₂-can with-O-,-S-or-the NH-displacement.

2. compound as claimed in claim 1 wherein, has the divalent group of formula (2-1) or formula (2-2) expression,

In the formula, Z ¹, Z ², Q ¹, Q ², Y ¹, D ¹, D ², G ¹And G ²Define the identical meaning in expression and the claim 1 respectively,

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

K and l represent 0～3 integer independently of one another.

3. compound as claimed in claim 1, with formula (3-1) or formula (3-2) expression,

In the 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 respectively with claim 1 and claim 2 in the identical meaning of definition,

F ¹And F ²The alkane 2 basis of representing 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, this alkane 2 basis-CH ₂-can with-O-or-the CO-displacement,

P ¹And P ²Represent hydrogen atom or polymerizable group independently of one another.

4. compound as claimed in claim 1, wherein, Y ¹Be formula (Y ¹-1) or formula (Y ¹-4) Biao Shi group,

In the formula, Z ³Represent halogen atom independently of one another; the alkyl of carbonatoms 1～6; cyano group; nitro; nitroso-group; 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-dialkyl amido; the N-alkylamino of carbonatoms 1～4; sulfamyl; the N-alkylsulfamoyl group of carbonatoms 1～6; the N of carbonatoms 2～12; the N-dialkyl sulfamine or-COOH

V ¹Expression-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 ³The alkyl of representing hydrogen atom or carbonatoms 1～4 independently of one another,

V ¹, W ¹, W ², W ³, W ⁴And W ⁵In at least one contain S, N, O or Se,

A represents 0～3 integer independently of one another.

5. compound as claimed in claim 4, wherein, formula (Y ¹-1) Biao Shi group is with formula (Y ³-1) Biao Shi group, formula (Y ¹-4) Biao Shi group is with formula (Y ³-3) Biao Shi group,

In the formula, Z ³, a, V ¹And W ²Define the identical meaning in expression and the claim 4 respectively.

6. compound as claimed in claim 4, wherein, V ¹For-S-,-NR ³-or-O-.

7. compound as claimed in claim 1, wherein, G ¹And G ²For instead-1,4-hexanaphthene two bases.

8. compound as claimed in claim 2, wherein, A ¹And A ²Represent 1 independently of one another, 4-phenylene or 1,4-hexanaphthene two bases, this 1,4-phenylene and 1,4-hexanaphthene two bases can have alkyl, trifluoromethyl, cyano group or the nitro of halogen atom, carbonatoms 1～4.

9. compound as claimed in claim 3, wherein, only with A ¹Bonded B ¹Only with A ²Bonded B ²Be independently of one another-CH ₂-CH ₂-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-O-CH ₂-,-CH ₂-O-or singly-bound,

10. compound as claimed in claim 3, wherein, P ¹And P ²Be hydrogen atom, acryloxy or methacryloxy independently of one another, and P ¹And P ²Be not hydrogen atom simultaneously.

11. a composition, it contains described compound of claim 1 and liquid crystalline cpd, and this liquid crystalline cpd is different from the described compound of claim 1.

12. composition as claimed in claim 11, wherein, liquid crystalline cpd is the liquid crystalline cpd shown in the formula (20),

In the formula, A ¹¹Represent divalence aromatic hydrocarbyl, 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 the alkyl of halogen atom, 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)-and CH=CH-or singly-bound, R ¹⁴And R ¹⁵The alkyl of representing hydrogen atom, fluorine atom or carbonatoms 1～4 independently of one another, perhaps R ¹⁴And R ¹⁵In conjunction with and the expression carbonatoms 4～7 alkane 2 basis, R ¹⁶The alkyl of expression hydrogen atom or carbonatoms 1～4,

E ¹¹The alkane 2 basis of expression 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 ¹¹The expression polymerizable group,

G represents the alkyl of hydrogen atom, halogen atom, 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, perhaps expression has the alkyl of the carbonatoms 1～18 of polymerizable group, this alkyl can have the alkoxy or halogen atom of carbonatoms 1～6

T represents 1～5 integer.

13. composition as claimed in claim 11 wherein, also contains polymerization starter.

14. composition as claimed in claim 13, wherein, polymerization starter contains acetophenone compound.

15. a blooming is by obtaining the described compound polymerization of claim 1.

16. a blooming is by obtaining each described composition polymerization in the claim 11～14.

17. as claim 15 or 16 described bloomings, the phase difference value Re (550) that is used for wavelength 550nm place is λ/4 plates of 113～163nm.

18. as claim 15 or 16 described bloomings, the phase difference value Re (550) that is used for wavelength 550nm place is λ/2 plates of 250～300nm.

19. a polaroid wherein, contains each described blooming and polarizing coating in the claim 15～18.

20. a colour filter wherein, is formed with each described blooming in the claim 15～18 on the alignment films on coating filter substrate.

21. a liquid crystal indicator wherein, contains the described colour filter of claim 20.

22. a panel display apparatus wherein, possesses the liquid crystal panel that contains the described polaroid of claim 19.

23. an organic EL display wherein, possesses the organic electroluminescence panel that contains the described polaroid of claim 19.

24. the manufacture method of polymeric membrane not is characterized in that, the solution coat that will contain the described compound of claim 1 is on the supporting substrate or be coated on the alignment films that is formed on the supporting substrate, and makes it dry.

25. the manufacture method of a blooming is characterized in that, the not polymeric membrane that obtains by the described manufacture method of claim 24 is solidified.