CN103214620A

CN103214620A - Composition for manufacturing optical film and optical film

Info

Publication number: CN103214620A
Application number: CN2013100220967A
Authority: CN
Inventors: 小林忠弘
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2012-01-23
Filing date: 2013-01-21
Publication date: 2013-07-24
Anticipated expiration: 2033-01-21
Also published as: TW201335706A; CN107488249B; KR20130086168A; CN103214620B; CN107488249A; KR20190031216A; KR101989195B1; KR102079896B1; TWI599848B

Abstract

The invention provides a composition for manufacturing an optical film, exhibiting excellent attaching performance between a substrate or a polarizing film and the optical film, and the optical film manufactured with the composition. Provided are a composition containing (A) a polymerized liquid crystal compound, (B) a compound of which the molecule containing a carbon-carbon unsaturated bond and active hydrogen reactive groups and (C) an optical polymerization initiator and an optical film formed by the composition. Preferably, B is a compound containing isocyanate groups serving as active hydrogen reactive groups.

Description

Composition and optical thin film for the manufacture of optical thin film

Technical field

The present invention relates to composition and optical thin film.

Background technology

Using the member of optical thin films such as containing Polarizer and phase-contrast film in panel display apparatus (FPD).As optical thin film, knownly by the composition that will contain polymerizable liquid crystal compound, photo-induced polymerization initiator and solvent, be coated on the optical thin film that on base material, manufacture forms.For example, in patent documentation 1, putting down in writing coating composition on the base material of having implemented orientation process and obtaining coated film, after the polymerizable liquid crystal compound orientation that makes to comprise in coated film, by the optical thin film that the polymerizable liquid crystal compound polymerization is formed.

[prior art document]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 2007-148098 communique

Summary of the invention

The means of dealing with problems

The present invention includes following invention.

[1] a kind of following (A), (B) and composition (C) of containing.

(A) polymerizable liquid crystal compound

(B) there is the compound of carbon-to-carbon unsaturated bond and reactive with active hydrogen group in molecule

(C) photo-induced polymerization initiator

[2] according to the composition of [1] record, (B) be the compound had as the isocyanato of reactive with active hydrogen group.

[3] according to the composition of [1] record, (B) be the represented compound of following formula (X),

[in formula (X),

N means 1～10 integer, R ¹' mean the divalent aliphatics of carbonatoms 2～20 or the divalent aryl of ester ring type alkyl or carbonatoms 5～20.2 R in each repeating unit ²' in one be-NH-, another is-[N-C(=O)-R ³']-represented group.R ³' mean to have the group of hydroxyl or carbon-to-carbon unsaturated bond.

The R of formula (X) ³' among, at least 1 R ³' be the group with carbon-to-carbon unsaturated bond.]

[4] composition of putting down in writing according to any one of [1]～[3], (A) be the represented compound of formula (A).

[in formula (A),

X ¹mean Sauerstoffatom, sulphur atom or-NR ¹-.R ¹the alkyl that means hydrogen atom or carbonatoms 1～4.

Y ¹mean the 1 valency heteroaromatic formula base that there is or do not have 1 valency aryl of substituent carbonatoms 6～12 or there is or do not have substituent carbonatoms 3～12.

Q ³and Q ⁴mean independently respectively hydrogen atom, have or do not have 1 valency aliphatic alkyl of substituent carbonatoms 1～20, the ester ring type alkyl of carbonatoms 3～20, the 1 valency aryl that there is or do not have substituent carbonatoms 6～20, halogen atom, cyano group, nitro ,-NR ²r ³or-SR ², or Q ³and Q ⁴mutual bonding, they and its carbon atom of bonding respectively form aromatic nucleus or fragrant heterocycle jointly.R ²and R ³the alkyl that means independently respectively hydrogen atom or carbonatoms 1～6.

D ¹and D ²mean independently respectively singly-bound ,-C(=O)-O-,-C(=S)-O-,-CR ⁴r ⁵-,-CR ⁴r ⁵-CR ⁶r ⁷-,-O-CR ⁴r ⁵-,-CR ⁴r ⁵-O-CR ⁶r ⁷-,-CO-O-CR ⁴r ⁵-,-O-CO-CR ⁴r ⁵-,-CR ⁴r ⁵-O-CO-CR ⁶r ⁷-,-CR ⁴r ⁵-CO-O-CR ⁶r ⁷-or-NR ⁴-CR ⁵r ⁶-or-CO-NR ⁴-.

R ⁴, R ⁵, R ⁶and R ⁷the alkyl that means independently respectively hydrogen atom, fluorine atom or carbonatoms 1～4.

G ¹and G ²the divalent ester ring type alkyl that means independently respectively carbonatoms 5～8, form described ester ring type alkyl methylene radical can by Sauerstoffatom, sulphur atom or-NH-replaces, the methyne that forms described ester ring type alkyl can be replaced by tertiary N atom.

L ¹and L ²mean independently respectively 1 valency organic group, L ¹and L ²among at least one be the organic group with polymerizable group.]

[5] according to the composition of [4] record, (A) be following compound, wherein, the L of formula (A) ¹the represented group of formula (A1), and L ²it is the represented group of formula (A2).

P ¹-F ¹-（B ¹-A ¹） _k-E ¹- （A1）

P ²-F ²-（B ²-A ²） _l-E ²- （A2）

[in formula (A1) and formula (A2),

B ¹, B ², E ¹and E ²difference is expression-CR independently ⁴r ⁵-,-CH ₂-CH ₂-,-O-,-S-,-CO-O-,-O-CO-O-,-CS-O-,-O-CS-O-,-CO-NR ¹-,-O-CH ₂-,-S-CH ₂-or singly-bound.

A ¹and A ²mean independently respectively the divalent ester ring type alkyl of carbonatoms 5～8 or the divalent aryl of carbonatoms 6～18, form described ester ring type alkyl methylene radical can by Sauerstoffatom, sulphur atom or-NH-replaces, the methyne that forms described ester ring type alkyl can be replaced by tertiary N atom.

K and l mean respectively 0～3 integer independently.When k is the integer more than 2, a plurality of B ¹can be mutually identical also can be different, a plurality of A ¹can be mutually identical also can be different.When l is the integer more than 2, a plurality of B ²can be mutually identical also can be different, a plurality of A ²can be mutually identical also can be different.

F ¹and F ²the divalent aliphatic alkyl that means carbonatoms 1～12.

P ¹mean polymerizable group.

P ²mean hydrogen atom or polymerizable group.

R ¹, R ⁴and R ⁵mean the meaning same as described above.]

[6] a kind of optical thin film, the polymerizable liquid crystal compound polymerization comprised in the composition of its record of any one by [1]～[5] forms.

[7] a kind of manufacture method of optical thin film, comprise following (1) and (2).

(1) composition of any one of [1]～[5] record is coated on to the operation on base material;

(2) by the operation that the polymerizable liquid crystal compound polymerization comprised in the coated film on base material forms optical thin film that is coated on that makes to be obtained by (1).

The manufacture method of the optical thin film of [8] putting down in writing according to [7], wherein, base material consists of the material with hydroxyl.

The manufacture method of the optical thin film of [9] putting down in writing according to [8], the material with hydroxyl is the material that the triacetyl cellulose saponification is obtained.

The manufacture method of the optical thin film of [10] putting down in writing according to any one of [7]～[9], wherein, be provided with the alignment films by light orientation polymer formation on the surface of base material.

The manufacture method of the optical thin film of [11] putting down in writing according to [10], wherein, alignment films has formed crosslinking structure setting by light orientation polymkeric substance through rayed.

[12] a kind of optical thin film, the manufacture method of its record of any one by [7]～[11] makes.

[13] according to the optical thin film of [6] or [12] record, it has phase differential.

[14] a kind of Polarizer, the optical thin film that it contains [6], [12] or [13] record.

[15] a kind of panel display apparatus, it possesses the optical thin film of [6], [12] or [13] record.

[16] a kind of composition, it contains following (D) and reaches (B).

(D) light orientation polymkeric substance

[17] according to the composition of [16] record, be (D) to form by rayed the light orientation polymkeric substance of crosslinking structure.

[18] according to the composition of [16] or [17] record, (B) be the compound had as the isocyanato of reactive with active hydrogen group.

[19] according to the composition of [16] or [17] record, (B) be the represented compound of following formula (X).

[in formula (X),

R ³' among, at least 1 R ³' be the group with carbon-to-carbon unsaturated bond.]

[20] a kind of optical thin film, the light orientation crosslinked polymer comprised in the composition of its record of any one by [16]～[19] forms.

[21] a kind of manufacture method of optical thin film, comprise following (1) and (2).

(1) composition of any one of [16]～[19] record is coated on to the operation on base material;

(2) by the operation that the light orientation crosslinked polymer comprised in the coated film on base material forms optical thin film that is coated on that makes to be obtained by (1).

The manufacture method of the optical thin film of [22] putting down in writing according to [21], wherein, base material consists of the material with hydroxyl.

The manufacture method of the optical thin film of [23] putting down in writing according to [22], wherein, the material with hydroxyl is the material that the triacetyl cellulose saponification obtains.

[24] a kind of optical thin film, the manufacture method of its record of any one by [21]～[23] makes.

[25] a kind of polarizer, it is further to form optical anisotropic layer to form on the optical thin film of [20] or [24] record.

[26] a kind of Polarizer, the optical thin film that it contains [20] or [24] record.

[27] a kind of panel display apparatus, it possesses the optical thin film of [20] or [24] record.

[28] a kind of optical thin film, its sequential lamination according to base material, the A layer that formed by composition (A) and the B layer that formed by composition (B) forms, wherein,

Composition (A) contains following (D) and reaches (B-1), and composition (B) contains following (A), (B-2) reaches (C).

(D) light orientation polymkeric substance

(B-1) there is the compound of carbon-to-carbon unsaturated bond and reactive with active hydrogen group

(A) polymerizable liquid crystal compound

(B-2) there is the compound of carbon-to-carbon unsaturated bond and reactive with active hydrogen group

(C) photo-induced polymerization initiator

[29] according to the optical thin film of [28] record, wherein, be (D) to form by rayed the light orientation polymkeric substance of crosslinking structure.

[30] according to the composition of [28] or [29] record, (B-1) reaching (B-2) is all the compound had as the isocyanato of reactive with active hydrogen group.

[31] according to the optical thin film of [28] or [29] record, wherein, (B-1) reaching (B-2) is the represented compound of following formula (X) respectively independently.

[in formula (X),

R ³' among at least 1 R ³' be the group with carbon-to-carbon unsaturated bond.]

[32] optical thin film of putting down in writing according to any one of [28]～[31], wherein, (D) that the A layer contains in composition (A) is cross-linked to form.

[33] optical thin film of putting down in writing according to any one of [28]～[32], wherein, base material consists of the material with hydroxyl.

[34] according to the optical thin film of [33] record, wherein, the material with hydroxyl is the material obtained by the triacetyl cellulose saponification.

[35] optical thin film of putting down in writing according to any one of [28]～[34], it has phase differential.

[36] a kind of manufacture method of optical thin film, it comprises following<1 >～<4 operation.

<1 > contain following (D) and composition (A) (B-1) by coating on base material, form the operation of the 1st coated film on base material;

(D) light orientation polymkeric substance

<2 > by making by<1 > obtain to be coated on (D) that comprise in the 1st coated film on base material crosslinked, the 1st coated film is changed into to the operation of A layer;

<3 > by by<2 > on the A layer that forms coating contain following (A), (B-2) and composition (B) (C), form the operation of the 2nd coated film on the A layer;

(A) polymerizable liquid crystal compound

(C) photo-induced polymerization initiator

<4 > make by<3 the operation of the polymerizable liquid crystal compound polymerization that comprises in the 2nd coated film that forms.

[37] a kind of optical thin film, its manufacture method by [36] record makes.

[38] a kind of Polarizer, the optical thin film of any one that it contains [28]～[35] or [37] record.

[39] a kind of panel display apparatus, it possesses any one of [28]～[35] or the optical thin film of [37] record.

The accompanying drawing explanation

[Fig. 1] is the schematic cross-section that shows an example that relates to Polarizer of the present invention.

[Fig. 2] is the schematic cross-section that shows an example that relates to liquid crystal indicator of the present invention.

[Fig. 3] is the schematic cross-section that shows an example that relates to organic EL display of the present invention.

Nomenclature

1,1 ', 12: this phase retardation film

2: the polarisation rete

3,3 ': bond layer

4a, 4b, 4c, 4d, 4e, 4,4 ': Polarizer

5,5 ': bonding coat

6: liquid crystal panel

7: organic EL panel

10a, 10b: liquid crystal indicator

11: organic EL display

Embodiment

I. the 1st mode of the present invention

The 1st composition of the present invention (below, according to circumstances, claim the 1st composition of the present invention for " this composition (1) ", according to circumstances, claim that the optical thin film of being manufactured by this composition (1) is " this optical thin film (1) ".）

This composition (1) contain the compound that there is carbon-to-carbon unsaturated bond and reactive with active hydrogen group in (A) polymerizable liquid crystal compound, (B) molecule (below, according to circumstances, be referred to as " compound (B) ".) and (C) photo-induced polymerization initiator.

1-1. compound (B)

There is carbon-to-carbon unsaturated bond and reactive with active hydrogen group in the molecule of compound (B)." reactive with active hydrogen group " refers to carboxyl (COOH), hydroxyl (OH), amino (NH ₂) etc. there is active hydrogen group there is reactive group, can list glycidyl, oxazoline group, carbodiimide, '-aziridino, imide, isocyanato, isothiocyanic acid base, maleic anhydride base etc.The carbon-to-carbon unsaturated bond that compound (B) has and the number of reactive with active hydrogen group are respectively 1～20, are preferably 1～10.

Preferred compound (B) has at least 2 reactive with active hydrogen groups.A plurality of reactive with active hydrogen groups that exist can be identical, also can be different.

The carbon-to-carbon unsaturated bond that compound (B) has refers to carbon-to-carbon double bond or carbon-to-carbon triple bond, also or their combination, but is preferably carbon-to-carbon double bond.Wherein, preferred vinyl and/or (methyl) acryl.Further, preferably the reactive with active hydrogen group is at least a kind that from the group consisted of epoxy group(ing), glycidyl and isocyanato, selects, and particularly preferably has the compound (B) of acryl and isocyanato.

As the concrete example of compound (B), can list the compound that methacryloxy glycidyl ether or acryloxy glycidyl ether etc. have (methyl) acryl and epoxy group(ing); Vinylformic acid oxetane or methacrylic acid oxetane etc. have the compound of (methyl) acryl and oxa-cyclobutyl; Lactone acrylate or lactone methacrylic ester etc. have the compound of (methyl) acryl and lactone group; Vinyl oxazoline or pseudoallyl oxazoline etc. have the compound of vinyl and oxazoline group; Vinylformic acid isocyanato methyl esters, methacrylic acid isocyanato methyl esters, vinylformic acid 2-isocyanato ethyl ester and methacrylic acid 2-isocyanato ethyl ester etc. have the oligopolymer etc. of the compound of (methyl) acryl and isocyanato.In addition, can list methacrylic anhydride, acrylic anhydride, maleic anhydride and vinyl maleic anhydride etc. and there is compound of vinyl or vinylene and acid anhydrides etc.Wherein, preferable methyl acryloxy glycidyl ether, acryloxy glycidyl ether, vinylformic acid isocyanato methyl esters, methacrylic acid isocyanato methyl esters, vinyl oxazoline, vinylformic acid 2-isocyanato ethyl ester, methacrylic acid 2-isocyanato ethyl ester and oligopolymer, particularly preferably vinylformic acid isocyanato methyl esters, vinylformic acid 2-isocyanato ethyl ester and oligopolymer.

Preferred compound (B) is that for example following formula (X) is represented.

[in formula (X),

R in formula (X) ³' among, at least 1 R ³' be the group with carbon-to-carbon unsaturated bond.]

Among the represented compound (B) of formula (X), particularly preferably the represented compound of following formula (XX) (below, according to circumstances, be referred to as " compound (XX) ".) (and, n and above-mentioned equivalent in meaning).

Compound (XX) can directly be used the commercially available product of easily obtaining from market, after also can as required it being purified, uses.As commercially available product, can enumerate the registered trademark as Laromer() LR-9000(BASF society system) etc.

With respect to the total mass of this composition (1), preferably the content of the compound (B) in this composition (1) is 0.01～10 quality %, more preferably 0.1～5 quality %.

1-2. polymerizable liquid crystal compound

Polymerizable liquid crystal compound refers to have polymerizable group, and shows the compound of mesomorphic state.Polymerizable group refers to the group of the polyreaction that participates in polymerizable liquid crystal compound.

Preferred 1 example of polymerizable liquid crystal compound be for example the represented compound of formula (A) (below, according to circumstances, be referred to as " compound (A) ".）。

[in formula (A),

As R ¹the alkyl of represented carbonatoms 1～4, can list methyl, ethyl, propyl group, sec.-propyl, butyl and sec-butyl etc.Wherein, the alkyl of preferred carbonatoms 1～3, more preferably methyl and ethyl, particularly preferably methyl.

As Y ¹represented aryl, can list the monocycles such as phenyl is aryl; The polycyclic system aryls (comprising the fused polycyclic system aryl) such as naphthyl, anthryl, phenanthryl and xenyl.Wherein, as Y ¹represented aryl, preferably phenyl and naphthyl, more preferably phenyl.

As Y ¹represented heteroaromatic formula base, can list the monocycles such as furyl, pyrryl, thienyl, pyridyl and thiazolyl is aromatic heterocyclic; The polycyclic system aromatic heterocyclics such as benzothiazolyl, benzofuryl and benzothienyl (comprising the fused polycyclic system aromatic heterocyclic) etc. contain the heteroatomic heteroaromatic formula bases such as at least one nitrogen-atoms, Sauerstoffatom and sulphur atom.Wherein, preferred furyl, thienyl, thiazolyl, benzothiazolyl, benzofuryl and benzothienyl.

Y ¹represented aryl and heteroaromatic formula base can have substituting group (below, according to circumstances, be referred to as " substituting group Z ¹").As substituting group Z ¹can list the alkyl, cyano group, nitro, nitroso-group, carboxyl, 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 alkyl sulfenyl of carbonatoms 1～6, the N-alkylamino of carbonatoms 1～6, the N of carbonatoms 2～12 of halogen atom, carbonatoms 1～6; the N-alkyl amino sulfonyl of N-dialkyl amido, carbonatoms 1～6 and the N of carbonatoms 2～12, N-dialkyl amino sulfonyl etc.

Substituting group Z ¹among, as halogen atom, can list fluorine atom, chlorine atom, bromine atoms and iodine atom, preferably fluorine atom, chlorine atom and bromine atoms.

Substituting group Z ¹among, the concrete example of alkyl can list as R ¹the substituting group that illustrates for example of alkyl.Wherein, more preferably methyl and ethyl, particularly preferably methyl.

Substituting group Z ¹among; as alkyl sulphinyl, can list 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 etc.Wherein, the alkyl sulphinyl of preferred carbonatoms 1～4, the more preferably alkyl sulphinyl of carbonatoms 1～2, particularly preferably methylsulfinyl.

Substituting group Z ¹among, as alkyl sulphonyl, can list methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, sec.-propyl alkylsulfonyl, butyl alkylsulfonyl, isobutyl-sulphonyl, sec-butyl alkylsulfonyl, tertiary butyl alkylsulfonyl, amyl group alkylsulfonyl and hexyl alkylsulfonyl etc.Wherein, the alkyl sulphonyl of preferred carbonatoms 1～4, the more preferably alkyl sulphonyl of carbonatoms 1～2, particularly preferably methyl sulphonyl.

Substituting group Z ¹among, as fluoroalkyl, can list methyl fluoride, trifluoromethyl, fluoro ethyl, pentafluoroethyl group, seven fluoropropyls and nine fluorine butyl etc.Wherein, the fluoroalkyl of preferred carbonatoms 1～4, the more preferably fluoroalkyl of carbonatoms 1～2, particularly preferably trifluoromethyl.

Substituting group Z ¹among, as alkoxyl group, can list methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy and hexyloxy etc.Wherein, the alkoxyl group of preferred carbonatoms 1～4, the more preferably alkoxyl group of carbonatoms 1～2, particularly preferably methoxyl group.

Substituting group Z ¹among, as the alkyl sulfenyl, can list methylthio group, ethylmercapto group, rosickyite base, isopropyl sulfenyl, butylthio, isobutyl sulfenyl, secondary butylthio, tertiary butylthio, penta sulfenyl and own sulfenyl etc.Wherein, the alkyl sulfenyl of preferred carbonatoms 1～4, more preferably the alkyl sulfenyl of carbonatoms 1～2, particularly preferably methylthio group.

Substituting group Z ¹among, as the N-alkylamino, can list N-methylamino, N-ethylamino, N-propyl group amino, N-isopropylamino, N-butyl amino, N-isobutylamino, N-sec-butyl amino, N-tertiary butyl amino, N-amyl group amino and N-hexyl amino etc.Wherein, the N-alkylamino of preferred carbonatoms 1～4, more preferably the N-alkylamino of carbonatoms 1～2, particularly preferably N-methylamino.

Substituting group Z ¹among, as N, the N-dialkyl amido, can list N, N-dimethylamino, N-methyl-N-ethylamino, N, N-diethylamino, N, the N-dipropyl is amino, N, N-diisopropylaminoethyl, N, N-dibutylamino, N, the N-diisobutyl is amino, N, N-diamyl amino and N, N-dihexyl amino etc.Wherein, the preferred N of carbonatoms 2～8, N-dialkyl amido, the more preferably N of carbonatoms 2～4, N-dialkyl amido, N particularly preferably, N-dimethylamino.

Substituting group Z ¹among; as the N-alkyl amino sulfonyl, can list N-methylamino alkylsulfonyl, N-ethylamino alkylsulfonyl, N-propyl group amino-sulfonyl, N-isopropylamino alkylsulfonyl, N-butyl amino-sulfonyl, N-isobutylamino alkylsulfonyl, N-sec-butyl amino-sulfonyl, N-tertiary butyl amino-sulfonyl, N-amyl group amino-sulfonyl and N-hexyl amino-sulfonyl etc.Wherein, the N-alkyl amino sulfonyl of preferred carbonatoms 1～4, more preferably the N-alkyl amino sulfonyl of carbonatoms 1～2, particularly preferably N-methylamino alkylsulfonyl.

Substituting group Z ¹among; as N, the N-dialkyl amino sulfonyl, can list N; N-dimethylamino-sulfonyl, N-methyl-N-ethylamino alkylsulfonyl, N; N-diethylamino alkylsulfonyl, N, N-dipropyl amino-sulfonyl, N, N-diisopropylaminoethyl alkylsulfonyl, N; N-dibutylamino alkylsulfonyl, N; N-diisobutyl amino-sulfonyl, N, N-diamyl amino-sulfonyl and N, N-dihexyl amino-sulfonyl etc.Wherein, the preferred N of carbonatoms 2～8, N-dialkyl amino sulfonyl, the more preferably N of carbonatoms 2～4, N-dialkyl amino sulfonyl, N particularly preferably, N-dimethylamino-sulfonyl.

Wherein, preferred substituents Z ¹for the alkyl of halogen atom, carbonatoms 1～2, cyano group, nitro, the alkyl sulphonyl of carbonatoms 1～2, the fluoroalkyl of carbonatoms 1～2, the alkoxyl group of carbonatoms 1～2, the alkyl sulfenyl of carbonatoms 1～2, the N-alkylamino of carbonatoms 1～2, the N of carbonatoms 2～4; the alkyl amino sulfonyl of N-dialkyl amido and carbonatoms 1～2; particularly preferably halogen atom, methyl, cyano group, nitro, sulfonic group, carboxyl, trifluoromethyl, methoxyl group, methylthio group, N, N-dimethylamino and N-methylamino.

Y ¹for to have or do not have substituent monocycle be aryl or have or do not have substituent monocycle while being aromatic heterocyclic, its preferred example can list the group by formula (Y-1)～formula (Y-6) means respectively.

[in formula (Y-1)～formula (Y-6),

* mean bonding position, Z ¹mean above-mentioned substituting group Z ¹.

A1 means that 0～5 integer, a2 mean that 0～4 integer, b1 mean that 0～3 integer, b2 mean 0～2 integer.R ⁸mean hydrogen atom or methyl.

And, when a1, a2, b1 and b2 are the integer more than 2, a plurality of Z that exist in same group ¹can be mutually identical also can be different.]

If Y ¹for formula (Y-1) or the represented group of formula (Y-3), from compound (A), easily manufacture view and cost aspect are considered and particularly preferably.

Y ¹for thering is or not having substituent polycyclic system aryl or having or while not having substituent polycyclic system aromatic heterocyclic, its preferred example can list by formula (Y ¹-1)～formula (Y ¹-7) group meaned respectively.

[formula (Y ¹-1)～formula (Y ¹-7) in,

* mean bonding position, Z ¹mean above-mentioned substituting group Z ¹.

V ¹and V ²respectively independently expression-CO-,-S-,-NR ⁹-,-O-,-Se-or-SO ₂-.R ⁹the alkyl that means hydrogen atom or carbonatoms 1～4.

W ¹～W ⁵respectively independently expression-CH=or-N=.

But, V ¹, V ²and W ¹～W ⁵among at least 1 mean the heteroatoms such as S, N, O or Se or contain this heteroatomic group.

A means 0～3 integer.

B means 0～2 integer.

And, when a, b are the integer more than 2, a plurality of Z that exist in same group ¹can be mutually identical also can be different.]

Preferred V ¹and V ²be independently respectively-S-,-NR ⁹-or-O-, preferably W ¹～W ⁵be independently respectively-CH=or-N=.

Preferably a is 0 or 1, and preferably b is 0.

Further, if at Y ¹for thering is or do not have substituent polycyclic system aryl or having or do not have in the situation of substituent polycyclic system aromatic heterocyclic, talk about, its formula (Y more preferably ²-1)～formula (Y ²-6) represented group.

[formula (Y ²-1)～formula (Y ²-6) in,

*, Z ¹, a, b, V ¹, V ²and W ¹mean the meaning same as described above.]

By formula (Y ²-1)～formula (Y ²-6) in the group meaned respectively, as Z ¹preferred halogen atom, methyl, ethyl, sec.-propyl, sec-butyl, cyano group, nitro, sulfonic group, nitroso-group, carboxyl, trifluoromethyl, methoxyl group, methylthio group, N, N-dimethylamino and N-methylamino, more preferably halogen atom, methyl, ethyl, sec.-propyl, sec-butyl, cyano group, nitro, trifluoromethyl, particularly preferably methyl, ethyl, sec.-propyl, sec-butyl, amyl group and hexyl.

As Q ³and Q ⁴represented aliphatic alkyl, can list methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, 1-methyl butyl, 3-methyl butyl, hexyl, 1-methyl amyl, 4-methyl amyl, heptyl, 1-methyl hexyl, 5-methyl hexyl, octyl group, 1-methylheptyl, nonyl, 1-Methyl Octyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl etc.The alkyl of preferred carbonatoms 1～12, particularly preferably methyl and ethyl.

As Q ³and Q ⁴represented ester ring type alkyl, can list cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl and ring decyl etc., preferably the cyclic alkyl of carbonatoms 3～12.

As Q ³and Q ⁴represented aryl, can list phenyl, xenyl, 1-naphthyl, 2-naphthyl, 1-fluorenyl, 2-fluorenyl and 3-fluorenyl etc., preferably the aryl of carbonatoms 6～14.

Q ³and Q ⁴represented aliphatic alkyl, ester ring type alkyl and aryl can have respectively substituting group.As substituting group, can list as Z ¹the substituting group illustrated for example.

R ²and R ³for the alkyl of carbonatoms 1～6, wherein, the alkyl of preferred carbonatoms 1～4, more preferably methyl and ethyl, particularly preferably methyl.

Q ³and Q ⁴bonding forms aromatic nucleus or fragrant heterocycle mutually.As Q ³with Q ⁴the ring formed, preferred fragrant heterocycle, for example, the more preferably formula in compound (A) (Q ')

Represented substructure is the represented structure of formula (Q).

[in formula (Q),

X ²with the X as in formula (A) ¹the atom or the group that illustrate for example are identical, Y ²with the Y as in formula (A) ¹the group illustrated for example is identical.]

If X ¹, Y ¹, Q ³and Q ⁴the compound for concrete example (A) of combination in formula (ar)

Represented substructure means, can list the substructure of selecting from the group by forming with following formula (ar-1)～formula (ar-135).

Among the represented substructure of formula (ar), the compound (A) that contains the represented structure of formula (ar-86) is easily controlled because of the wavelength dispersion of the phase differential of the optical thin film that the manufacture of compound (A) itself is easier, formed by this composition that contains compound (A), so preferably.

D in preferred formula (A) ¹and D ²be independently-O-C(=O respectively)-,-O-C(=S)-,-O-CR ⁴r ⁵-,-NR ⁴-CR ⁵r ⁶-or-NR ⁴-CO-, more preferably *-O-C(=O)-, *-O-C(=S)-, *-O-CR ⁴r ⁵-, *-NR ⁴-CR ⁵r ⁶-or *-NR ⁴-CO-, more preferably *-O-C(=O)-, *-O-C(=S)-or *-NR ⁴-CO-(* means the bonding position with phenyl ring, described phenyl ring be in the represented substructure of formula (ar) with Q ¹and Q ²the phenyl ring of institute's bonding).

Preferred R ⁴, R ⁵, R ⁶and R ⁷be the alkyl of hydrogen atom or carbonatoms 1～4, more preferably hydrogen atom, methyl or ethyl independently respectively.

As G ¹and G ²represented divalent ester ring type alkyl, can list monocyclic alkyl, endocyclic alkyl, is preferably 5 rings or 6 rings.Described ester ring type alkyl can be saturated also can be unsaturated, but be preferably saturated fat ring type alkyl.In addition, G is also arranged ¹and G ²in represented ester ring type alkyl, form it-CH ₂-quilt-O-,-S-or-situation that NH-replaces and form the situation that its methyne is replaced by tertiary N atom.That is, G ¹and G ²can be to contain heteroatomic group.If enumerate G ¹and G ²concrete example, the group by formula (g-1)～formula (g-10) means is respectively arranged.

G ¹and G ²the hydrogen atom comprised in represented divalent ester ring type alkyl can be substituted base (below, according to circumstances, be referred to as " substituting group Z ²") replace.As substituting group Z ², can list the alkyl of the carbonatomss 1～4 such as methyl, ethyl, sec.-propyl, the tertiary butyl; The alkoxyl group of the carbonatoms such as methoxyl group, oxyethyl group 1～4; The fluoroalkyl of the carbonatomss such as trifluoromethyl 1～4; The Fluoroalkyloxy of the carbonatomss such as trifluoromethoxy 1～4; Cyano group; Nitro; The halogen atoms such as fluorine atom, chlorine atom, bromine atoms.

As G ¹and G ², be preferably the represented divalent ester ring type alkyl of formula (g-1).Wherein, more preferably G ¹and G ²be all Isosorbide-5-Nitrae-cyclohexylene, be particularly preferably anti-form-1, the 4-cyclohexylene.

L in formula (A) ¹and L ²be respectively 1 valency organic group independently, L ¹and L ²among at least one be the organic group with polymerizable group.

More preferably L ¹for the represented group of formula (A1) (below, according to circumstances, be referred to as " group (A1) "), L ²for the represented group of formula (A2) (below, according to circumstances, be referred to as " group (A2) ").

P ¹-F ¹-（B ¹-A ¹） _k-E ¹- （A1）

P ²-F ²-（B ²-A ²） _l-E ²- （A2）

[in formula (A1) and formula (A2),

F ¹and F ²the divalent aliphatic alkyl that means carbonatoms 1～12.

P ¹mean polymerizable group.

P ²mean hydrogen atom or polymerizable group.

R ⁴and R ⁵mean the meaning same as described above.]

In group (A1) and group (A2), A ¹and A ²the concrete example of represented divalent ester ring type alkyl is as G ¹and G ²the group that illustrates for example of divalent ester ring type alkyl, its preferred example also with G ¹and G ²preferred example identical.As A ¹and A ²represented divalent aryl, it can also can be polycycle (comprising polycycle and fused polycyclic that a plurality of aromatic nucleus form by singly bound) for monocyclic.As A ¹and A ²represented divalent aryl, can enumerate as the group by formula (a-1)～formula (a-8) means respectively.In addition, as A ¹and A ²represented aryl, preferably have the group of symmetry axis or the plane of symmetry.

A ¹and A ²the hydrogen atom comprised in represented ester ring type alkyl and aryl can be substituted base and replace.As substituting group, can list as G ¹and G ²the substituting group Z that represented ester ring type alkyl can have arbitrarily ²the group illustrated for example.

As A ¹and A ², be preferably independently respectively Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylene, from the manufacture of compound (A) the easier aspect that becomes, consider, be preferably Isosorbide-5-Nitrae-phenylene.

Become and be easy to tendency and consider from the manufacture of compound (A), preferably B ¹and B ²for congener group.In addition, when k, l are the integer more than 2, if at 2 A ¹between B ¹, at 2 A ²between B ²for-CH ₂-CH ₂-,-C(=O)-O-,-CO-NH-,-O-CH ₂-or singly-bound, the manufacture of compound (A) becomes easier tendency so preferably.This optical thin film aspect that shows high liquid crystal liquid crystal property from easy formation is considered, preferably at 2 A ¹between B ¹, at 2 A ²between B ²be all-C(=O)-O-.

More preferably with F ¹the B of bonding ¹, and and F ²the B of bonding ²be independently respectively-O-,-C(=O)-O-,-O-C(=O)-,-O-C(=O)-O-,-CO-NH-,-NH-CO-or singly-bound.

Preferably k and l mean respectively 0～3 integer independently, and more preferably k and l are 0～2.More preferably k and l add up to below 4.If k and l are in described scope, compound (A) has to become and more easily shows the tendency of liquid crystal liquid crystal property.

Preferred F ¹and F ²be the alkylidene group of carbonatoms 1～12, more preferably straight-chain alkyl-sub-independently respectively.Unsubstituted alkylidene group particularly preferably.The hydrogen atom comprised in described alkylidene group can be replaced by the alkoxyl group of carbonatoms 1～5 or halogen atom.In addition, form described alkylidene group-CH ₂-can by-O-or-C(=O)-replace.

P ¹and P ²for hydrogen atom or polymerizable group, its at least one be polymerizable group.While going for more excellent this optical thin film of hardness, preferred P ¹and P ²be all polymerizable group.

Polymerizable group refers to the characteristic group that can make compound (A) polymerization, particularly, vinyl, vinyloxy group, styryl can be shown for example, (2-phenyl vinyl) phenyl, acryl, methacryloyl, acryloxy, methacryloxy etc. be there is to the polymerizable group of ethene unsaturated group; Carboxyl; Ethanoyl; Hydroxyl; Formamyl; The alkylamino of carbonatoms 1～4; Amino; Epoxy ethyl; Oxa-cyclobutyl, formyl radical, isocyanato or isothiocyanic acid base etc.

As polymerizable group, preferably be applicable to the free-radical polymerised group and cationically polymerizable group, particularly preferably acryl, methacryloyl, acryloxy and the methacryloxy that make compound (A) carry out photopolymerization.Wherein, the preferred polymeric group is acryloxy or methacryloxy respectively independently, is particularly preferably acryloxy.

If consider the easiness of compound (A) on manufacturing, preferred group (A1) is identical with group (A2), that is, and and L ¹with L ²identical.

Similarly, in compound (A), if D ¹with D ²identical, G ¹with G ²identical, in compound (A), if-D ¹-G ¹-L ¹represented group and-D ²-G ²-L ²represented group is identical, preferred.Now, can more easily manufacture compound (A).

As L ¹during for the represented group of formula (A1)-D ¹-G ¹-L ¹concrete example and as L ²during for the represented group of formula (A2)-D ²-G ²-L ²concrete example, can list group by following formula (R-1)～formula (R-134) means respectively etc.

And the n in formula (R-1)～formula (R-134) means 2～12 integer, is preferably 3～10, more preferably 4～8.

Further preferred L ¹for group (A1), L ²for the compound (A) of group (A2) meets the relation of formula (1) and formula (2) simultaneously.

（N _π-4）/3<k+l+4 （1）

12≦N _π≦22 （2）

[in formula (1) and formula (2), N _πremoved-D in expression (A) ¹-G ¹-L ¹,-D ²-G ²-L ²the aromatic nucleus that has of part in the π-electron number that comprises.K and l mean the meaning same as described above.]

As compound (A), can be listed below and state compound (i)～compound (xxvii).And, the L in table ¹expression-D ¹-G ¹-L ¹, L ²expression-D ²-G ²-L ².

[table 1]

In table, for example, (i) represented compound (A) (below, corresponding to the numbering in table, this compound (A) is called as " compound (xvi) ") what mean is following compound, wherein, the represented substructure of formula (ar) be the represented structure of formula (ar-39) ,-D ¹-G ¹-L ¹represented group for the group from selecting in (R-1)～(R-48), (R-56)～(R-120) and the group that (R-129)～(R-131) forms ,-D ²-G ²-L ²represented group is from by (R-1)～(R-48), reaching the group of selecting in the group (R-56)～(R-131) formed.

For example, compound (xvi) is the mixture of following compound: a kind of compound, wherein, the represented substructure of formula (ar) be the represented structure of formula (ar-39) ,-D ¹-G ¹-L ¹represented group be group from selecting in (R-1)～(R-48), (R-56)～(R-120) and the group that (R-129)～(R-131) forms ,-D ²-G ²-L ²represented group is from by (R-1)～(R-48) and the group of selecting in the group (R-56)～(R-131) formed, another kind of compound, wherein, the represented substructure of formula (ar) be (ar-40) represented structure ,-D ¹-G ¹-L ¹represented group be group from selecting in (R-1)～(R-48), (R-56)～(R-120) and the group that (R-129)～(R-131) forms ,-D ²-G ²-L ²represented group is that, compound (xvi) refers to the mixture of 2 kinds of compounds (A) from by (R-1)～(R-48), reaching the group of selecting in the group (R-56)～(R-131) formed.

As the concrete example of the compound (A) in table, can enumerate like following such compound.Below illustrate for example compound (i) among the compound shown in table (A), compound (iii), compound (iv), compound (v), compound (viii), the representational structural formula of compound (ix), compound (x), compound (xv), compound (xvii), compound (xviii), compound (xix), compound (xx), compound (xxii), compound (xxiii), compound (xxiv) and compound (xxv).Following chemical formula comprises the steric isomer that they are whole.In addition, the Isosorbide-5-Nitrae-cyclohexylene of preferred compound (i)～(xxv) is all anti-form-1, the 4-cyclohexylene.

(2 * in formula (A1) and the * bonding of (A1-1)～(A1-8) arbitrarily.）

(2 * in formula (A2) and the * bonding of (A2-1)～(A2-8) arbitrarily.）

(2 * in formula (A3) and the * bonding of (A3-1)～(A3-8) arbitrarily.）

(2 * in formula (A4) and the * bonding of (A4-1)～(A4-8) arbitrarily.）

(2 * in formula (A5) and the * bonding of (A5-1)～(A5-8) arbitrarily.）

(2 * in formula (A6) and the * bonding of (A6-1)～(A6-8) arbitrarily.）

(2 * in formula (A7) and the * bonding of (A7-1)～(A7-8) arbitrarily.）

(2 * in formula (A8) and the * bonding of (A8-1)～(A8-8) arbitrarily.）

(2 * in formula (A9) and the * bonding of (A9-1)～(A9-8) arbitrarily.）

(2 * in formula (A10) and the * bonding of (A10-1)～(A10-8) arbitrarily.）

(2 * in formula (A11) and the * bonding of (A11-1)～(A11-8) arbitrarily.）

(2 * in formula (A12) and the * bonding of (A12-1)～(A12-8) arbitrarily.）

(2 * in formula (A13) and the * bonding of (A13-1)～(A13-8) arbitrarily.）

(2 * in formula (A14) and the * bonding of (A14-1)～(A14-8) arbitrarily.）

(2 * in formula (A15) and the * bonding of (A15-1)～(A15-8) arbitrarily.）

(2 * in formula (A16) and the * bonding of (A16-1)～(A16-8) arbitrarily.）

(2 * in formula (A17) and the * bonding of (A17-1)～(A17-8) arbitrarily.）

(2 * in formula (A18) and the * bonding of (A18-1)～(A18-8) arbitrarily.）

(2 * in formula (A19) and the * bonding of (A19-1)～(A19-8) arbitrarily.）

(2 * in formula (A20) and the * bonding of (A20-1)～(A20-8) arbitrarily.）

(2 * in formula (A21) and the * bonding of (A21-1)～(A21-8) arbitrarily.）

(2 * in formula (A22) and the * bonding of (A22-1)～(A22-8) arbitrarily.）

(2 * in formula (A23) and the * bonding of (A23-1)～(A23-8) arbitrarily.）

(2 * in formula (A24) and the * bonding of (A24-1)～(A24-8) arbitrarily.）

(2 * in formula (A25) and the * bonding of (A25-1)～(A25-8) arbitrarily.）

(2 * in formula (A26) and the * bonding of (A26-1)～(A26-8) arbitrarily.）

(2 * in formula (A27) and the * bonding of (A27-1)～(A27-8) arbitrarily.）

(2 * in formula (A28) and the * bonding of (A28-1)～(A28-8) arbitrarily.）

(2 * in formula (A29) and the * bonding of (A29-1)～(A29-8) arbitrarily.）

(2 * in formula (A30) and the * bonding of (A30-1)～(A30-8) arbitrarily.）

(2 * in formula (A31) and the * bonding of (A31-1)～(A31-8) arbitrarily.）

(2 * in formula (A32) and the * bonding of (A32-1)～(A32-8) arbitrarily.）

(2 * in formula (A33) and the * bonding of (A33-1)～(A33-8) arbitrarily.）

(2 * in formula (A34) and the * bonding of (A34-1)～(A34-8) arbitrarily.）

(2 * in formula (A35) and the * bonding of (A35-1)～(A35-8) arbitrarily.）

(2 * in formula (A36) and the * bonding of (A36-1)～(A36-8) arbitrarily.）

(2 * in formula (A37) and the * bonding of (A37-1)～(A37-8) arbitrarily.）

(2 * in formula (A38) and the * bonding of (A38-1)～(A38-8) arbitrarily.）

(2 * in formula (A39) and the * bonding of (A39-1)～(A39-8) arbitrarily.）

(2 * in formula (A40) and the * bonding of (A40-1)～(A40-8) arbitrarily.）

(2 * in formula (A41) and the * bonding of (A41-1)～(A41-8) arbitrarily.）

(2 * in formula (A42) and the * bonding of (A42-1)～(A42-8) arbitrarily.）

(2 * in formula (A43) and the * bonding of (A43-1)～(A43-8) arbitrarily.）

(2 * in formula (A44) and the * bonding of (A44-1)～(A44-8) arbitrarily.）

(2 * in formula (A45) and the * bonding of (A45-1)～(A45-8) arbitrarily.）

(2 * in formula (A46) and the * bonding of (A46-1)～(A46-8) arbitrarily.）

(2 * in formula (A47) and the * bonding of (A47-1)～(A47-8) arbitrarily.）

(2 * in formula (A48) and the * bonding of (A48-1)～(A48-8) arbitrarily.）

(2 * in formula (A49) and the * bonding of (A49-1)～(A49-8) arbitrarily.）

(2 * in formula (A50) and the * bonding of (A50-1)～(A50-8) arbitrarily.）

(2 * in formula (A51) and the * bonding of (A51-1)～(A51-8) arbitrarily.）

(2 * in formula (A52) and the * bonding of (A52-1)～(A52-8) arbitrarily.）

(2 * in formula (A53) and the * bonding of (A53-1)～(A53-8) arbitrarily.）

(2 * in formula (A54) and the * bonding of (A54-1)～(A54-8) arbitrarily.）

(2 * in formula (A55) and the * bonding of (A55-1)～(A55-8) arbitrarily.）

(2 * in formula (A56) and the * bonding of (A56-1)～(A56-8) arbitrarily.）

(2 * in formula (A57) and the * bonding of (A57-1)～(A57-8) arbitrarily.）

(2 * in formula (A58) and the * bonding of (A58-1)～(A58-8) arbitrarily.）

(2 * in formula (A59) and the * bonding of (A59-1)～(A59-8) arbitrarily.）

(2 * in formula (A60) and the * bonding of (A60-1)～(A60-8) arbitrarily.）

(2 * in formula (A61) and the * bonding of (A61-1)～(A61-8) arbitrarily.）

In addition, as compound (A), can also use following material.

Compound (A) can be according to its structure, by appropriate combination Methoden der Organischen Chemie(organic chemistry method), Organic Reactions(organic reaction), Organic Syntheses(organic synthesis), the comprehensive organic synthesis of Comprehensive Organic Synthesis(), the condensation reaction of record in new experimental chemistry lecture etc., esterification, Williamson's reaction, ullmann reaction, Wittig reaction, the Schiff's base formation reaction, the benzyl reaction, the reaction of Yuan head, Suzuki-Pu, palace reaction, the reaction of root bank, the reaction of bear field, the Hui Shan reaction, Buchwald-Hartwig reaction, Freed-Kerafyrm thatch reaction, the He Ke reaction, the manufactures such as aldol reaction.

With D ¹and D ²compound (A) during for *-O-CO-is example, its manufacture method of simple declaration.At first, prepare respectively the represented compound (compound (1-2)) of the represented compound of formula (1-1) (compound (1-1)) and formula (1-2), by compound (1-1) is reacted with compound (1-2), obtain the represented compound of formula (1-3) (compound (1-3)).

[in formula, X ¹, Y ¹, Q ¹, and Q ²mean and the meaning identical in formula (A).]

[in formula, G ¹, E ¹, A ¹, B ¹, F ¹, P ¹and k means the meaning same as described above.]

[in formula, X ¹, Y ¹, Q ¹, Q ², G ¹, E ¹, A ¹, B ¹, F ¹, P ¹and k means the meaning same as described above.]

Then, by the compound (1-3) that makes to make, the compound (compound (1-4)) represented with formula (1-4) reacts to manufacture compound (A).

[in formula, G ², E ², A ², B ², F ², P ²and l means the meaning same as described above.]

Preferred compound (1-1) and compound (1-2) react and compound (1-3) is implemented with reacting under the existence of esterifying agent of compound (1-4).

As esterifying agent (condensing agent), can list 1-cyclohexyl-3-(2-morpholino ethyl) carbodiimide methyl tosilate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (part water-soluble carbodiimide: as Water Soluble Carbodiimide(water-soluble carbodiimide) is sold in market), two (2, the 6-diisopropyl phenyl) carbodiimide, two (trimethyl silyl) carbodiimide, the carbodiimides such as DIC, 2-methyl-6-nitrobenzoyl acid anhydrides, 2,2 '-carbonyl diurethane-1H-imidazoles, 1,1 '-oxalyl group diimidazole, diphenyl phosphoryl azide, 1-(4-oil of mirbane alkylsulfonyl)-1H-1,2,4-triazole, 1H-benzotriazole-1-base oxygen tripyrrole Wan Ji Phosphonium hexafluorophosphate, 1H-benzotriazole-1-base oxygen three (dimethylamino) Phosphonium hexafluorophosphate, N, N, N ', N '-tetramethyl--O-(N-succinimido) the urea a tetrafluoro borate, N-(1,2,2,2-tetrachloro ethoxy carbonyl oxygen) succinimide, N-carbobenzoxy-(Cbz) succinimide, O-(6-chlorobenzotriazole-1-yl)-N, N, N ', N '-tetramethyl-urea a tetrafluoro borate, O-(6-chlorobenzotriazole-1-yl)-N, N, N ', N '-tetramethyl-urea hexafluorophosphate, the bromo-1-ethylpyridine of 2-a tetrafluoro borate, 2-is chloro-1,3-methylimidazole quinoline muriate, 2-is chloro-1,3-methylimidazole quinoline hexafluorophosphate, the chloro-1-picoline of 2-iodide, the chloro-1-picoline of 2-tosilate, the fluoro-1-picoline of 2-tosilate, trichoroacetic acid(TCA) pentachlorophenyl ester etc.Wherein, from reactivity, cost, can use widely the solvent aspect to consider, as the preferred dicyclohexylcarbodiimide of condensing agent, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, two (2, the 6-diisopropyl phenyl) carbodiimide, two (trimethyl silyl) carbodiimide, DIC, 2,2 '-carbonyl diurethane-1H-imidazoles.

When this composition (1) contains the compound (A) as polymerizable liquid crystal compound, use the content ratio expression with respect to the solid state component of this composition (1), preferably its content is 10～99.9 quality %, 20～99 quality % more preferably, more preferably 50～97 quality %, be particularly preferably 80～95 quality %.If the content of compound (A) is in described scope, the optical thin film made (1) becomes the optical thin film that same polarization conversion may be arranged in wavelength region widely.Solid state component refers to the total amount of the composition low volatile components such as removing desolventizing from this composition (1).In this composition (1), can use separately compound (A), also can be as shown in the compound (xvi) in table like that and with compound of more than two kinds (A).

As polymerizable liquid crystal compound, (the liquid crystal brief guide is compiled the council and is compiled can to list the liquid crystal brief guide, ball kind (strain) is put down into distribution on October 30th, 12) " 3.8.6 network-type (cross-linking type fully) ", there is the compound of polymerizable group in " 6.5.1 liquid crystal material b. polymerizability nematic liquid crystalline material " among the compound of record, Japanese Patent Laid-Open 2010-31223 communique, Japanese Patent Laid-Open 2010-270108 communique, the polymerizable liquid crystal compound of putting down in writing in Japanese Patent Laid-Open 2011-6360 communique and Japanese Patent Laid-Open 2011-207765 communique.

As polymerizable liquid crystal compound, can enumerate compound represented suc as formula (3) (below, according to circumstances, be referred to as " compound (3) ") etc.

P ¹¹-E ¹¹-（B ¹¹-A ¹¹） _t-B ¹²-G （3）

[in formula (3),

A ¹¹mean to there is or do not have substituent fragrant heterocycle, have or do not have substituent aryl or there is or do not have substituent ester ring type alkyl.

B ¹¹and B ¹²respectively independently expression-C ≡ C-,-CH=CH-,-CH ₂-CH ₂-,-O-,-S-,-CO-,-CO-O-,-CS-,-O-CO-O-,-CR ¹³r ¹⁴-,-CR ¹³r ¹⁴-CR ¹⁵r ¹⁶-,-O-CR ¹³r ¹⁴-,-CR ¹³r ¹⁴-O-CR ¹⁵r ¹⁶-,-CO-O-CR ¹³r ¹⁴-,-O-CO-CR ¹³r ¹⁴-,-CR ¹³r ¹⁴-O-CO-CR ¹⁵r ¹⁶-,-CR ¹³r ¹⁴-CO-O-CR ¹⁵r ¹⁶-,-NR ¹³-CR ¹⁴r ¹⁵-,-CH=N-,-N=N-,-CO-NR ¹⁶-,-OCH ₂-,-OCF ₂-,-CH ₂o-,-CF ₂o-,-CH=CH-CO-O-or singly-bound.R ¹³～R ¹⁶the alkyl that means hydrogen atom or carbonatoms 1～4.

G mean fluoroalkyl, the carbonatoms 1～13 of alkoxyl group, the carbonatoms 1～13 of alkyl, the carbonatoms 1～13 of hydrogen atom, halogen atom, carbonatoms 1～13 N-alkylamino, cyano group, nitro or-E ¹²-P ¹².

E ¹¹and E ¹²mean the alkylidene group of carbonatoms 1～18, the hydrogen atom comprised in described alkylidene group can be replaced by halogen atom, the methylene radical comprised in described alkylidene group can by Sauerstoffatom or-CO-replaces.

P ¹¹and P ¹²mean polymerizable group.

T means 1～5 integer.When t is the integer more than 2, a plurality of B ¹¹can be mutually identical also can be different, a plurality of A ¹¹can be mutually identical also can be different.]

As A ¹¹represented aromatic hydrocarbon ring, can list phenyl ring, naphthalene nucleus, anthracene nucleus and phenanthroline ring etc., as fragrant heterocycle, can list furan nucleus, pyrrole ring, thiphene ring, pyridine ring, thiazole ring and benzothiazole ring etc.Wherein, preferred phenyl ring, thiazole ring and benzothiazole ring.As A ¹¹represented aromatic hydrocarbon ring or fragrant heterocycle, can enumerate as the divalent group by formula (Ara-1)～formula (Ara-11) means respectively.

[in formula (Ara-1)～formula (Ara-11),

X ³x in expression and formula (A) ³the identical meaning.A plurality of X that exist in same group ¹can be mutually identical also can be different.

Y ³mean with as the Y in formula (A) ¹the group that the group illustrated for example is identical.

Z ³mean with as the Z in formula (A) ¹the group that the group illustrated for example is identical.

W ^aand W ^bmean independently respectively hydrogen atom, cyano group, methyl or halogen atom.

M means 0～6 integer.

N means 0～4 integer.

O means 0～2 integer.

When m, n and o are the integer more than 2, a plurality of Z that exist in same group ³can be mutually identical also can be different.]

As A ¹¹represented aromatic hydrocarbon ring or fragrant heterocycle, the group preferably meaned respectively by formula (Ara-1) and formula (Ara-7), particularly, can illustrate following radicals for example.

A ¹¹the carbonatoms of represented ester ring type alkyl is for example 3～18, is preferably 5～12, is particularly preferably 5 or 6.As A ¹¹represented ester ring type alkyl, can list Isosorbide-5-Nitrae-cyclohexylene etc.The substituting group that can have as described ester ring type alkyl, can list there is or do not have halogen atom, alkyl, the alkoxyl group that there is or do not have fluorine-based carbonatoms 1～6, nitro and the cyano group of fluorine-based carbonatoms 1～6.

As P ¹¹and P ¹²represented polymerizable group, can list and P as compound (A) ¹and P ²represented polymerizable group and the identical group of group that illustrates for example.From considering in polymerization (solidifying) low temperature more, preferred photic polymerizable group, further preferred free-radical polymerised group or cationically polymerizable group, particularly from not only easily processing, the manufacture of compound (3) also is easy to aspect to be considered, as P ¹¹and P ¹²represented polymerizable group, the group preferably meaned respectively by formula (P-1)～(P-5).

[in formula (P-1)～(P-5),

R ¹⁷～R ²¹the alkyl or the hydrogen atom that mean independently respectively carbonatoms 1～6.* mean and B ¹¹bonding position.]

E ¹¹and E ¹²for the alkylidene group of carbonatoms 1～18, be preferably the straight chain shape or the alkylidene group of the carbonatoms 1～12 of 1 tapping point is arranged.

As compound (3), can enumerate as following material.

When this composition (1) contains compound (3) as polymerizable liquid crystal compound and/or compound (A), total amount 100 mass parts with respect to compound (A) and compound (3), its content is below 90 mass parts for for example compound (3), be preferably below 70 mass parts, more preferably below 40 mass parts.And, for example, by adjusting, derive from compound (A) structural unit content and derive from the content of the structural unit of compound (3), can form this optical thin film (1) with required wavelength dispersion characteristics.If increase the content of the structural unit that derives from compound (A), this optical thin film (1) has the tendency that more easily shows anti-wavelength dispersion characteristics.In order to form this optical thin film (1) with required wavelength dispersion characteristics, preparation derives from this composition (1) of 2～5 kinds of different left and right of the content of structural unit of compound (A), for each this composition (1), manufacture the optical thin film of identical thickness and try to achieve its phase difference value.Then, according to result, try to achieve the relation between the phase difference value of the content of the structural unit that derives from compound (A) and optical thin film, can be according to the correlationship obtained, determine that optical thin film in order to give described thickness is with the needed content that derives from the structural unit of compound (A) of required phase difference value.

As polymerizable liquid crystal compound, can enumerate compound as contained the represented group of formula (X1) (below, according to circumstances, be referred to as " compound (X1) ".) etc.

P ¹¹-B ¹¹-E ¹¹-B ¹²-A ¹¹-B ¹³-* （X1）

(in formula (X1), P ¹¹mean polymerizable group.

A ¹¹mean divalent ester ring type alkyl or divalent aryl.The hydrogen atom comprised in described divalent ester ring type alkyl and divalent aryl can be replaced by the alkyl of halogen atom, carbonatoms 1～6, carbonatoms 1～6 alkoxyl group, cyano group or nitro, and the hydrogen atom comprised in the alkoxyl group of the alkyl of described carbonatoms 1～6 and described carbonatoms 1～6 can be replaced by fluorine atom.

B ¹¹expression-O-,-S-,-CO-O-,-O-CO-,-O-CO-O-,-CO-NR ¹⁶-,-NR ¹⁶-CO-,-CO-,-CS-or singly-bound.R ¹⁶the alkyl that means hydrogen atom or carbonatoms 1～6.

B ¹²and B ¹³respectively independently expression-C ≡ C-,-CH=CH-,-CH ₂-CH ₂-,-O-,-S-,-C(=O)-,-C(=O)-O-,-O-C(=O)-,-O-C(=O)-O-,-CH=N-,-N=CH-,-N=N-,-C(=O)-NR ¹⁶-,-NR ¹⁶-C(=O)-,-OCH ₂-,-OCF ₂-,-CH ₂o-,-CF ₂o-,-CH=CH-C(=O)-O-,-O-C(=O)-CH=CH-or singly-bound.

E ¹¹mean the alkylidene group of carbonatoms 1～12, the hydrogen atom comprised in described alkylidene group can be replaced by the alkoxyl group of carbonatoms 1～5, and the hydrogen atom comprised in described alkoxyl group can be replaced by halogen atom.In addition, form described alkylidene group-CH ₂-can by-O-or-CO-replaces.

* mean bonding position.）

A ¹¹aryl and the carbonatoms of ester ring type alkyl be for example 3～18, be preferably 5～12, be particularly preferably 5 or 6.As A ¹¹, be preferably Isosorbide-5-Nitrae-cyclohexylene, Isosorbide-5-Nitrae-phenylene.

As E ¹¹, the alkylidene group of the carbonatoms 1～12 of preferred straight chain shape.Form described alkylidene group-CH ₂-can be replaced by-O-.

Particularly, methylene radical, ethylidene, trimethylene, tetramethylene, 1 are arranged, 5-pentylidene, 1,6-hexylidene, 1, the inferior heptyl of 7-, octamethylene, 1,9-is nonamethylene, 1, the inferior decyl, 1 of 10-, the straight chain shape alkylidene group of the carbonatomss 1～12 such as the inferior undecyl of 11-and the inferior dodecyl of 1,12-;-CH ₂-CH ₂-O-CH ₂-CH ₂-,-CH ₂-CH ₂-O-CH ₂-CH ₂-O-CH ₂-CH ₂-and-CH ₂-CH ₂-O-CH ₂-CH ₂-O-CH ₂-CH ₂-O-CH ₂-CH ₂-etc.

As P ¹¹represented polymerizable group, from polymerisation reactivity, particularly the reactive high aspect of photopolymerization is considered, preferred free-radical polymerised group or cationically polymerizable group, from not only easily also easy aspect consideration of the manufacture of processing, liquid crystalline cpd itself, as the preferred following formula of polymerizable group (P-11)～represented group of formula (P-15).

[in formula (P-11)～(P-15),

R ¹⁷～R ²¹the alkyl or the hydrogen atom that mean independently respectively carbonatoms 1～6.]

If formula (P-11)～represented group of formula (P-15) further is shown particularly for example, can list following formula (P-16)～represented group of formula (P-20).

Preferred P ¹¹for formula (P-14)～represented group of formula (P-20), even more preferably vinyl, to Stilbene base, epoxy group(ing), oxa-cyclobutyl etc.

P particularly preferably ¹¹-B ¹¹-represented group is acryloxy or methacryloxy.

As compound (X1), can enumerate as formula (I), formula (II), formula (III), formula (IV), formula V or the represented compound of formula (VI).

P ¹¹-B ¹¹-E ¹¹-B ¹²-A ¹¹-B ¹³-A ¹²-B ¹⁴-A ¹³-B ¹⁵-A ¹⁴-B ¹⁶-E ¹²-B ¹⁷-P ¹² （I）

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

P ¹¹-B ¹¹-E ¹¹-B ¹²-A ¹¹-B ¹³-A ¹²-B ¹⁴-A ¹³-B ¹⁵-E ¹²-B ¹⁷-P ¹² （III）

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

P ¹¹-B ¹¹-E ¹¹-B ¹²-A ¹¹-B ¹³-A ¹²-B ¹⁴-E ¹²-B ¹⁷-P ¹² （V）

P ¹¹-B ¹¹-E ¹¹-B ¹²-A ¹¹-B ¹³-A ¹²-F ¹¹ （VI）

(in formula,

A ¹²～A ¹⁴with A ¹¹equivalent in meaning, B ¹⁴～B ¹⁶with B ¹²equivalent in meaning, B ¹⁷with B ¹¹equivalent in meaning, E ¹²with E ¹¹equivalent in meaning.

F ¹¹mean hydrogen atom, the alkyl of carbonatoms 1～13, the alkoxyl group of carbonatoms 1～13, cyano group, nitro, trifluoromethyl, dimethylamino, hydroxyl, methylol, formyl radical, sulfonic group (SO ₃h), alkoxy carbonyl or the halogen atom of carboxyl, carbonatoms 1～10, form described alkyl and alkoxyl group-CH ₂-can be replaced by-O-.）

As the concrete example of compound (X1), can enumerate as by following formula (I-1)～formula (I-4), formula (II-1)～formula (II-4), formula (III-1)～formula (III-26), formula (IV-1)～formula (IV-19), formula (V-1)～formula (V-2), compound that formula (VI-1)～formula (VI-6) means respectively etc.But, in formula, k1 and k2 mean 2～12 integer.If these compounds, compound itself is easily manufactured and is on sale etc. in market, because obtaining easily so preferred.

Use the content ratio expression with respect to the solid state component content of composition (1), preferably the content of the compound (X1) in this composition (1) is 10～99.9 quality %, 20～99 quality % more preferably, more preferably 50～98 quality %, be particularly preferably 80～97 quality %.If in described scope, manufacture this optical thin film the time, the excellent composition of coating (coating) can be used as with respect to base material is used.Solid state component refers to the total amount of the composition low volatile components such as removing desolventizing from composition (B).

1-3. photo-induced polymerization initiator

Photo-induced polymerization initiator is to produce by the effect of light the compound of the polymerization of living radical, initiated polymerization liquid crystalline cpd.As photo-induced polymerization initiator, can list alkyl phenyl ketone compound, st-yrax compound, benzophenone cpd and oxime compound etc.

As the alkyl phenyl ketone compound, can list alpha-aminoalkyl phenyl ketone compound, Alpha-hydroxy alkyl phenyl ketone compound and alpha-alkoxy base alkyl phenyl ketone compound.

As alpha-aminoalkyl phenyl ketone compound, can list 2-methyl-2-morpholinyl-1-(4-methylthio group phenyl)-1-acetone, 2-dimethylamino-1-(4-morpholinyl phenyl)-2-benzyl-1-butanone and 2-dimethylamino-1-(4-morpholinyl phenyl)-2-(4-aminomethyl phenyl methyl)-the 1-butanone etc., be preferably 2-methyl-2-morpholinyl-1-(4-methylthio group phenyl)-1-acetone and 2-dimethylamino-1-(4-morpholinyl phenyl)-2-benzyl-1-butanone etc.Alpha-aminoalkyl phenyl ketone compound can use gorgeous good solid (Irgacure) (registered trademark) 369,379EG, more than 907(, BASF Japan (strain) system) and SEIKUOL(セイクオー Le) (registered trademark) BEE(Seiko chemistry society system) and etc. commercially available product.

As Alpha-hydroxy alkyl phenyl ketone compound, can list 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl)-1-acetone, 1-hydroxy-cyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) oligopolymer etc. of 1-acetone.Alpha-hydroxy alkyl phenyl ketone compound can use gorgeous good solid 184,2959, more than 127(, BASF Japan (strain) system) and SEIKUOL Z(Seiko chemistry society system) etc. commercially available product.

As alpha-alkoxy base alkyl phenyl ketone compound, can list diethoxy acetophenone, benzyl dimethyl ketal etc.More than alpha-alkoxy base alkyl phenyl ketone compound can be used gorgeous good solid 651(, BASF Japan (strain) system) etc. commercially available product.

As the alkyl phenyl ketone compound, preferred alpha-aminoalkyl phenyl ketone compound, the more preferably represented compound of formula (C-1).Thermotolerance by containing described compound, have the optical thin film made and the tendency of humidity resistance excellence.

[in formula (C-1), Q ³mean hydrogen atom or methyl.]

As the st-yrax compound, can enumerate as st-yrax, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether etc.

As benzophenone cpd, can enumerate as benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide and 3,3 '; 4; 4 '-tetra-(t-butylperoxy carbonyl) benzophenone, 2,4,6-tri-methyl benzophenone etc.

As oxime compound; can list N-benzoyloxy-1-(4-thiophenyl phenyl)-1-butanone-2-imines, N-benzoyloxy-1-(4-thiophenyl phenyl)-1-octanone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethane-1-imines and N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3; 3-dimethyl-2,4-dioxane amyl group methoxyl group) benzoyl }-9H-carbazole-3-yl] ethane-1-imines etc.As oxime compound, can use gorgeous good solid OXE-01, more than OXE-02(, BASF Japan society system), N-1919(Ai Dike society system) etc. commercially available product.

Photo-induced polymerization initiator can be used separately acetophenone compound, st-yrax compound, benzophenone cpd, oxime compound etc., but also two or more is also used.Wherein, as photo-induced polymerization initiator, preferably use acetophenone compound.With respect to the photo-induced polymerization initiator total amount, preferably the consumption of acetophenone compound is more than 90 mass parts, and more preferably photo-induced polymerization initiator is all acetophenone compound.

With respect to the solid state component of this composition (1), preferably the content of the photo-induced polymerization initiator in this composition (1) is 0.1 quality %～30 quality %, more preferably 0.5 quality %～10 quality %.If in described scope, during the polymerizable liquid crystal compound polymerization that makes to comprise in this composition (1), the confusion of the orientation of Inhibitor (A) better.And solid state component refers to the total amount of the composition low volatile components such as removing desolventizing from this composition (1).

1-4. organic solvent

Operability in order to make to manufacture optical thin film is good, and preferably this composition (1) contains solvent, particularly organic solvent.As organic solvent, preferably can dissolve the organic solvent of the moiety of this composition (1), further more preferably the polyreaction of the polymerizable liquid crystal compound that comprises in this composition (1) is to inactive solvent.Particularly, can list the pure series solvents such as methyl alcohol, ethanol, ethylene glycol, Virahol, propylene glycol, methylcyclohexane, ethylene glycol butyl ether, propylene glycol monomethyl ether and phenol; The ester series solvents such as ethyl acetate, butylacetate, ethylene glycol monomethyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; The ketone series solvents such as acetone, ethyl methyl ketone, cyclopentanone, pimelinketone, Methyl amyl ketone and methyl iso-butyl ketone (MIBK); The chlorine-free aliphatic hydrocarbon solvents such as pentane, hexane and heptane; The chlorine-free such as toluene and dimethylbenzene aromatic solvent; The nitrile series solvents such as acetonitrile; The ether such as tetrahydrofuran (THF) and glycol dimethyl ether series solvent; The chlorine such as chloroform and chlorobenzene series solvent; Deng.Organic solvent can be used separately, but also multiple combination is used.Wherein, preferred alcohols series solvent, ester series solvent, ketone series solvent, chlorine-free aliphatic hydrocarbon solvent and chlorine-free aromatic solvent.Particularly due to the moiety consistency excellence of this composition, even being dissolvable in water pure series solvent, ester series solvent, ketone series solvent, chlorine-free aliphatic hydrocarbon solvent and chlorine is aromatic solvent etc., even, therefore do not use the chlorine series solvent such as chloroform, also can make and can manufacture by coating on suitable base material this composition of this optical thin film.

This composition (1) is while containing organic solvent, and with respect to solid state component 100 mass parts, preferably its content is 10 mass parts～10000 mass parts, more preferably 100 mass parts～5000 mass parts.In addition, preferably the solid component concentration in this composition (1) is 2 quality %～50 quality %, more preferably 5～50 quality %.Solid state component refers to the total amount of the composition low volatile components such as removing desolventizing from this composition (1).

This composition (1) can contain the additives such as photosensitizer, flow agent, chiral reagent, stopper.

1-5. photosensitizer

As photosensitizer, can list the xanthones such as xanthone and thioxanthone; There is the substituent anthracene classes such as anthracene and alkyl oxide; Thiodiphenylamine; Rubrene.

By using photosensitizer, can make highly sensitiveization of polymerization of polymerizable liquid crystal compound etc.In addition, with respect to polymerizable liquid crystal compound 100 mass parts, as the consumption of photosensitizer, be for example 0.1 mass parts～30 mass parts, be preferably 0.5 mass parts～10 mass parts.

1-6. flow agent

As flow agent, can list the oily system of organically-modified silicone, polyacrylic ester system and perfluoroalkyl is flow agent etc.Particularly, can enumerate as DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, more than FZ2123(, all by the beautiful DOW CORNING in east (strain), made), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, more than KF6001(, all by SHIN-ETSU HANTOTAI's chemical industry (strain), made), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, more than TSF4460(all by figure new high-tech material advanced in years Japan contract commercial firm system), fluorinert(Off ロリナート) (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, more than fluorinert FC-3283(all by Sumitomo 3M(strain) system), Megafac(メガ Off ァッ Network) (registered trademark) R-08, Megafac R-30, Megafac R-90, Megafac F-410, Megafac F-411, Megafac F-443, Megafac F-445, Megafac F-470, Megafac F-477, Megafac F-479, Megafac F-482, more than Megafac F-483(, all by Dainippon Ink. & Chemicals Inc's (strain), made), EFTOP(エ Off トップ) (trade(brand)name) EF301, EFTOP EF303, EFTOP EF351, all by the Mitsubishi Materials electronics, change into (strain) system more than EFTOP EF352(), Surflon(サー Off ロ Application) (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, all by AGC, beautify clearly (strain) system more than SA-100(), trade(brand)name E1830, trade(brand)name E5844((strain) great Jin fine chemistry industry institute system), BM-1000, BM-1100, BYK-352, BYK-353, BYK-361N(is all trade(brand)name: BM Chemie society system) etc.Flow agent can be used separately, but also two or more is also used.

By using flow agent, can make the optical thin film made become more level and smooth.Further, in the manufacturing processed of optical thin film, mobility that can the control group compound, regulate the cross-linking density of the optical thin film that the polymerizable liquid crystal compound polymerization is obtained.In addition, with respect to polymerizable liquid crystal compound 100 mass parts, the consumption of flow agent is for example 0.1 mass parts～30 mass parts, is preferably 0.1 mass parts～10 mass parts.

1-7. chiral reagent

As chiral reagent, can use known chiral reagent (for example, liquid crystal device handbook, the 3rd chapter 4-3 item, TN, STN chiral reagent, 199 pages, JSPS the 142nd council compiles, record in 1989).

Chiral reagent contains unsymmetrical carbon usually, but also the axle asymmetric compound or the face asymmetric compound that do not contain unsymmetrical carbon can be used as chiral reagent.In the example of axle asymmetric compound or face asymmetric compound, can list dinaphthalene, helicene, p-Xylol ring disome and their derivative.

For example, can list the compound as putting down in writing in Japanese Patent Laid-Open 2007-269640 communique, Japanese Patent Laid-Open 2007-269639 communique, Japanese Patent Laid-Open 2007-176870 communique, Japanese Patent Laid-Open 2003-137887 communique, the special table of Japanese Patent 2000-515496 communique, Japanese Patent Laid-Open 2007-169178 communique, Japanese Patent JP-A 9-506088 communique, can preferably list the paliocolor(registered trademark of BASF Japan (strain) system) LC756.

For example, with respect to polymerizable liquid crystal compound 100 mass parts, the consumption of chiral reagent is 0.1 mass parts～30 mass parts, is preferably 1.0 mass parts～25 mass parts.If in described scope, during the polymerizable liquid crystal compound polymerization that makes to comprise in this composition (1), can suppress better the confusion of the orientation of polymerizable liquid crystal compound.

1-8. stopper

As stopper, can enumerate as: Resorcinol and there is the substituent hydroquinone type such as alkyl oxide; Butyl-catechol etc., there is the substituent catechols such as alkyl oxide; Pyrogallol class, 2,2,6,6-tetramethyl--radical scavengers such as piperidino oxyradical; The thiophenol class; Beta-naphthylamine class or 2-Naphthol class etc.

By using stopper, can control the polymerization of polymerizable liquid crystal compound, can improve the stability of optical thin film (1).With respect to polymerizable liquid crystal compound 100 mass parts, the content of stopper is for example 0.1 mass parts～30 mass parts, is preferably 0.5 mass parts～10 mass parts.If in described scope, can there is no chaotic situation in the orientation of polymerizable liquid crystal compound, make the polymerizable liquid crystal compound polymerization.

2. optical thin film

This optical thin film (1) is the optical thin film that polymerizable liquid crystal compound is polymerized.This optical thin film (1) is the film that can see through light, is the film with optical function.Optical function refers to refraction, double refraction etc.

Among this optical thin film (1) in visible-range the excellent optical thin film of the transparency, because it can be used as various display device components, use, so preferably.The thickness of this optical thin film (1) can suitably be regulated according to the purposes of this optical thin film (1), is preferably 0.1 μ m～10 μ m, from reducing the photoelasticity aspect, considers more preferably 0.2 μ m～5 μ m.

While using this optical thin film (1) in display unit, this optical thin film (1) can be used individual layer, also can make this optical thin film of multilayer (1) lamination obtain laminate, also can with other film combinations.By using with other film combinations, can be used for phase retardation film, compensation film for angular field of view, visual angle expansion film, antireflection film, light polarizing film, rotatory polarization film, elliptical polarized light film and brightness enhancement film etc.

Particularly this optical thin film (1) is by being used in combination compound (A) and compound (3) polymerizable liquid crystal compound as this composition (1), make changes in optical properties according to both state of orientation, can be adjusted to the VA(vertical alignment, vertical alignment) pattern, the IPS(in-plane changes, in-plane switching) pattern, OCB(is optical compensation curved, optically compensated bend) pattern, the TN(twisted nematic, twisted nematic) pattern, the STN(super-twist nematic, super twisted nematic) the various liquid crystal indicator phase-contrast films such as pattern.

2-1. phase-contrast film

As a kind of phase-contrast film of optical thin film, its be this optical thin film (1) one of preferred embodiment.Phase-contrast film is for being transformed to rectilinearly polarized light circularly polarized light or elliptically polarized light, making circularly polarized light or elliptically polarized light be transformed to rectilinearly polarized light conversely, reaching the polarization direction that changes rectilinearly polarized light.

As phase-contrast film (1), known, if establish the specific refractory power of the slow-axis direction in face, be n _x, with the specific refractory power of direction (quick shaft direction) of slow axis quadrature in face be n _y, thickness direction specific refractory power be n _z, can as following, classify.That is, can list

N _xn _y≒ n _zpositive A-plate,

N _x≒ n _yn _znegative C-plate,

N _x≒ n _y<n _zpositive C-plate,

N _x≠ n _y≠ n _zpositive O-plate and negative O-plate.

The phase difference value of phase-contrast film (1) can suitably be selected according to the display unit of using from 30～300nm.

Phase-contrast film (1) is during as wide band λ/4 plate, can be by Re(549) be adjusted into 113～163nm, preferably be adjusted into 130～150nm.It is during as wide band λ/2 plate, can be by Re(549) be adjusted into 250～300nm, preferably be adjusted into 265～285nm.If phase difference value is above-mentioned value, with respect to the light of wavelength widely, the similarly tendency of polarization conversion is arranged, so preferably.Wide band λ/4 plates refer to the light with respect to each wavelength, present the phase-contrast film of its phase difference value of 1/4, and wide band λ/2 plates refer to the light with respect to each wavelength, present the phase-contrast film of its phase difference value of 1/2.

And the content by the polymerizable liquid crystal compound that comprises in suitable this composition of adjusting (1), can be prepared into the thickness that gives required phase differential.The phase difference value (length of delay, Re(λ) of the phase-contrast film that cause makes) as formula (4), be determined, therefore in order to obtain required Re(λ), can suitably regulate Δ n(λ) and thickness d.

Re（λ）=d×Δn（λ）（4）

(in formula, Re(λ) means phase difference value corresponding to wavelength X nm, and d means thickness, Δ n(λ) degree of birefringence corresponding to expression wavelength X nm.）

2-2. the manufacture method of this optical thin film (1)

This optical thin film (1) can be by preparing suitable base material, coating this composition (1) on base material, and drying, manufacture the polymerizable liquid crystal compound polymerization comprised in this composition (1).

2-2-0. base material

As the base material of the manufacture that can be used for this optical thin film, preferably as: glass, plastics sheet, plastics film, transparent thin-film.As transparent thin-film, can enumerate as the polyolefin films such as polyethylene, polypropylene, norbornene-based polymer, PVA (PVOH) FILM, pet film, polymethacrylate film, polyacrylate film, cellulose ester film, PEN film, polycarbonate film, polysulphone film, polyethersulfone film, polyetherketone film, PPS (polyphenylene sulfide) films and polyphenylene oxide film etc.

As the base material for the manufacture of this optical thin film (1), the article that preferably formed by the material with hydroxyl, the film more preferably formed by the material with hydroxyl.Film with material formation of hydroxyl can be the film obtained by the material filming with hydroxyl, also can be at the material filming of the growth precursor with hydroxyl and, after becoming film (precursor thin film), change the growth precursor comprised in precursor thin film into hydroxyl.Such transformation can enumerate as: under vacuum or the Cement Composite Treated by Plasma under normal atmosphere, laser treatment, ozonize, saponification processing or flame treating etc.In addition, it can be also the base material obtained by following method, the film that described method does not have the material formation of hydroxyl or its growth precursor for preparation, the primary coat that is coated with coupling agent at film surface is processed, after the polymkeric substance that makes to have the monomer of hydroxyl or have hydroxyl is attached to surface, irradiates radioactive rays, plasma body, ultraviolet ray and make it react to carry out the method for graft polymerization.The film that also will set the material with hydroxyl at film surface is in this manual regarded the film consisted of the material with hydroxyl as.If use the film (base material) formed by the material with hydroxyl, the tendency that has the close property between base material and this optical thin film to become higher.

Among the film formed by the material with hydroxyl (base material), preferably by being implemented to saponification, triacetylcellulose film processes the film obtained.By triacetylcellulose film is implemented to saponification, process, the triacetyl cellulose in film, by saponification, can easily make the film consisted of the material with hydroxyl, and the processing aspect during from cost, manufacture is considered also particularly preferably.

In addition, preferably, on the surface of this optical thin film of formation of the base material of the manufacture for this optical thin film (1), alignment films is set.According to the differently-oriented directivity of alignment films, the polymerizable liquid crystal compound in this optical thin film is orientated to desirable direction, can make the polymerizable liquid crystal compound polymerization.During base material that use consists of the material with hydroxyl, alignment films can be set on base material.

2-2-1. the making of unpolymerized film

By coating this composition (1) on base material or on alignment films, can on base material, make unpolymerized film.During the mesomorphic phases such as unpolymerized film demonstration nematic phase, it has the birefringence that single domain orientation (Monodomain Alignment) causes.

As the coating process on the base material in this composition (1), can enumerate as the extrusion coated method, direct intaglio plate coating method (Direct gravure coating method), reverse intaglio plate coating method (Reverse gravure coating method), the CAP coating method, die coating method (Die coating method), ink-jet printing process (Ink jet method), dip coated method (Dip coating method), slot coated method (Slit coating method), the coating of method of spin coating (Spin coating method) and use metering bar coater (Bar Coater) etc.

Wherein, from considering in this Composition Aspects of base material coating continuously according to the form of reel-to-reel (Roll to Roll), the preferably coating of CAP coating method, ink-jet printing process, dip coated method, slot coated method, die coating method and use metering bar coater.

This optical thin film (1) also can be processed under the state with the base material lamination.By make in advance the base material lamination on this optical thin film, when the transportation of carrying out film, keeping etc., can suppress this optical thin film damaged, can easily be processed.

If make in advance alignment films form on base material, coating this composition (1) on alignment films then, because of without by this optical thin film of stretching (1), carrying out specific refractory power control, therefore birefringent interior deviation diminishes.Therefore, this large optical thin film that connects the panel display apparatus (FPD) that can tackle maximization can be manufactured.

As the method that forms alignment films, can list use by friction given the orientation polymkeric substance of orientation anchorage force method (below, according to circumstances, be referred to as " rubbing manipulation "), use the method for having given the light orientation polymkeric substance of orientation anchorage force by irradiating polarized light (below, according to circumstances, be referred to as " optical alignment method "), in the method for substrate surface oblique angle evaporation silicon oxide and use Lang Gemiaoer-Blodget method (LB method) to form the method etc. of the unimolecular film with chain alkyl.Wherein, the consideration of the viewpoint of the orientation uniformity of the polymerizable liquid crystal compound comprised from this composition (1), the treatment time of manufacturing this optical thin film and processing cost, more preferably optical alignment method.As alignment films, preferably there is solvent resistance, described solvent resistance refers to, even be coated with this composition thereon, also can not be dissolved in the composition comprised in this composition (1), the solvent resistance of the degree of the solvent for example comprised in this composition (1).In addition, alignment films also requires to have thermotolerance, and described thermotolerance refers to, for from undried film except desolventizing, heat treated thermotolerance when the liquid crystal aligning of polymerizable liquid crystal compound.

About optical alignment method, identical with the content illustrated in the 2nd mode of the present invention.

The thickness of the alignment films formed on base material, for for example 10nm～10000nm, is preferably 10nm～1000nm.If make it in described scope, can make the polymerizable liquid crystal compound orientation comprised in this composition (1) to required angle.

2-2-2. the polymerization of unpolymerized film

Polymerizable liquid crystal compound polymerization by comprising in the unpolymerized film that makes on base material or form on alignment films, solidify, can make this optical thin film (1).In this optical thin film (1), the orientation of polymerizable liquid crystal compound is immobilized, and it is not vulnerable to the impact of the birefringent variation that caused by heat.

As the method that makes the polymerizable liquid crystal compound polymerization, preferred photic polymerization.By the photopolymerization method, because implementing at low temperatures polymerization, therefore the stable on heating range of choice of the base material used enlarges.The photopolymerization reaction is undertaken by irradiate visible ray, UV-light or laser on unpolymerized film.From the aspect of processing, consider, particularly preferably UV-light.

The unpolymerized film formed for being coated with this composition (1) on base material or on alignment films, although also can directly carry out rayed, make unpolymerized film hardening, preferably in advance dry unpolymerized film, from unpolymerized film except desolventizing.

Although removing also of solvent can parallelly with polyreaction be carried out, preferably before carrying out polymerization, remove in advance desolventizing.Remove method as this, can enumerate as seasoning, air seasoning, heat drying or drying under reduced pressure etc., or by the method for their combinations.Wherein, preferred seasoning or heat drying, the temperature while preferably carrying out seasoning or heat drying is 0 ℃～250 ℃, more preferably 50 ℃～220 ℃, more preferably 80 ℃～170 ℃.Preferably be 10 second～60 minute heat-up time, more preferably 30 second～30 minute.If Heating temperature and heat-up time in described scope, as base material, can use thermotolerance base material fully.

By peeling off base material, obtain the film (laminated film) that alignment films and this optical thin film lamination form.Further, peel off alignment films, can make this optical thin film (1) of individual layer.In addition, can also, by fitting on laminated film by other base materials (film or plate) in advance, then peeling off base material or alignment films at the upper lamination of this optical thin film (1), carry out transfer printing.

3. Polarizer

This optical thin film (1) can be for the manufacture of Polarizer.Polarizer of the present invention at least has this phase-contrast film (1).The Polarizer that uses this phase retardation film (1) is illustrated.

As Polarizer, as shown in Fig. 1 (a)～Fig. 1 (e), can list Polarizer 4a(Fig. 1 (a) that (1) this phase retardation film 1 and the direct lamination of polarisation rete 2 form); (2) Polarizer 4b(Fig. 1 (b) that this phase retardation film 1 and polarisation rete 2 form by bond layer 3 ' laminating); (3) make this phase retardation film 1 and this phase retardation film 1 ' lamination, the Polarizer 4c(Fig. 1 (c) that further makes this phase retardation film 1 ' and polarisation rete 2 laminations form); (4) this phase retardation film 1 and this phase retardation film 1 ' are fitted by bond layer 3, the Polarizer 4d(Fig. 1 (d) that further on this phase retardation film 1 ', makes polarisation rete 2 laminations form); And (5) make this phase retardation film 1 and this phase retardation film 1 ' pass through bond layer 3 laminatings, the Polarizer 4e(Fig. 1 (e) that further makes this phase retardation film 1 ' and polarisation rete 2 fit and form by bond layer 3 ') etc.Caking agent refers to the general name of caking agent and/or tackiness agent.

Polarisation rete 2 is so long as have the film of polarisation function and get final product, and can enumerate as the film that adsorbed iodine or dichroism pigment and stretched on polyvinyl alcohol film, polyvinyl alcohol film stretched and adsorb iodine or film that the dichroism pigment forms etc.

Polarisation rete 2, further, as required, can be equipped with the film that becomes protective membrane.As protective membrane; can enumerate as the polyolefin films such as polyethylene, polypropylene, norbornene-based polymer, pet film, polymethacrylate film, polyacrylate film, cellulose ester film, PEN film, polycarbonate film, polysulphone film, polyethersulfone film, polyetherketone film, PPS (polyphenylene sulfide) films and polyphenylene oxide film etc.

The caking agent preferably used in bond layer 3 and bond layer 3 ' is for the transparency is high, the caking agent of excellent heat resistance.As such a caking agent, can use as: acrylic acid series caking agent, epoxy are that caking agent or ammonia ester are caking agent etc.

In addition, in Polarizer, as shown in Fig. 1 (c)～Fig. 1 (e), can be by this phase retardation film more than 2 layers (1) of containing this optical thin film (1) directly or fitted by bond layer.

4. panel display apparatus

Panel display apparatus of the present invention contains this optical thin film (1), and it is extremely useful as the member that relates to panel display apparatus.Can enumerate as: possess the liquid crystal panel that the laminating of this optical thin film (1) and liquid crystal panel forms liquid crystal indicator, possess the organic EL display of the organic electroluminescent that this optical thin film (1) and luminescent layer laminating form (below, also be referred to as " EL ") panel.

4-1. liquid crystal indicator

As liquid crystal indicator of the present invention, can enumerate the liquid crystal indicator shown in like Fig. 2 (a) and Fig. 2 (b) etc.The liquid crystal indicator 10a shown in Fig. 2 (a) liquid crystal indicator that to be Polarizer 4 of the present invention form by bonding coat 5 laminatings with liquid crystal panel 6, to be Polarizer 4 of the present invention fit in by bonding coat 5 and bonding coat 5 ' liquid crystal indicator that the two sides of liquid crystal panel 6 forms with Polarizer 4 ' of the present invention to the liquid crystal indicator 10b shown in Fig. 2 (b).According to above-mentioned composition, the electrode by not showing in use figure, apply voltage on liquid crystal panel, the change in orientation of liquid crystal molecule, can show black and white.

4-2. organic EL display

As organic EL display of the present invention, can list the organic EL display shown in Fig. 3 etc.As organic EL display, can list the organic EL display 11 that Polarizer 4 of the present invention and organic EL panel 7 form by bonding coat 5 laminatings.Organic EL panel 7 is layers of at least 1 layer that consist of the electroconductibility organic compound.According to above-mentioned composition, the electrode by not showing in use figure, apply voltage on organic EL panel, the compound light-emitting comprised in the luminescent layer that organic EL panel has, can show black and white.

And, in organic EL display 11, the preferred Polarizer of Polarizer 4 for working as wide band rotatory polarization plate.If the Polarizer worked as wide band rotatory polarization plate, can prevent the lip-deep outer reflection of light of organic EL display 11.

According to the present invention, can provide manufacture method, the optical thin film of the optical thin film manufacture of close property excellence with the optical thin film of composition and use composition.

II. the 2nd mode of the present invention

The 2nd composition of the present invention (below, according to circumstances, the 2nd composition of the present invention is called to " this composition (2) ", according to circumstances, the optical thin film that will be manufactured by this composition (2) be called " this optical thin film (2) ".）

This composition (2) contain (D) light orientation polymkeric substance (below, according to circumstances, be referred to as " polymkeric substance (D) ".) and (B) have in molecule carbon-to-carbon unsaturated bond and reactive with active hydrogen group compound (below, according to circumstances, be referred to as " compound (B) ".）。

1-1. polymkeric substance (D)

When polymkeric substance (D) forms optical anisotropic layer for this optical thin film (2) being manufactured by this composition (2) is upper, make the liquid crystalline cpd orientation.

Make the method for this optical thin film (2) (as this optical thin film (2) of alignment films) of liquid crystalline cpd orientation use as formation, can list by friction give polymkeric substance (D) orientation anchorage force method (rubbing manipulation), by irradiating polarized light, give polymkeric substance (D) orientation anchorage force method (below, according to circumstances, be referred to as " optical alignment method ") etc.Wherein, from the viewpoint of orientation uniformity, treatment time and the processing cost of liquid crystalline cpd, consider, preferably effectively utilize the optical alignment method of the ability of the polymkeric substance (D) comprised in this composition (2).As this optical thin film now (2), even preferably it has and has been coated with the also solvent resistance of undissolved degree of liquid crystalline cpd.In addition, while manufacturing this optical thin film (2), also seeking for from undried film, except desolventizing, thermal treatment when liquid crystalline cpd is orientated, thering is thermotolerance.

As polymkeric substance (D), use the polymkeric substance with photosensitive structure.If there is the upper polarized light that irradiates of the polymkeric substance of photosensitive structure (D), the photosensitive structure isomerization by irradiated part or crosslinked, polymkeric substance (D) orientation, thus give this optical thin film (2) orientation made anchorage force.As photosensitive structure, can enumerate as nitrogen benzide structure, maleimide amine structure, cinnamophenone structure, styracin structure, vinylene structure, 1,2-acetylene structure, spiro-pyrans structure, spirobenzopyran structure and fulgide structure etc.Polymkeric substance (D) with photosensitive structure can be separately for this composition (2), but also two or more and use.And polymkeric substance (D) can be used the monomer with photosensitive structure, the chain polymerizations such as the polycondensation caused by dehydration, deamination etc., radical polymerization, anionoid polymerization, cationoid polymerisation, polycoordination or ring-opening polymerization etc. makes.In addition, can be also to use the multiple multipolymer with monomer of different photosensitive structure.As polymkeric substance (D), the light orientation polymkeric substance of record in can list Japanese Patent No. 4450261, No. 4011652nd, Japanese Patent, Japanese Patent Laid-Open 2010-49230 communique, No. 4404090th, Japanese Patent, Japanese Patent Laid-Open 2007-156439 communique, Japanese Patent Laid-Open 2007-232934 communique etc.

As polymkeric substance (D), particularly preferably by rayed, form the material of crosslinking structure.If polymkeric substance (D), for forming the material of crosslinking structure, while forming optical anisotropic layer, can guarantee that optical anisotropic layer forms the sufficient weather resistance when being coated with composition.

With respect to the total mass of this composition (2), preferably the content of the polymkeric substance (D) in this composition (2) is 0.1～30 quality %, more preferably 0.2～15 quality %.

By this composition (2) is coated on base material, can manufacture this optical thin film (2).As base material, can list the base material of enumerating in the 1st mode of the present invention.

In order to manufacture this optical thin film (2) on base material, if use this composition (2) that contains solvent, the manufacture because of this optical thin film becomes easy to be preferred.As the solvent comprised in this composition (2), can enumerate water outlet and organic solvent.As organic solvent, can list the organic solvent of enumerating in the 1st mode of the present invention.During this composition that use contains solvent (2), solvent can be used separately, but also multiple combination is used.

Composition of the present invention (2) is while containing solvent, and with respect to solid state component 100 mass parts of this composition (2), preferably its content is 100 mass parts～20000 mass parts, more preferably 200 mass parts～15000 mass parts.Solid state component refers to the total amount of the composition low volatile components such as removing desolventizing from this composition (2).

1-2. compound (B)

As compound (B), can list with this composition (1) illustrated in the 1st mode of the present invention in the same material of the compound (B) that comprises.

With respect to the total mass of this composition (2), preferably the content of the compound (B) in this composition (2) is 0.01～10 quality %, more preferably 0.02～5 quality %.If in described scope, do not make the situation of the reactivity reduction of the polymkeric substance (D) in this composition (2).

2. this optical thin film (2)

Preferably this optical thin film (2) is for making the crosslinked optical thin film formed of polymkeric substance (D) comprised in this composition (2).

In order to be formed this optical thin film coated film (undried film) for manufacture by this composition (2), at first, coating this composition (2) on base material.As the coating process on base material, can list and illustrate in the 1st mode of the present invention, the method for this composition of coating (1) on base material.

Then, drying coated coated film on base material, remove the low boiling point components such as solvent that comprise in coated film.

As drying means, can enumerate as seasoning, air seasoning, heat drying or drying under reduced pressure etc., or combine their method.As drying temperature, be preferably 10～250 ℃, more preferably 25～200 ℃.In addition, as time of drying, be preferably 5 second～60 minute, more preferably 10 second～30 minute.Some dry temperature and time of drying, in described scope, while using any one base material, all can be suppressed the damage to base material.

2-1. this optical thin film as alignment films

Among this optical thin film (2), by polymkeric substance (D) being carried out to polarizing light irradiation, make its crosslinked optical thin film formed can be used as alignment films to work.Particularly, if this composition that will contain solvent (2) is coated on base material, carried out polarizing light irradiation and make polymkeric substance (D) crosslinked on the coated film made, this optical thin film made (2) becomes alignment films.Preferably coated film (undried film) is dry in advance before carrying out polarizing light irradiation, makes dry film.

In order to give the orientation anchorage force by optical alignment method, carry out polarizing light irradiation (for example, rectilinearly polarized light ultraviolet ray) on the coated film formed by this composition (2).Polarizing light irradiation can be used the device of putting down in writing in Japanese Patent Laid-Open 2006-323060 communique for example to carry out.In addition, can also on the coated film formed by this composition (2), prepare the photomask corresponding to required a plurality of zones, in each this zone, be situated between and repeatedly (for example carry out polarizing light irradiation by photomask, the rectilinearly polarized light ultraviolet ray), form thus pattern (Pattern) and change alignment films.As photomask, can use such as being provided with the article of light-shielding pattern on the film at silica glass, soda-lime glass or polyester etc.The part covered by light-shielding pattern has been avoided being exposed in the light of exposure, and unlapped part sees through the light of exposure.Because of the impact of thermal expansion little, therefore preferably silica glass as the base material used in photomask.

Below enumerate the example of manufacturing the patterning alignment films.At first, on the coated film formed by this composition (2), by thering is the 1st photomask (remaining zone becomes light-shielding pattern) corresponding to the space part of the 1st area of the pattern, irradiate the 1st polarized light (irradiating the 1st polarized light) with the 1st polarization direction.By irradiating the 1st polarized light, make the direction of the orientation anchorage force of the 1st area of the pattern correspond to the 1st polarization direction.Then, by thering is the 2nd photomask (remaining zone becomes light-shielding pattern) corresponding to the space part of the 2nd area of the pattern, irradiation has the 2nd polarized light (irradiating the 2nd polarized light) of 2nd polarization direction different from the 1st polarization direction (for example, with respect to the 1st polarization direction vertical direction).By irradiating the 2nd polarized light, make the direction of the orientation anchorage force of the 2nd area of the pattern correspond to the 2nd polarization direction.Thus, make the mutual alignment films of different a plurality of area of the pattern of direction with orientation anchorage force.Further, by the photomask more than 3 kinds, repeatedly irradiate polarized light, can also make and there is the orientation anchorage force direction patterned orientation film of the different area of the pattern more than 3 mutually.From the reactive aspect of polymkeric substance (D), consider, the light preferably irradiated in each polarizing light irradiation is all ultraviolet ray.

The thickness of this optical thin film (2), for for example 10nm～10000nm, is preferably 10nm～1000nm.If make it in described scope, when the upper formation of this optical thin film (2) optical anisotropic layer, can make the liquid crystalline cpd orientation to required angle.

2-2. phase retardation film (2)

Upper at this optical thin film (2), the article that form optical anisotropic layer, show phase differential become phase retardation film (below, according to circumstances, be referred to as " this phase retardation film (2) ".）。According to circumstances, be called " optical anisotropic layer forms and uses composition " at the following composition that optical anisotropic layer is formed to use.

2-2-1. liquid crystalline cpd

Optical anisotropic layer can be orientated to form by for example making liquid crystalline cpd, and optical anisotropic layer forms and contains such liquid crystalline cpd with composition, preferably contains polymerizable liquid crystal compound.Form with containing a kind of liquid crystalline cpd in composition at optical anisotropic layer, also can contain different liquid crystalline cpds of more than two kinds.

As liquid crystalline cpd, can enumerate the polymerizable liquid crystal compound illustrated as in the 1st mode of the present invention, preferably contain the compound of the represented group of formula (X1).

2-2-2. additive

Form with in composition at optical anisotropic layer, except liquid crystalline cpd, can also contain the additives such as photo-induced polymerization initiator, stopper, photosensitizer, photo-induced polymerization initiator, solvent, chiral reagent.Particularly, when optical anisotropic layer forms, from optical anisotropic layer, form by the easy aspect of the film forming transfiguration of composition own and consider, preferably contain solvent, particularly organic solvent.In addition, when liquid crystalline cpd is polymerizable liquid crystal compound, preferably optical anisotropic layer forms with composition and contains and have the polymerization starter that optical anisotropic layer is formed to the function of the film hardening formed with composition.

As each additive, can list the additive of enumerating in the 1st mode of the present invention.

By at the upper coating of this optical thin film (2) optical anisotropic layer, forming and use composition, can on this optical thin film (2), make unpolymerized film.During the mesomorphic phases such as unpolymerized film demonstration nematic phase, it has the birefringence that the single domain orientation causes.

As at the upper coating of this optical thin film (2) optical anisotropic layer, forming the method with composition, can suitablely be used as the method for this composition (2) being coated to the method on base material and illustrating for example.Wherein, from forming by Composition Aspects and consider at this optical thin film coating optical anisotropic layer continuously according to the form of reel-to-reel, the preferably coating of CAP coating method, ink-jet printing process, dip coated method, slot coated method, die coating method and use metering bar coater.For example, while adopting the form of reel-to-reel, can be implemented in continuously coating this composition (2) on base material, form this optical thin film (2) on base material, further at this optical thin film made (2), above form optical anisotropic layer.

This optical thin film (2) can be used under the state with the base material lamination.,, when the transportation of carrying out film, keeping etc., can suppress this optical thin film (2) breakage, can easily process at the upper laminated base material of this optical thin film (2) by advance.

By making in the upper optical anisotropic layer liquid crystalline cpd polymerization comprised in coated film (unpolymerized film) for formation formed of this optical thin film (2), solidifying, make this phase retardation film (2).The orientation of liquid crystalline cpd is immobilized in phase retardation film (2), and it is not vulnerable to the impact of the birefringent variation that caused by heat.

As making liquid crystalline cpd polymerization, curing method, can list the method for enumerating in the 1st mode of the present invention.

This phase retardation film (2) be this optical thin film (2) use one of preferred embodiment.This phase retardation film (2) is for making rectilinearly polarized light be transformed to circularly polarized light or elliptical polarized light, make circularly polarized light or elliptically polarized light be transformed to rectilinearly polarized light conversely, reach the polarization direction that changes rectilinearly polarized light.

The characteristic of this phase retardation film (2) with that illustrate in the 1st mode of the present invention, characteristic this phase retardation film (1) is identical.

4. Polarizer

This optical thin film (2) can be used for the manufacture of Polarizer.

As Polarizer, can list the Polarizer identical with the Polarizer illustrated in the 1st mode of the present invention.

5. panel display apparatus

Panel display apparatus of the present invention contains this optical thin film (2).

As panel display apparatus, can list the panel display apparatus identical with the panel display apparatus illustrated in the 1st mode of the present invention.

III. the 3rd mode of the present invention

The 3rd mode of the present invention be the optical thin film that forms of the sequential lamination according to base material, the A layer that formed by composition (A) and the B layer that formed by composition (B) (below, according to circumstances, be referred to as " this optical thin film (3) ".）。

1. base material

As base material, can enumerate base material as identical as the base material with illustrating in the 1st mode of the present invention.

The more preferably base material film (base material) that the material with hydroxyl that illustrates in the 1st mode of the present invention forms of serving as reasons.The film (base material) consist of the material with hydroxyl if use,, because of the close property except A layer/B interlayer uprises, the tendency that the close property of base material/A interlayer uprises in addition, therefore can make this more high-quality optical thin film.

Among the film formed at the material by having hydroxyl, the film consist of the material that the triacetyl cellulose saponification is made if use, by the synergy with composition (A), because the close property of base material/A interlayer becomes better so preferably.In addition, the film formed by the material that the triacetyl cellulose saponification is made, the viewpoint that the film (triacetylcellulose film) itself formed from the triacetyl cellulose as its precursor thin film easily obtains from market is considered also preferred.

2. composition (A)

The composition (2) of composition (A) for illustrating in the 2nd mode of the present invention.(D) light orientation polymkeric substance in composition (A) is equivalent to the polymkeric substance (D) in composition (2), and the compound that (B-1) in composition (A) has carbon-to-carbon unsaturated bond and reactive with active hydrogen group is equivalent to the compound (B) in composition (2).

3. composition (B)

The composition (1) of composition (B) for illustrating in the 1st mode of the present invention.Polymerizable liquid crystal compound in composition (B) is equivalent to the polymerizable liquid crystal compound in composition (1), the compound that (B-1) in composition (B) has carbon-to-carbon unsaturated bond and reactive with active hydrogen group is equivalent to the compound (B) in composition (1), and (C) photo-induced polymerization initiator in composition (B) is equivalent to (C) photo-induced polymerization initiator in composition (1).

As compound (B-1) and compound (B-2), preferably as compound (2), can list commercially available Laromer(registered trademark) LR-9000(BASF society system) etc.And, the compound (B-1) contained in composition (A) and the compound (B-2) contained in composition (B) can be identical mutually also can be different, but preferably both are identical.If compound (B-1) and compound (B-2) are all the commercially available products such as Laromer LR-9000, from composition (A) and easily preparation aspect of composition (B), consider and preferably.

4. this optical thin film

This optical thin film (3) is can be through the film of light, for having the film of optical function.Optical function refers to refraction, double refraction etc.

Preferably this optical thin film (3) is the excellent optical thin film of the transparency in visible-range, and it can be used as various display device components, particularly the panel display apparatus member.The thickness of this optical thin film (3) can suitably be regulated according to the purposes of this optical thin film, is preferably 0.1～10 μ m, from reducing the photoelasticity aspect, considers more preferably 0.2～5 μ m.

The thickness of preferred substrates is 10～200 μ m, more preferably 15～100 μ m.In addition, preferably the thickness (thickness) of A layer is 0.01～10 μ m(10～10000nm), 0.01～1 μ m(10～1000nm more preferably).The thickness of B layer (thickness), for for example 0.1～10 μ m, is preferably 0.2～5 μ m.

While using this optical thin film (3) in display unit, this optical thin film can be used individual layer, also can make this optical thin film multilayer laminated boards use as laminate, also can with other film combinations.By using with other film combinations, can be used for phase retardation film, compensation film for angular field of view, visual angle expansion film, antireflection film, light polarizing film, rotatory polarization film, elliptical polarized light film and brightness enhancement film etc.In addition, among the concrete example of the base material illustrated for example, optical thin film of the present invention can be the optical thin film that multiple base material lamination forms, and also can have multilayer A layer, also can have multilayer B layer.And, for example, while thering is multilayer A layer, after it refers to and uses composition (A) to form the 1st A layer on base material, before forming the B layer, on the 1st A layer, use the composition (A) different from composition (A) to form the 2nd A layer etc.

This optical thin film particularly, the state of orientation of polymerizable liquid crystal compound makes changes in optical properties when forming according to the B layer, can be adjusted to VA(vertical alignment) pattern, IPS(in-plane switching) pattern, OCB(optically compensated bend) pattern, TN(twisted nematic) pattern, STN(super twisted nematic) the various liquid crystal indicator phase retardation films such as pattern.

4-1. phase retardation film

Phase retardation film be this optical thin film (3) use one of preferred embodiment.

As phase retardation film, can list the phase retardation film of enumerating in the 1st mode of the present invention.

4-2. the manufacture method of this optical thin film

The manufacture method of this optical thin film for example comprises following<1 >～<4 operation.And this manufacture method is that composition (A) and composition (B) are all used the method for the material that contains solvent, is the manufacture method that base material, A layer and B layer respectively have this optical thin film of a kind.

<1 >, by composition (A) is coated on base material, form the operation (the 1st coated film forms operation) of the 1st coated film on base material;

<2 > by making according to<1 > (B-1) that comprise in the 1st coated film that obtains crosslinked, the 1st coated film changed into to the operation (the A layer forms operation) of A layer;

<3 > by<2 > on the A layer that forms, by coating composition (B), form the operation (the 2nd coated film forms operation) of the 2nd coated film on the A layer;

<4 > make by<3 the operation (the B layer forms operation) of the polymerizable liquid crystal compound polymerization that comprises in the 2nd coated film that forms

It is coating composition (A) by preparing base material, on base material that the 1st coated film forms operation, thereby forms the operation of the 1st coated film on base material.

As the coating process of composition (A), can list the method for enumerating in the 2nd mode of the present invention.

At the A layer, form in operation, make the light orientation polymkeric substance comprised in the 1st coated film of the 1st coated film formed on base material by the 1st coated film formation operation, preferred drying carry out light orientation (crosslinked), give thus its orientation anchorage force, thereby change the 1st coated film into the A layer.The A layer works as alignment films (oriented layer) because being endowed the orientation anchorage force.

As drying means, can list the method for enumerating in the 2nd mode of the present invention.

As be orientated the method for giving the orientation anchorage force by light, can list the method for enumerating in the 2nd mode of the present invention.

It is by being formed coating composition (B) on the A layer that operation forms by the A layer, forming the operation of the 2nd coated film (unpolymerized film) that the 2nd coated film forms operation.During the mesomorphic phases such as the polymerizable liquid crystal compound demonstration nematic phase comprised in the 2nd coated film, it has the birefringence that the single domain orientation causes.

As form in operation the method for coating composition (B) on the A layer in the 2nd coated film, can list the method for enumerating in the 1st mode of the present invention.

In the B layer forms operation, the polymerizable liquid crystal compound polymerization by comprising in the 2nd coated film that makes to form on the A layer, solidify, can make this optical thin film (3).In the B layer, the orientation of polymerizable liquid crystal compound is immobilized, and it is not vulnerable to the impact of the birefringent variation that caused by heat.In addition, by the effect of the compound (B-2) that comprises in the compound (B-1) that comprises in A layer or the 1st coated film and B layer or the 2nd coated film, it is very excellent that the close property of its A layer/B interlayer becomes.

As the method that makes the polymerizable liquid crystal compound polymerization, preferred photic polymerization.By the photopolymerization method, can implement at low temperatures polymerization, therefore the stable on heating range of choice of the base material used enlarges.The photopolymerization reaction can be undertaken by the 2nd coated film, irradiating visible ray, UV-light or laser.From the aspect of processing, consider, particularly preferably UV-light.

The 2nd coated film formed for coating composition (B) on the A layer, form the B layer although also can directly carry out rayed, preferred dry the 2nd coated film in advance, from the 2nd coated film except low volatile components such as desolventizings.

And, although low removing of volatile component can parallelly with polyreaction be carried out, preferably before carrying out polymerization, remove in advance most solvent.Remove method as this, the method that can adopt the drying means as the 1st coated film to illustrate for example.Wherein, preferred seasoning or heat drying, the temperature while preferably carrying out seasoning or heat drying is 0 ℃～250 ℃, more preferably 50 ℃～220 ℃, more preferably 80 ℃～170 ℃.Preferably be 10 second～60 minute heat-up time, more preferably 30 second～30 minute.If Heating temperature and heat-up time, base material and/or A layer can be used thermotolerance article fully in described scope.

5. as the use of the Polarizer of this optical thin film

This optical thin film can be used as the manufacture of phase retardation film for Polarizer.

6. panel display apparatus

Panel display apparatus of the present invention contains this optical thin film (3).

According to the present invention, can provide the optical thin film of the close property excellence between oriented layer and optical anisotropic layer.

[embodiment]

Below enumerate embodiment and be described more specifically the present invention.As long as, without explanation separately, it is quality % and mass parts that " % " in example reaches " part ".

1. the synthesis example of polymerizable liquid crystal compound

Compound (A11-1) is synthesized according to following synthetic route.

1-1.4,6-dimethyl benzofuran-2-carboxylic acid synthetic

Make 4,6-dimethyl salicylic aldehyde 146.6g, salt of wormwood 330.7g be scattered in N, in N '-N,N-DIMETHYLACETAMIDE 700mL.After the dispersion liquid obtained is warming up to 80 ℃, drip the bromo-acetic acid tert-butyl 190.5g of 30 minutes.Mixed solution after making to dropwise reacts 2 hours under 130 ℃.After reaction solution is cooled to room temperature, add methyl iso-butyl ketone (MIBK) 600mL, use pure water 1200mL to be washed.Further, with the pure water washing organic layer of 2 1000mL, reclaim organic layer.With after anhydrous sodium sulfate dehydration, with the evaporation unit distillation, remove desolventizing.Residue is dissolved in acetic acid 240g, adds hydrobromic acid aqueous solution 72g, stir 1 hour under 40 ℃.Let cool to room temperature, add 1N(1mol/L)-hydrochloric acid 150g, the white powder that leaching is separated out.After the white powder obtained is further used to 1N-salt acid elution, by making its vacuum-drying, obtain 4 of 81.7g yellow powder form, 6-dimethyl benzofuran-2-carboxylic acid.With 4,6-dimethyl salicylic aldehyde, for benchmark, yield is 44%.

1-2. compound (11-a) is synthetic

Mix 4,6-dimethyl benzofuran-2-carboxylic acid 80g, 2,5-dimethoxyaniline 96.6g and chloroform 400g.With after the cooling suspension liquid obtained of ice bath, with within 4 hours, adding 1-ethyl-3-(3-dimethylaminopropyl) mixed solution of carbodiimide hydrochloride 88.7g and chloroform 300g, it is at room temperature reacted 48 hours.The concentrated mixed solution obtained, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of 1N-hydrochloric acid, water-methanol to make crystallization.The throw out that leaching obtains, add the mixing solutions (water 2 parts by volume, methyl alcohol 1 parts by volume) of water-methanol.The faint yellow precipitation that leaching is separated out, with mixing solutions (water 2 parts by volume, the methyl alcohol 1 parts by volume) washing of water-methanol, vacuum-drying, obtain compound (11-a) 124.2g of pale yellow powder form.With 4,6-dimethyl benzofuran-2-carboxylic acid, for benchmark, yield is 91%.

1-3. compound (11-b) is synthetic

Mixing cpd (11-a) 123g, 2, two (the 4-p-methoxy-phenyls)-1 of 4-, 3-dithia-2,4-bis-phosphorus heterocycle butane-2,4-disulphide (lawesson reagent) 9.2g and toluene 1200g.After the mixed solution obtained is warming up to 110 ℃, it is reacted 8 hours at same temperature.After being cooled to room temperature, by the 1N-aqueous sodium hydroxide washes, wash.Reclaim organic layer, add normal heptane 800mL.The yellow mercury oxide that leaching is separated out, with the normal heptane washing, obtain compound (11-b) 109.2g of aureus powder type by making its vacuum-drying.The compound (11-a) of take is benchmark, and yield is 85%.

1-4. compound (11-c) is synthetic

Mixing cpd (11-b) 60g, potassium hydroxide 53.8g and water 1000g.

The mixed solution obtained in ice-cold lower stirring.Then add Tripotassium iron hexacyanide 133g, methyl alcohol 51g, make its reaction.Further, at room temperature make its reaction 36 hours, the yellow mercury oxide that leaching is separated out.With the precipitation of the mixed solvent (normal heptane 3 parts by volume, toluene 1 parts by volume) of normal heptane-toluene washing leaching, the yellow powder that vacuum-drying obtains, obtain compound (11-c) 51.3g of yellow solid form.The compound (11-b) of take is benchmark, and yield is 86%.

1-5. compound (11-d) is synthetic

Mixing cpd (11-c) 40g and pyridine hydrochloride 400g(10 times quality), the mixture obtained is warming up to 180 ℃, make its reaction 3 hours at same temperature.The mixed solution obtained is added in ice to the throw out that leaching is separated out.After water is suspended washing, use toluene wash, make its vacuum-drying, obtain compound (11-d) for the yellow solid 36.6g of principal constituent.The compound (11-c) of take is benchmark, and yield is 99%.

1-6. compound (R-1a) is synthetic

Compound (R-1a) is synthesized with reference to the paragraph 0244 of Japanese Patent Laid-Open 2010-31223 communique.

1-7. compound (A11-1) is synthetic

Mixing cpd (11-d) 35g, compound (R-1a) 98.8g, dimethyl aminopyridine 1.37g and toluene 700mL.Add N, N '-dicyclohexylcarbodiimide 55.6g in the mixed solution obtained under ice-cold.The reaction soln reaction that at room temperature makes to obtain is spent the night, after having used precoating the filter material of silica gel filtering, and concentrating under reduced pressure.In residue, add methyl alcohol to make its crystallization.After the leaching crystallization, make it again be dissolved in chloroform, add the 2.3g gac, at room temperature stir one hour.Filtering solution, concentrating under reduced pressure filtrate in evaporation unit, until, after its volume becomes 1/3, add while stirring methyl alcohol, the white depositions that leaching is separated out, use heptane wash, vacuum-drying obtains compound (A11-1) 74.5g of white powder form.The compound (11-d) of take is benchmark, and yield is 60%.

1-8. compound (ix-1) is synthetic

Compound (ix-1) is synthesized according to the method for Japanese Patent Laid-Open 2010-31223 communique record.

1-9. light orientation polymkeric substance (Z) is synthetic

Light orientation polymkeric substance (Z) is according to Macromol.Chem.Phys.197,1919-1935(1996) the middle method manufacture of putting down in writing.

0.1 part of 1.5 parts of represented monomers of formula (Z-a) [monomer (Z-a)] and methyl methacrylate is dissolved in 16 parts of tetrahydrofuran (THF)s, makes its reaction 24 hours under 60 ℃.Then, cooling reaction solution, to room temperature, by it is splashed in the mixed solution of toluene and methyl alcohol, makes light orientation polymkeric substance (Z).The number-average molecular weight of light orientation polymkeric substance (Z) is 33000.In light orientation polymkeric substance (Z), the containing ratio that derives from the structure of monomer (Z-a) is 75mol%.

The mensuration of the polystyrene conversion number-average molecular weight (Mn) of the light orientation polymkeric substance (Z) obtained is used the GPC method to carry out under the following conditions.

Device; HLC-8220GPC(TOSOH Co., Ltd system)

Post; TOSOH TSKgel MultiporeH _xL-M

Column temperature; 40 ℃

Solvent; The THF(tetrahydrofuran (THF))

Flow velocity; 1.0mL/min

Detector; RI

The calibration standard product; TSK polystyrene standards F-40, F-4, F-288, A-5000, A-500

2. the preparation of composition

Each composition shown in mixture table, after the solution obtained is stirred to 1 hour under 80 ℃, be cooled to room temperature and prepare composition.

[table 2]

The Japanese society of the gorgeous good solid 369(BASF of photo-induced polymerization initiator use Irg369(system)), flow agent is used the Japanese system of BYK361N(Bi Ke chemistry).Polymerizable liquid crystal compound (LC242) is BASF society system, and it is the compound of following formula.

3. the Production Example of optical thin film

Be coated with 5% toluene solution of lighting orientation polymkeric substance (Z) on the triacetylcellulose film of having implemented the saponification processing, after drying, form the film of thickness 300nm.Then, from the vertical direction with respect to face, use polarized light UV to irradiate with the SpotCure(ス Port ットキュア that is equipped with fixture) (SP-7, the prosperous motor of excellent will (strain) system) with illumination 15mW/cm ²irradiate 5 minutes rectilinearly polarized lights (polarized light UV irradiation).Implementing, on the face that polarized light UV irradiates, to use the composition in metering bar coater coating table, heating under 130 ℃, make the film be orientated towards mesomorphic phase.Afterwards, by using ユニキュア (VB-15201BY-A, Ushio Electric Inc's system) with illumination 40mW/cm being cooled under the state of room temperature ²the ultraviolet ray of illumination wavelength 365nm 1 minute, make optical thin film.

[close property evaluation]

According to JIS-K5600, use the コーテッ Cross cut processed guide I of Network Co., Ltd. series (CCI-1,1mm interval, 25 lattice with) to estimate anti-separability, the residual of liquid crystal layer is counted.The results are shown in table.Confirmed this optical thin film close property excellence.

[mensuration of optical characteristics]

Measure the phase difference value of optical thin film by mensuration machine (KOBRA-WR, prince's instrumentation machine society system).Phase difference value is measured in wavelength (λ) 549nm.The results are shown in table.

[table 3]

1. synthesis example

Similarly synthesize light orientation polymkeric substance (Z) with " synthesizing of 1-9. light orientation polymkeric substance (Z) " in the 1st mode of the present invention.

2. the preparation of composition

Each composition shown in mixture table after 1 hour, is cooled to the solution stirring that obtains room temperature and prepares composition under 80 ℃.

[table 4]

	Light orientation polymkeric substance	Compound (B)	Solvent
				Embodiment 4	Z（5.0%）	LR9000（0.2%）	Toluene (94.8%)
Embodiment 5	Z（5.0%）	LR9000（0.35%）	Toluene (94.7%)
				Comparative example 2	Z（5.0%）	-	Toluene (95.0%)

Compound (B) is used the Laromer(registered trademark) LR-9000(BASF Japan society system).

[table 5]

The Japanese society of the gorgeous good solid 369(BASF of photo-induced polymerization initiator use Irg369(system)), flow agent is used the Japanese system of BYK361N(Bi Ke chemistry).LC242 is BASF society system, and it is the compound of following formula.

3. the Production Example of optical thin film

The composition shown in coating embodiment 3,4 and comparative example 2 on complete triacetylcellulose film in saponification, after drying, form the film of thickness 280nm.Then, from the vertical direction with respect to face, use polarized light UV to irradiate with the SpotCure(SP-7 that is equipped with fixture, the prosperous motor of excellent will (strain) system) with illumination 15mW/cm ²irradiate 5 minutes rectilinearly polarized lights.Implementing on the face that polarized light UV irradiates, using optical anisotropic layer in metering bar coater coating table to form and use composition, heating under 120 ℃, making the film be orientated towards mesomorphic phase.Afterwards, by using ユニキュア (VB-15201BY-A, Ushio Electric Inc's system) with illumination 40mW/cm being cooled under the state of room temperature ²the ultraviolet ray of illumination wavelength 365nm 1 minute, make optical thin film.

[close property evaluation]

[mensuration of optical characteristics]

[table 6]

	Residual after stripping test	Re（549）
			Embodiment 4	25	135.2
Embodiment 5	25	138.3
			Comparative example 2	0	137.0

1. synthesis example

2. the preparation of composition

[table 7]

Composition (A-1)	Light orientation polymkeric substance	Compound (B-1)	Solvent
				Embodiment 6	Z（5.0%）	LR9000（0.2%）	Toluene (94.8%)
Comparative example 3	Z（5.0%）	-	Toluene (95.0%)

Compound (B-1) is used the Laromer(registered trademark) LR-9000(BASF Japan society system).

[table 8]

3. the Production Example of optical thin film

The coating composition (A-1) on complete triacetylcellulose film in saponification, after drying, form the film of thickness 280nm.Then, from the vertical direction with respect to face, use polarized light UV to irradiate with the SpotCure(SP-7 that is equipped with fixture, the prosperous motor of excellent will (strain) system) with illumination 15mW/cm ²irradiate 5 minutes rectilinearly polarized lights.Implementing, on the face that polarized light UV irradiates, to use metering bar coater coating composition (B-1), heating under 120 ℃, make the film be orientated towards mesomorphic phase.Afterwards, by using ユニキュア (VB-15201BY-A, Ushio Electric Inc's system) with illumination 40mW/cm being cooled under the state of room temperature ²the ultraviolet ray of illumination wavelength 365nm 1 minute, make optical thin film.

[close property evaluation]

[mensuration of optical characteristics]

[table 9]

	Residual after stripping test	Re（549）
			Embodiment 6	25	133.1
Comparative example 3	0	132.4

Utilizability on industry

The present invention is extremely useful in the manufacture of the optical thin film for liquid crystal indicator and organic EL display etc., and the value on industry is high.

Claims

1. one kind contains following (A), (B) and composition (C),

(A) polymerizable liquid crystal compound

(C) photo-induced polymerization initiator.

2. according to the composition of claim 1 record, wherein, be (B) to there is the compound of isocyanato as the reactive with active hydrogen group.

3. according to the composition of claim 1 record, wherein, (B) be the represented compound of following formula (X),

In formula (X),

N means 1～10 integer, R ¹' mean the divalent aliphatics of carbonatoms 2～20 or the divalent aryl of ester ring type alkyl or carbonatoms 5～20,2 R in each repeating unit ²' in one be-NH-, another is-[N-C(=O)-R ³']-represented group, R ³' mean to have the group of hydroxyl or carbon-to-carbon unsaturated bond,

R ³' among, at least 1 R ³' be the group with carbon-to-carbon unsaturated bond.

4. the composition of putting down in writing according to any one of claim 1～3, wherein, (A) be the represented compound of formula (A),

In formula (A),

X ¹mean Sauerstoffatom, sulphur atom or-NR ¹-, R ¹the alkyl that means hydrogen atom or carbonatoms 1～4,

Y ¹mean the 1 valency heteroaromatic formula base that there is or do not have 1 valency aryl of substituent carbonatoms 6～12 or there is or do not have substituent carbonatoms 3～12,

Q ³and Q ⁴mean independently respectively hydrogen atom, have or do not have 1 valency aliphatic alkyl of substituent carbonatoms 1～20, the ester ring type alkyl of carbonatoms 3～20, the 1 valency aryl that there is or do not have substituent carbonatoms 6～20, halogen atom, cyano group, nitro ,-NR ²r ³or-SR ², or Q ³and Q ⁴mutual bonding, they and its carbon atom of bonding respectively form aromatic nucleus or fragrant heterocycle, R jointly ²and R ³the alkyl that means independently respectively hydrogen atom or carbonatoms 1～6,

D ¹and D ²mean independently respectively singly-bound ,-C(=O)-O-,-C(=S)-O-,-CR ⁴r ⁵-,-CR ⁴r ⁵-CR ⁶r ⁷-,-O-CR ⁴r ⁵-,-CR ⁴r ⁵-O-CR ⁶r ⁷-,-CO-O-CR ⁴r ⁵-,-O-CO-CR ⁴r ⁵-,-CR ⁴r ⁵-O-CO-CR ⁶r ⁷-,-CR ⁴r ⁵-CO-O-CR ⁶r ⁷-or-NR ⁴-CR ⁵r ⁶-or-CO-NR ⁴-,

R ⁴, R ⁵, R ⁶and R ⁷the alkyl that means independently respectively hydrogen atom, fluorine atom or carbonatoms 1～4,

G ¹and G ²the divalent ester ring type alkyl that means independently respectively carbonatoms 5～8, the methylene radical that forms described ester ring type alkyl by Sauerstoffatom, sulphur atom or-NH-replaces or is not substituted, the methyne that forms described ester ring type alkyl can be replaced by tertiary N atom or not be substituted

L ¹and L ²mean independently respectively 1 valency organic group, L ¹and L ²among at least one be the organic group with polymerizable group.

5. according to the composition of claim 4 record, wherein, (A) be the L of formula (A) ¹for formula (A1) represented group and L ²compound during for the represented group of formula (A2),

P ¹-F ¹-（B ¹-A ¹） _k-E ¹- （A1）

P ²-F ²-（B ²-A ²） _l-E ²- （A2）

In formula (A1) and formula (A2),

B ¹, B ², E ¹and E ²difference is expression-CR independently ⁴r ⁵-,-CH ₂-CH ₂-,-O-,-S-,-CO-O-,-O-CO-O-,-CS-O-,-O-CS-O-,-CO-NR ¹-,-O-CH ₂-,-S-CH ₂-or singly-bound,

A ¹and A ²mean independently respectively the divalent ester ring type alkyl of carbonatoms 5～8 or the divalent aryl of carbonatoms 6～18, the methylene radical that forms described ester ring type alkyl by Sauerstoffatom, sulphur atom or-NH-replaces or is not substituted, the methyne that forms described ester ring type alkyl is replaced by tertiary N atom or is not substituted

K and l mean respectively 0～3 integer independently, when k is the integer more than 2, and a plurality of B ¹identical or different mutually, a plurality of A ¹identical or different mutually, when l is the integer more than 2, a plurality of B ²identical or different mutually, a plurality of A ²it is identical or different mutually,

F ¹and F ²the divalent aliphatic alkyl that means carbonatoms 1～12,

P ¹mean polymerizable group,

P ²mean hydrogen atom or polymerizable group,

R ¹, R ⁴and R ⁵mean the meaning same as described above.

6. an optical thin film, the polymerizable liquid crystal compound polymerization comprised in the composition of its record of any one by claim 1～5 forms.

7. the manufacture method of an optical thin film, comprise following (1) and (2),

(1) composition of any one of claim 1～5 record is coated on to the operation on base material;

8. the manufacture method of the optical thin film of putting down in writing according to claim 7, wherein, base material consists of the material with hydroxyl.

9. the manufacture method of the optical thin film of putting down in writing according to Claim 8, wherein, the material with hydroxyl is the material that the triacetyl cellulose saponification is obtained.

10. the manufacture method of the optical thin film of putting down in writing according to any one of claim 7～9, wherein, be provided with the alignment films by light orientation polymer formation on the surface of base material.

11. the manufacture method of the optical thin film of putting down in writing according to claim 10, wherein, alignment films has formed crosslinking structure setting by light orientation polymkeric substance through rayed.

12. an optical thin film, the manufacture method of its record of any one by claim 7～11 makes.

13., according to the optical thin film of claim 6 or 12 records, it has phase differential.

14. a Polarizer, the optical thin film that it contains claim 6,12 or 13 records.

15. a panel display apparatus, it possesses the optical thin film of claim 6,12 or 13 records.

16. a composition, it contains following (D) and (B),

(D) light orientation polymkeric substance

(B) there is the compound of carbon-to-carbon unsaturated bond and reactive with active hydrogen group in molecule.

17., according to the composition of claim 16 record, wherein, be (D) can form the light orientation polymkeric substance of crosslinking structure by rayed.

18., according to the composition of claim 16 or 17 records, wherein, be (B) to there is the compound of isocyanato as the reactive with active hydrogen group.

19. the composition according to claim 16 or 17 records, wherein, (B) be the represented compound of following formula (X),

In formula (X),

20. an optical thin film, the light orientation crosslinked polymer comprised in the composition of its record of any one by claim 16～19 forms.

21. the manufacture method of an optical thin film, comprise following (1) and (2),

(1) composition of any one of claim 16～19 record is coated on to the operation on base material;

22. the manufacture method of the optical thin film of putting down in writing according to claim 21, wherein, base material consists of the material with hydroxyl.

23. the manufacture method of the optical thin film of putting down in writing according to claim 22, wherein, the material with hydroxyl is the material that the triacetyl cellulose saponification obtains.

24. an optical thin film, the manufacture method of its record of any one by claim 21～23 makes.

25. a polarizer, it is further to form optical anisotropic layer to form on the optical thin film of claim 20 or 24 records.

26. a Polarizer, the optical thin film that it contains claim 20 or 24 records.

27. a panel display apparatus, it possesses the optical thin film of claim 20 or 24 records.

28. an optical thin film, its sequential lamination according to base material, the A layer that formed by composition (A) and the B layer that formed by composition (B) forms, wherein,

Composition (A) contains following (D) and reaches (B-1), and composition (B) contains following (A), (B-2) reaches (C),

(D) light orientation polymkeric substance

(A) polymerizable liquid crystal compound

(C) photo-induced polymerization initiator.

29., according to the optical thin film of claim 28 record, wherein, be (D) can form the light orientation polymkeric substance of crosslinking structure by rayed.

30., according to the optical thin film of claim 28 or 29 records, wherein, (B-1) reaching (B-2) is all the compound had as the isocyanato of reactive with active hydrogen group.

31. according to the optical thin film of claim 28 or 29 records, wherein, (B-1) reaching (B-2) is the represented compound of following formula (X) respectively independently,

In formula (X),

R ³' among at least 1 R ³' be the group with carbon-to-carbon unsaturated bond.

32. the optical thin film of putting down in writing according to any one of claim 28～31, wherein, the A layer contains the layer that (D) is cross-linked to form in composition (A).

33. the optical thin film of putting down in writing according to any one of claim 28～32, wherein, base material consists of the material with hydroxyl.

34., according to the optical thin film of claim 33 record, wherein, the material with hydroxyl is the material obtained by the triacetyl cellulose saponification.

35. the optical thin film of putting down in writing according to any one of claim 28～34, it has phase differential.

36. the manufacture method of an optical thin film, it comprises following<1 >～<4 operation,

(D) light orientation polymkeric substance

(A) polymerizable liquid crystal compound

(C) photo-induced polymerization initiator

37. an optical thin film, its manufacture method by claim 36 record makes.

38. a Polarizer, the optical thin film of any one that it contains claim 28～35 or claim 37 record.

39. a panel display apparatus, it possesses any one of claim 28～35 or the optical thin film of claim 37 record.