CN108369358A - Liquid crystal orientation film manufacture composition indicates element and its manufacturing method using the liquid crystal orientation film of the composition and its manufacturing method and the liquid crystal with liquid crystal orientation film - Google Patents

Liquid crystal orientation film manufacture composition indicates element and its manufacturing method using the liquid crystal orientation film of the composition and its manufacturing method and the liquid crystal with liquid crystal orientation film Download PDF

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CN108369358A
CN108369358A CN201680071493.5A CN201680071493A CN108369358A CN 108369358 A CN108369358 A CN 108369358A CN 201680071493 A CN201680071493 A CN 201680071493A CN 108369358 A CN108369358 A CN 108369358A
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liquid crystal
group
carbon number
side chain
formula
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CN108369358B (en
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原田佳和
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Abstract

The present invention provides：Expand the range for stablizing the light irradiation amount for generating tropism control ability, energy efficiency obtains the liquid crystal orientation film manufacture composition of the good liquid crystal orientation film of quality well.The present invention provides a kind of liquid crystal orientation film manufacture composition, which is characterized in that contains：(A) side chain type macromolecule, has following side chain, and the side chain shows liquid crystal liquid crystal property and within the specified temperature range with the photoreactive group that photo-crosslinking, photoisomerization or light fries' rearrangement occurs；(B) organic solvent；(C) additive, the minimum triplet energies of (C) additive are less than the minimum triplet energies of the compound from photoreactive group.

Description

Liquid crystal orientation film manufacture composition uses the liquid crystal orientation film of the composition and its Manufacturing method and the liquid crystal expression element with liquid crystal orientation film and its manufacture Method
Technical field
The present invention relates to liquid crystal orientation film manufacture compositions, particularly the driving liquid crystal of transverse electric field to indicate element liquid Brilliant alignment films manufacture composition.
Moreover, it relates to use the liquid crystal orientation film, particularly the driving liquid crystal of transverse electric field of the composition manufacture Indicate element liquid crystal orientation film and the substrate with the film and its manufacturing method.
In turn, the present invention relates to the liquid crystal with the liquid crystal orientation film or substrate to indicate element and its manufacturing method.
Especially the present invention relates to expand light irradiation amount in optical alignment method used in the orientation process in liquid crystal orientation film The liquid crystal orientation film manufacture composition, particularly the driving liquid of transverse electric field of range, the manufacture efficiency of raising liquid crystal orientation film Crystalline substance indicates that element is manufactured with composition, the liquid crystal orientation film manufactured using the composition with liquid crystal orientation film or has liquid crystal aligning The substrate of film indicates that element and liquid crystal orientation film, the substrate with liquid crystal orientation film or liquid crystal are indicated with their liquid crystal The manufacturing method of element.
Background technology
It is known that liquid crystal, which indicates element as light weight, slim and expression device low power consumption, is used for large size in recent years Television applications etc. realize significant development.Liquid crystal indicates that element is, for example, to be clamped using a pair of of the transparent substrate for having electrode Liquid crystal layer and constitute.Also, liquid crystal indicate element in, by the organic film that organic material is formed be used as liquid crystal orientation film with So that liquid crystal is presented between the substrates and it is expected state of orientation.
That is, liquid crystal orientation film be liquid crystal indicate element member of formation, be formed in clamping liquid crystal substrate and liquid crystal The surface of contact, undertaking makes liquid crystal be orientated this effect along specific direction between the substrate.Also, for liquid crystal orientation film For, other than so that liquid crystal is orientated this effect along specific directions such as the directions for being for example parallel to substrate, also require sometimes Liquid crystal pretilt angle is carried out to control this effect.The ability of the control liquid crystal aligning of this liquid crystal orientation film (is hereinafter referred to as orientated Control ability.) be endowed by carrying out orientation process to the organic film for constituting liquid crystal orientation film.
As the method for orientation treatment of the liquid crystal orientation film for assigning tropism control ability, in addition to brushing all the time Except method, it is also known that have optical alignment method.Optical alignment method has the following advantages that：Compared with previous brushing method, brushing is not needed, no There are dust, the worries of generation electrostatic, and there is concave-convex liquid crystal for surface indicates that the substrate of element can also implement orientation position Reason.
Optical alignment method has various methods, and the organic of liquid crystal orientation film is being constituted by rectilinearly polarized light or collimated light Anisotropy is formed in film, so that liquid crystal is orientated according to the anisotropy.
As optical alignment method, it is known to the optical alignment method of breakdown type, the optical alignment method etc. of photo-crosslinking type, photoisomerization type.
The optical alignment method of breakdown type is：For example, irradiating polarized UV rays to polyimide film, the ultraviolet of molecular structure is utilized The polarization direction dependence of line absorption and bring it about anisotropic decomposition, make liquid using undecomposed and remaining polyimides The method that crystalline substance is orientated (referring for example to patent document 1).
Photo-crosslinking type, photoisomerization type optical alignment method be：For example, using poly- vinyl cinnamate, polarized UV is irradiated Line, make 2 side chains parallel with polarised light double bond part occur dimerization reaction (cross-linking reaction), make liquid crystal along with polarization side The method being orientated to vertical direction (referring for example to non-patent literature 1).In addition, using the side in side chain with azobenzene When chain macromolecule, polarized UV rays are irradiated, makes the azobenzene part of the side chain parallel with polarised light that isomerization reaction occur, makes Liquid crystal is orientated along the direction vertical with polarization direction (referring for example to non-patent literature 2).In turn, 3 disclosure of patent document The liquid crystal orientation film obtained using optical alignment method based on photo-crosslinking, photoisomerization or light fries' rearrangement.
Existing technical literature
Patent document
Patent document 1：No. 3893659 bulletins of Japanese Patent No.
Patent document 2：Japanese Unexamined Patent Publication 2-37324 bulletins
Patent document 3：WO2014/054785
Non-patent literature
Non-patent literature 1：M.Shadt et al.,Jpn.J.Appl.Phys.31,2155(1992).
Non-patent literature 2：K.Ichimura et al.,Chem.Rev.100,1847(2000).
Invention content
Problems to be solved by the invention
As previously discussed, with method for orientation treatment that element is indicated as liquid crystal and the brush that industrially utilizes all the time Mill method is compared, and optical alignment method is not necessarily to brushing process itself, therefore has clear advantage.Also, it is orientated with caused by brushing The substantially stationary brushing method of control ability is compared, and optical alignment method can change the exposure of polarised light to control tropism control energy Power.
However, when the tropism control ability of the principal component used in optical alignment method is excessively sensitive to the exposure of polarised light, In the part or entirety of liquid crystal orientation film, orientation becomes incomplete, cannot achieve stable liquid crystal aligning sometimes.
Then, the object of the present invention is to provide expand the range for stablizing the light irradiation amount for generating tropism control ability, energy Efficiency obtain well the good liquid crystal orientation film of quality, liquid crystal orientation film manufacture composition, particularly transverse electric field driving Type liquid crystal indicates that element is manufactured with liquid crystal orientation film and uses composition.
In addition, the purpose of the present invention also resides in other than above-mentioned purpose or on the basis of above-mentioned purpose, use is provided The liquid crystal orientation film or substrate with liquid crystal orientation film of the composition manufacture, indicated with their liquid crystal element, particularly The driving liquid crystal of transverse electric field indicates element.
In turn, the purpose of the present invention also resides in other than above-mentioned purpose or on the basis of above-mentioned purpose, provides liquid crystal Alignment films, the substrate with liquid crystal orientation film or liquid crystal indicate that element, particularly the driving liquid crystal of transverse electric field indicate element Manufacturing method.
The solution to the problem
The inventors of the present invention are found that invention below.
A kind of liquid crystal orientation film manufacture compositions of 1 ＞ of ＜, particularly the driving liquid crystal of transverse electric field indicate element Liquid crystal orientation film manufacture composition, which is characterized in that contain：
(A) side chain type macromolecule, has following side chain, and the side chain shows liquid crystal liquid crystal property within the specified temperature range And with the photoreactive group that photo-crosslinking, photoisomerization or light fries' rearrangement occurs；
(B) organic solvent；With
(C) additive,
(C) the minimum triplet energies of additive are less than the minimum triplet energy of the compound from photoreactive group Amount.
The effect of invention
In accordance with the invention it is possible to which it is good to provide the range for expanding the light irradiation amount for stablizing generation tropism control ability, energy efficiency The good liquid crystal orientation film of quality, liquid crystal orientation film manufacture composition, particularly the driving liquid crystal of transverse electric field are obtained well It indicates that element is manufactured with liquid crystal orientation film and uses composition.
In addition, according to the present invention, in addition to the above-described effects or on the basis of the above effect, it is capable of providing and uses the group Close the liquid crystal orientation film of object manufacture or the substrate with liquid crystal orientation film, liquid crystal expression element, particularly transverse direction with them Electric field drive liquid crystal indicates element.
In turn, according to the present invention, in addition to the above-described effects or on the basis of the above effect, it is capable of providing liquid crystal aligning Film, the substrate with liquid crystal orientation film or liquid crystal indicate that element, particularly the driving liquid crystal of transverse electric field indicate the manufacture of element Method.
Specific implementation mode
The application provides：Liquid crystal orientation film manufacture composition, particularly the driving liquid crystal of transverse electric field indicate that element is used Expand light in the optical alignment method used in the orientation process of liquid crystal orientation film manufacture composition and then especially liquid crystal orientation film The composition of exposure range, the manufacture efficiency of raising liquid crystal orientation film.
In addition, the application provides：The liquid crystal orientation film, particularly the driving liquid crystal of transverse electric field manufactured using the composition Indicate element liquid crystal orientation film and with the substrate of the film and its manufacturing method.
In turn, the application provides the liquid crystal with the liquid crystal orientation film or substrate and indicates element and its manufacturing method.
＜ liquid crystal orientation films manufacture composition ＞
The driving liquid crystal of liquid crystal orientation film manufacture composition, particularly transverse electric field of the application indicates element liquid crystal Alignment films manufacture composition contains：
(A) side chain type macromolecule, has following side chain, and the side chain shows liquid crystal liquid crystal property within the specified temperature range And with the photoreactive group that photo-crosslinking, photoisomerization or light fries' rearrangement occurs；
(B) organic solvent；With
(C) additive.
Herein, (C) additive is characterized in that, minimum triplet energies are less than the compound from photoreactive group Minimum triplet energies.
Using the composition of the application, thus the light used in the orientation process of the liquid crystal orientation film obtained by the composition In alignment method, light irradiation amount range can be expanded, improve the manufacture efficiency of liquid crystal orientation film.
＜ ＜ (A) side chain type macromolecule ＞ ＞
(A) side chain type macromolecule is the side chain type high score for having the side chain for showing liquid crystal liquid crystal property within the specified temperature range Son.In addition, the side chain has the photoreactive group that photo-crosslinking, photoisomerization or light fries' rearrangement occurs.
(A) side chain type macromolecule is reacted using the light of the wave-length coverage of 250nm~400nm, and 100 DEG C~ It is preferable that 300 DEG C of temperature range, which shows liquid crystal liquid crystal property,.
(A) side chain type macromolecule preferably reacts to the light of the wave-length coverage of 250nm~400nm.
(A) side chain type macromolecule is in order to show liquid crystal liquid crystal property in 100 DEG C~300 DEG C of temperature range and it is preferred that have mesomorphic Group.
(A) side chain type macromolecule is bonded with the side chain with photoreactive group on main chain, can incude light and occur Cross-linking reaction, isomerization reaction or light fries' rearrangement.The structure of side chain with photoreactive group is not particularly limited, It is ideal to incude light and crosslink the structure of reaction or light fries' rearrangement, and it is more preferably to crosslink reaction.At this point, It, also being capable of the realized tropism control ability of long-time stable holding if exposed to external stresses such as heat.It can show liquid crystal Property the high molecular structure of side chain type be not particularly limited as long as meeting this characteristic, preferably in side-chain structure have it is upright and outspoken Mesomorphic ingredient.At this point, when liquid crystal orientation film is made in the side chain type macromolecule, stable liquid crystal aligning can be obtained.
The high molecular structure can for example take following structure：With main chain and the side chain for being bonded to it, the side chain With mesomorphics ingredients such as xenyl, terphenyl, phenylcyclohexyl, phenylamino benzoic acid ester group, azobenzenes and it is bonded to front end Portion, induction light and carry out cross-linking reaction, the photoreactive group of isomerization reaction；With main chain and the side chain for being bonded to it, The side chain has also as mesomorphic ingredient and the phenylamino benzoic acid ester group of progress light Fries rearrangement.
More specific example as the high molecular structure of side chain type with photoreactive group that is can showing liquid crystal liquid crystal property Son, it is however preferred to have with selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, alpha-methylene- What the radically polymerizable group group of gamma-butyrolacton, styrene, vinyl, maleimide, norbornene etc. and siloxanes formed The structure of the main chain that at least one of group is constituted and the side chain comprising at least one formation by following formula (1)~(6).
In formula, A, B, D each independently represent singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH =CH-CO-O- or-O-CO-CH=CH-；
S is the alkylidene of carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
T is the alkylidene of singly-bound or carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
Y1In the ester ring type hydrocarbon for indicating phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 Ring, or be group made of 2~6 identical or different rings selected from these substituent groups are bonded by linking group B, bonding In their hydrogen atom each independently optionally by-COOR0(in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5) ,-NO2、- CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy substitution；
Y2For selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 ester ring type hydrocarbon and it Group in the group that is combined into of group, be bonded to their hydrogen atom each independently optionally by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy substitution；
R indicates the alkoxy of hydroxyl, carbon number 1~6, or expression and Y1Identical definition；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH When the quantity of=CH-, X become 2, X is optionally same or different to each other；
Cou indicates Coumarin-6-base or coumarin-7-base, be bonded to their hydrogen atom each independently optionally by- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy take Generation；
One is 1 in q1 and q2 and another one is 0；
Q3 is 0 or 1；
P and Q is each independently selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 Group in ester ring type hydrocarbon and the group of combination thereof composition；Wherein, X is the feelings of-CH=CH-CO-O- ,-O-CO-CH=CH- Under condition, the P or Q of the side that-CH=CH- is bonded are aromatic rings, and when the quantity of P becomes 2 or more, P is optionally mutually the same or not Together, when the quantity of Q becomes 2 or more, Q is optionally same or different to each other；
L1 is 0 or 1；
The integer that l2 is 0~2；
When l1 and l2 are 0, A also illustrates that singly-bound when T is singly-bound；
When l1 is 1, B also illustrates that singly-bound when T is singly-bound；
H and I is each independently in the phenyl ring selected from divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and combination thereof Group.
It is preferable that side chain, which is selected from any one of the group being made of following formula (7)~(10),.
In formula, A, B, D, Y1、X、Y2There is definition same as described above with R；
L indicates 1~12 integer；
M indicates that 0~2 integer, m1, m2 indicate 1~3 integer；
N indicates 0~12 integer (wherein, B is singly-bound when n=0).
It is preferable that side chain, which is selected from any one of the group being made of following formula (11)~(13),.
In formula, A, X, l, m, m2 and R have definition same as described above.
Side chain is that side chain shown in following formula (14) or (15) is preferable.
In formula, A, Y1, X, l, m1 and m2 have definition same as described above.
Side chain is that side chain shown in following formula (16) or (17) is preferable.
In formula, A, X, l and m have definition same as described above.
＜ ＜ have the side chain type macromolecule ＞ ＞ of liquid crystal liquid crystal property side chain
(A) side chain type macromolecule can have the side chain in addition to the side chain with photoreactive group.For example, the side (A) Chain macromolecule can have wantonly a kind of the liquid crystal liquid crystal property side chain in the group being made of following formula (21)~(31).
In formula, A, B, q1 and q2 have definition same as described above；
Y3For selected from the ester ring type hydrocarbon by the phenyl ring of monovalence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring and carbon number 5~8 And the group in the group of combination thereof composition, their hydrogen atom is bonded to each independently optionally by-NO2,-CN, halogen The alkoxy of plain group, the alkyl of carbon number 1~5 or carbon number 1~5 replaces；
R3Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the phenyl ring of monovalence, naphthalene nucleus, The ester ring type hydrocarbon of cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring, carbon number 5~8, the alkyl of carbon number 1~12 or the alcoxyl of carbon number 1~12 Base；
L indicates that 1~12 integer, m indicate 0 to 2 integer, wherein in formula (25)~(26), the summation of whole m be 2 with On, in formula (27)~(28), the summation of whole m is 1 or more, and m1, m2 and m3 each independently represent 1~3 integer；
R2Indicate hydrogen atom ,-NO2,-CN, halogen group, the phenyl ring of monovalence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring With the ester ring type hydrocarbon and alkyl or alkoxy of carbon number 5~8；
Z1、Z2Indicate singly-bound ,-CO- ,-CH2O- ,-CH=N- ,-CF2-。
The high molecular preparation method ＞ ＞ of ＜ ＜ side chain types
Above-mentioned side chain type macromolecule can obtain as follows：It will be provided with the light reaction of the above-mentioned side chain with photoreactive group Property side chain monomer is polymerize, or the photoreactivity side chain monomer is gathered with other monomers, such as liquid crystal liquid crystal property side chain monomer It closes, so as to obtain.
[photoreactivity side chain monomer]
Photoreactivity side chain monomer refers to that can be formed in high molecular side chain position when forming macromolecule to have light anti- The high molecular monomer of the side chain of answering property group.
As photoreactive group possessed by side chain, preferably following structures and its derivative.
More specific example as photoreactivity side chain monomer, it is however preferred to have following polymerizable group and side chain Structure, that is, the polymerizable group is used selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, α- The radically polymerizable group of methylene-y-butyrolactone, styrene, vinyl, maleimide, norbornene etc. is rolled into a ball and silica At least one of the group of alkane composition is constituted, and the side chain is the side chain formed by least one of above-mentioned formula (1)~(6), excellent It is selected as example by the side chain of above-mentioned formula (7)~(10) at least one formation, by above-mentioned formula (11)~(13) at least one formation Side chain shown in side chain, above-mentioned formula (16) or (17) shown in side chain, above-mentioned formula (14) or (15).
[liquid crystal liquid crystal property side chain monomer]
Liquid crystal liquid crystal property side chain monomer refers to that the high molecular form from the monomer reveals liquid crystal liquid crystal property, the macromolecule at side chain position The monomer of mesomorphic group can be formed.
Can be the base separately as mesomorphic structure such as biphenyl, phenol benzoate as mesomorphic group possessed by side chain , can also be that the side chain as benzoic acid etc. forms hydrogen bond and as the group of mesomorphic structure each other.As with side chain Mesomorphic group, preferably following structures.
More specific example as liquid crystal liquid crystal property side chain monomer, it is however preferred to have with selected from by hydrocarbon, (methyl) acrylate, Itaconate, fumarate, maleate, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norborneol The radically polymerizable group of alkene etc. is rolled into a ball with the polymerizable group of at least one of group of siloxanes composition composition and by above-mentioned The structure of the side chain of at least one formation of formula (21)~(31).
In the application, as photoreactivity and/or liquid crystal liquid crystal property side chain monomer, formula below (A01)~(A20) can be enumerated Compound represented, but it is not limited to them.
In formula, R indicates hydrogen atom or methyl；S indicates the alkylidene of carbon number 2~10；R10Indicate Br or CN；S indicates carbon number 2 ~10 alkylidene；U indicates 0 or 1；And Py indicates 2- pyridyl groups, 3- pyridyl groups or 4- pyridyl groups.In addition, v indicates 1 or 2.
(A) side chain type macromolecule can be by having the photoreactivity side chain list of the above-mentioned side chain with photoreactive group The polymerisation of body and obtain.Furthermore it is possible to photoreactivity side chain monomer and liquid crystal liquid crystal property side chain list by not showing liquid crystal liquid crystal property The copolymerization of body, the copolymerization of the photoreactivity side chain monomer for showing liquid crystal liquid crystal property and liquid crystal liquid crystal property side chain monomer and obtain.
It can also be copolymerized with other monomers in the range of not damaging the expressive ability of liquid crystal liquid crystal property.
As other monomers, such as the industrial retrievable monomer that can carry out Raolical polymerizable can be enumerated.
As the concrete example of other monomers, unsaturated carboxylic acid, acrylate compounds, methacrylated can be enumerated Close object, maleimide compound, acrylonitrile, maleic anhydride, distyryl compound and vinyl compound etc..
As the concrete example of unsaturated carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid can be enumerated Deng.
As acrylate compounds, such as the object described in [0152] of WO2014/054785 bulletins can be enumerated Matter.
As methacrylate compound, such as can enumerate described in [0153] of WO2014/054785 bulletins Substance.
As vinyl compound, distyryl compound or maleimide compound, such as WO2014/ can be enumerated Substance described in [0154] of No. 054785 bulletin.
The high molecular manufacturing method of side chain type about present embodiment, is not particularly limited, and can utilize industrial place The universal method of reason.Specifically, liquid crystal liquid crystal property side chain monomer, the sun using vinyl of photoreactivity side chain monomer can be passed through Ionic polymerization, free radical polymerization, anionic polymerisation and manufacture.Among them, from the viewpoints spy such as easness of reaction controlling Not preferred free radical polymerization.
As the polymerization initiator of free radical polymerization, radical polymerization initiator, reversible addition-fracture chain can be used to turn Move compound well known to (RAFT) polymerization agent etc..
Free radical thermal polymerization is the compound that is generated free radicals by being heated to decomposition temperature or more.As this Kind free radical thermal polymerization, such as the substance described in [0157] of WO2014/054785 bulletins can be enumerated.It is this Free radical thermal polymerization can be used alone, or two or more can also be applied in combination.
Radical photopolymerization initiator causes as long as irradiated by light by as long as the compound of free radical polymerization without special It limits.As this radical photopolymerization initiator, the object described in [0158] of WO2014/054785 bulletins can be enumerated Matter.These compounds can be used alone, and can also be mixed with two or more.
Radical polymerization is not particularly limited, and can use emulsion polymerization, suspension polymerization, dispersion copolymerization method, sink Shallow lake polymerization, mass polymerization, solution polymerization process etc..
As the organic solvent for obtaining using in the high molecular polymerisation of side chain type, as long as the height that dissolving is generated Molecule is just not particularly limited.As its concrete example, the object described in [0161] of WO2014/054785 bulletins can be enumerated Matter.
These organic solvents can be used alone, and can also be used in mixed way.In turn, even insoluble generated high score The solvent of son, as long as in the range of the macromolecule generated will not be precipitated, then can also mix into above-mentioned organic solvent makes With.
In addition, in free radical polymerization, the oxygen in organic solvent can become the reason of hindering polymerisation, therefore organic molten Agent uses after preferably deaerating as much as possible.
Polymerization temperature when free radical polymerization can select 30 DEG C~150 DEG C of arbitrary temp, preferably 50 DEG C~100 DEG C Range.In addition, reaction can be carried out with any concentration, but when concentration is too low, is difficult to obtain the polymer of high molecular weight, concentration When excessively high, the viscosity of reaction solution becomes excessively high and is difficult to equably stir, therefore monomer concentration is preferably 1 matter of mass %~50 Measure %, more preferably 5 mass of mass %~30 %.It can be carried out with high concentration in initial reaction stage, add organic solvent thereafter.
In above-mentioned Raolical polymerizable, when the ratio of radical polymerization initiator is more relative to monomer, gained is high The molecular weight of molecule becomes smaller, when the ratio of radical polymerization initiator is less relative to monomer, the high molecular molecule quantitative change of gained Greatly, therefore the ratio of radical initiator relative to the monomer to be polymerize is preferably 0.1 mole of %~10 mole %.In addition, poly- Various monomer components, solvent, initiator etc. can also be added when conjunction.
[recycling of polymer]
From by it is above-mentioned it is obtained by the reaction, generated macromolecule is recycled in the high molecular reaction solution of side chain type when, will Reaction solution is put into poor solvent, these polymer is made to precipitate.As the poor solvent for precipitation, first can be enumerated Alcohol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methylisobutylketone, ethyl alcohol, toluene, benzene, diethyl ether, first and second Ether, water etc..The polymer precipitated into poor solvent is put into can under normal or reduced pressure to carry out after being recovered by filtration Air drying or heat drying.In addition, repeating the polymer that 2 times~10 times make precipitation recycle is re-dissolved in organic solvent simultaneously When the operation of reprecipitation recycling, the impurity in polymer can be reduced.As poor solvent at this time, such as alcohol can be enumerated Class, ketone, hydrocarbon etc., when using 3 kinds or more poor solvents among these, purification efficiency further increases, so it is preferred that.
About the high molecular molecular weight of (A) side chain type of the present invention, when considering obtained coating strength, film formation Operability and film uniformity in the case of, pass through GPC (gel permeation chromatographies；Gel Permeation Chromatography) weight average molecular weight that method measures is preferably 2000~1000000, more preferably 5000~200000.
[preparation of composition]
The mode that the composition used in the present invention is preferably suitable for being formed liquid crystal orientation film is prepared into coating fluid.That is, this The resin component that the composition used in invention is preferably prepared to be used to form resin coating is dissolved in obtained from organic solvent Solution.Herein, which refers to being described above comprising the high molecular resin component of side chain type.At this point, resin component Content be preferably 1 mass of mass %~20 %, more preferably 3 mass of mass %~15 %, particularly preferably 3 mass %~10 Quality %.
In the composition of present embodiment, resin component above-mentioned can be with all above-mentioned side chain type macromolecules, can also Other polymer in addition are mixed in the range of not damaging liquid crystal expressive ability and photosensitive property.At this point, resin The content of other polymer in ingredient is 0.5 mass of mass %~80 %, preferably 1 mass of mass %~50 %.
This other polymer can for example be enumerated by poly- (methyl) acrylate, polyamic acid, polyimides, polyamide Acid esters, polyureas, the polyamide as obtained from diisocyanate cpd is made to polymerize with tetracarboxylic acid derivatives, diamine compound Polyimides-polyureas etc. obtained from acid-polyureas, further imidizate forms and is not that above-mentioned side chain type is high molecular Polymer etc..
＜ ＜ (B) organic solvent ＞ ＞
The organic solvent that uses as long as the organic solvent of dissolving resin ingredient as long as can not have in the composition of the present invention It is particularly limited to.It is exemplified below out its concrete example.
It can enumerate：N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- methyl oneself Lactams, 2-Pyrrolidone, N- ethyl pyrrolidones, n-vinyl pyrrolidone, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, two Methyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3- methoxyl groups-N, N- dimethylpropionamide, 3- ethyoxyls-N, N- dimethyl propionyl Amine, 3- butoxy-N, N- dimethylpropionamide, 1,3- dimethyl-imidazolinones, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, Methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4- hydroxyls- 4-methyl-2 pentanone, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethyl two Alcohol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropyl 2-ethoxyethanol, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- first Base -3- methoxybutyls acetic acid esters, tripropylene glycol methyl ether etc..They can be used alone, and can also be used in mixed way.
＜ ＜ (C) additive ＞ ＞
The composition of the application has (C) additive, is somebody's turn to do (C) additive and is characterized in that minimum triplet energies are low The minimum triplet energies of the compound for the photoreactive group having on from the high molecular side chain of side chain type.
(C) by using (C) additive with the above characteristics, i.e. with specific minimum triplet energies is added Agent in the optical alignment method used in the orientation process of the liquid crystal orientation film obtained by the composition, can expand light irradiation amount model It encloses, improves the manufacture efficiency of liquid crystal orientation film.
Herein, triplet energies refer to being excited by the molecule of the energy of light, the molecule for becoming triplet state is had Energy.In particular, lowest excited triplet (T1) and the energy difference of the molecule in ground state are known as minimum triplet Energy.
In addition, triplet refers to, for molecule by the energy of light and in the case of becoming excited state, 2 tracks respectively have 1 A unpaired electron spins 2 at this point, the identical state of the spin direction of 2 unpaired electrons is known as triplet state Direction be opposite state be known as a heavy state state.In general, the energy of triplet state is less than a corresponding heavy state shape State, but the long lifespan of excited triplet state, therefore, the chance of reaction is more, has distinctive light reaction and is mostly based on excited triplet state And it generates.
In general, lowest excited state (be then S1 if it is a heavy state state, be then T1 if it is triplet state) The short life of high excited state in addition, is reduced to rapidly S1, T1.Therefore, even with the high light of the energy of short wavelength, excitation For S2, S3, shine, reaction also occurs under S1, T1 as lowest excited state mostly.
Minimum triplet energies can measure as follows.
As the premise of measurement, the molecule in excited triplet state is chosen and is sent out in addition to various light reactions occur sometimes Phosphorescence restores to the radial migration process of one heavy state state of substrate.Herein, if measured by minimum triple with spectrophotometer etc. The phosphorescence that state excited state is sent out can then speculate minimum triplet energies.
That is, minimum triplet energies can be calculated according to the phosphorescence spectrum being measured to.Phosphorescence spectrum can use commercially available Spectrophotometer and measure.
The assay method of general phosphorescence spectrum has：It will be dissolved in solvent as the compound of object, irradiated at low temperature Exciting light and method for measuring (it is kind to compile ball) referring for example to the 4th edition experimental chemistry lecture 7p384-398 (1992) Japanization association； Alternatively, vapor deposition forms film as the compound of object on a silicon substrate, irradiation at low temperature excites light measurement phosphorescence spectrum Method etc. (referring for example to Japanese Unexamined Patent Publication 2007-022986 bulletins).
Excited triplet state energy level can calculate as follows：Read the wavelength or short at the 1st peak of the short wavelength side of phosphorescence spectrum The wavelength for the position that wavelength side rises is scaled the energy value of every 1 mole of light, so as to calculate according to following formula.It needs Illustrate, in following numerical expressions (E1), NAIndicate that Avgadro constant, E indicate that the value of minimum triplet energies, h indicate general Bright gram of constant (6.63 × 10-34Js), c indicates the light velocity (3.00 × 108M/s), λ indicates what the short wavelength side of phosphorescence spectrum rose The wavelength (nm) of position.
E (kJ/mol)=NA×(hc/λ) (E1)
For example, the high molecular side chain of (A) side chain type have formula below (A-1) (in formula, Y2Have with R same as described above Definition.* group shown in expression (A-1) be the high molecular side chain of side chain type a part, * place connection) shown in base Group when, be originated from photoreactive group compound be formula (A-2) (in formula, Y2There is definition same as described above with R) shown in The minimum triplet energies of compound, (C) additive are preferable less than the minimum triplet energies of formula (A-2) compound represented.
In addition, the high molecular side chain of (A) side chain type have formula below (A-3) (in formula, Y1Determine with same as described above Justice.* group shown in expression (A-3) be the high molecular side chain of side chain type a part, * place connection) shown in group when, Compound from photoreactive group be formula (A-4) (in formula, Y1With definition same as described above) compound represented, (C) the minimum triplet energies of additive are preferable less than the minimum triplet energies of formula (A-4) compound represented.
For example, group shown in formula (A-1) is shown in group, formula (A-2) shown in following formula (A-1-1) The case where compound is following formula (A-2-1) compound represented；
Group shown in formula (A-1) is group shown in following formula (A-1-2), formula (A-2) compound represented is following The case where formula (A-2-2) compound represented etc., but it is not limited to these.It should be noted that * determines with same as described above Justice.
In addition, for example, group shown in formula (A-3) be group shown in following formula (A-3-1), formula (A-4) institute The case where compound shown is following formula (A-4-1) compound represented etc., but it is not limited to these.It should be noted that * has There is definition same as described above.
In addition, at this point, as (C) additive, following formula (C-1)~(C-27) compound represented can be enumerated, but not It is defined in these.
In the present invention, it is believed that (C) additive plays a role as delustering agent.Below, by way of example, to (A) side chain type height Molecule has in the case that group is as photoreactive group shown in formula (A-1) or (A-3), specifically, to Chinese cassia tree The case where acid groups, accounts for.
In the case of being not added with (C) additive, when being used for the light of tropism control to the irradiation of (A) side chain type macromolecule, make (A) Photoreactive group, that is, cinnamate group excitation in side chain type macromolecule, (A) side chain type macromolecule send out irradiation photaesthesia Raw reaction.
On the other hand, the additive lower than the excited triplet state energy of cinnamic acid is imported, in (A) side chain type macromolecule Cinnamate group in excited state energy to play a role as delustering agent additive movement, inactivation and delustring.Cause This, the high molecular light reaction rate of (A) side chain type with photoreactive group, that is, cinnamate group reduces, to irradiation light or illumination The sensitivity decrease for the amount of penetrating, so as to expand the range for the light irradiation amount for steadily generating tropism control ability.
Above-mentioned effect is not limited to (A) the side chain type macromolecule with cinnamate group, with other photoreactivity bases It rolls into a ball, (A) side chain type macromolecule of the photoreactive group such as chalcone skeleton, coumarin skeleton, Stilbene skeleton, azo benzene skeleton In similarly generate.
Hereinafter, being illustrated for the photoreactive group other than the photoreactive group comprising cinnamate group.
(C) additive can contain one kind or two or more in the composition.
At this point, 100 mass of the content of (C) additive in composition relative to the resin component contained in composition Part, can be the mass parts of 0.01 mass parts~200, the mass parts of preferably 0.05 mass parts~100.
In addition, for (C) additive, if (C) additive used is liquid, (B) organic solvent can be used as to make With.At this point, when obtaining film by using the heating of baking oven etc., major part is evaporated and is disappeared.When considering the disappearance part, make When using (C) additive as (B) organic solvent, the content for being somebody's turn to do (C) additive can be 2 mass % of (B) organic solvent entirety ~80 mass %, preferably 5 mass of mass %~50 %.
The composition used in the present invention in addition to above-mentioned (A) side chain type macromolecule, (B) organic solvent and (C) additive, Other compositions can be contained.It is when can enumerate coating composition, flat for improving film thickness uniformity, surface as its example The solvent of slip, compound, the compound of adaptation etc. for improving liquid crystal orientation film and substrate, but not limited thereto.
As the concrete example of the solvent (poor solvent) for improving film thickness uniformity, surface smoothness, can enumerate Substance described in [0171] of WO2014/054785 bulletins.
These poor solvents can use a kind, can also be used in mixed way a variety of.When using solvent as described above, in order to Significantly reduce the dissolubility of the solvent for including in composition entirety, preferably 5 mass of mass %~80 % of solvent entirety, More preferably 20 mass of mass %~60 %.
As the compound for improving film thickness uniformity, surface smoothness, fluorine system surfactant, organic can be enumerated Silicon-based surfactant and nonionic surfactants etc..
More specifically, such as Eftop (registered trademark) 301, EF303, EF352 (Tohkem products can be enumerated Corporation systems), Megafac (registered trademark) F171, F173, R-30 (DIC CORPORATION systems), Fluorad FC430, FC431 (Sumitomo 3M Limited systems), AsahiGuard (registered trademark) AG710 (Asahi Glass Co., Ltds System), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC SEIMI CHEMICAL CO., LTD. system) etc..The use ratio of these surfactants is relative to the resin component contained in composition 100 mass parts are preferably the mass parts of 0.01 mass parts~2, the mass parts of more preferably 0.01 mass parts~1.
The concrete example of compound as the adaptation for improving liquid crystal orientation film and substrate, can enumerate WO2014/ The compound etc. containing functional silanes described in [0174] of No. 054785 bulletin.
In turn, in order to improve the adaptation of substrate and liquid crystal orientation film and prevent constitute liquid crystal indicate element when by backlight Caused electrical characteristics reduce etc., can contain phenoplasts system as following in the composition, contains epoxides add Add agent.Specific phenoplasts system additive described below, but it is not limited to the structure.
As specific contains epoxides, can enumerate described in [0177] of WO2014/054785 bulletins Substance.
Using for improve with the compound of the adaptation of substrate when, dosage relative to the resin contained in composition at Point 100 mass parts are preferably the mass parts of 0.1 mass parts~30, the mass parts of more preferably 1 mass parts~20.Dosage is less than 0.1 matter When measuring part, the effect for improving adaptation can not be expected, when being more than 30 mass parts, the orientation of liquid crystal is deteriorated sometimes.
In the composition of the application in addition to the foregoing, if within the scope of the effect of the invention, for The purpose for changing the electrical characteristics such as dielectric constant, the electric conductivity of liquid crystal orientation film, can add dielectric, conductive materials, and then go out In the hardness, the purpose of consistency that improve film when liquid crystal orientation film is made, cross-linked compound can be added.
＜ has the system of the substrate of liquid crystal orientation film using the liquid crystal orientation film of above-mentioned composition and its manufacturing method ＞, ＜ Make the manufacturing method ＞ that method ＞ and ＜ liquid crystal indicates element
Using liquid crystal orientation film and the WO2014/054785 of above-mentioned composition, (its content is used as to be contained in reference to whole In application) similarly, using based on can be obtained to using the film that the composition obtains to carry out the optical alignment method of polarisation irradiation It arrives.
Specifically, the substrate with liquid crystal orientation film can be obtained, can be assigned by with following process The liquid crystal orientation film, particularly the driving liquid crystal of transverse electric field for having given tropism control ability indicate element liquid crystal orientation film：
Above-mentioned composition is coated on the substrate of the conductive film with conductive film, particularly transverse electric field driving by [I] And the process for forming film；
The process that [II] irradiates the film obtained in [I] polarized UV rays；With
The process that [III] heats the film obtained in [II].
In addition, in addition to the substrate (the 1st substrate) obtained among the above, prepare the 2nd substrate, member is indicated to obtain liquid crystal Part, particularly the driving liquid crystal of transverse electric field indicate element.
2nd substrate uses the conductive film with conductive film, particularly transverse electric field driving in the same manner as the 1st substrate Substrate, using above-mentioned operation [I]~[III], so as to obtain with the liquid crystal orientation film for imparting tropism control ability 2nd substrate.
In addition, the 2nd substrate uses the substrate without the conductive film to replace driving with conductive film, particularly transverse electric field The substrate of conductive film, in addition to this, using above-mentioned operation [I]~[III] (due to the use of the substrate without conductive film, Therefore, for the sake of convenient, in the application, brief note makees process [I ']~[III '] sometimes), impart orientation so as to obtain having 2nd substrate of the liquid crystal orientation film of control ability.
Liquid crystal indicates that element, particularly the driving liquid crystal of transverse electric field indicate that the manufacturing method of element has following process：
[IV] is opposite with the liquid crystal orientation film of the 1st and the 2nd substrate across liquid crystal by the 1st and the 2nd substrate obtained among the above Mode carry out it is oppositely disposed and obtain liquid crystal indicate element process.
Thus, it is possible to which obtaining liquid crystal indicates that element, particularly the driving liquid crystal of transverse electric field indicate element.
Hereinafter, being illustrated to each process of [I] possessed by the manufacturing method of the present invention~[III] and [IV].
＜ processes [I] ＞
In process [I], above-mentioned group is coated on the substrate of the conductive film with conductive film, particularly transverse electric field driving It closes object and forms film.
＜ substrates ＞
Substrate is not particularly limited, manufactured liquid crystal indicates when element is transmission-type, it is preferable to use the transparency is high Substrate.At this point, being not particularly limited, the plastics base such as glass substrate or acrylic compounds substrate, polycarbonate substrate can be used Plate etc..
Additionally, it is contemplated that indicating the application of element to the liquid crystal of reflection-type, the opaque substrates such as silicon wafer can also be used.
＜ conductive films ＞
Substrate has conductive film, particularly the conductive film of transverse electric field driving.
As the conductive film ITO (Indium Tin Oxide can be enumerated when liquid crystal indicates that element is transmission-type：Oxidation Indium tin), IZO (Indium Zinc Oxide：Indium zinc oxide) etc., but it is not limited to them.
In addition, in the case that the liquid crystal of reflection-type indicates element, as conductive film, the material of the meeting reflected light such as aluminium can be enumerated Material etc., but it is not limited to them.
The method that conductive film is formed on substrate can make by a conventionally known method.
The method that above-mentioned composition is applied on the substrate with conductive film is not particularly limited.
About coating method, industrial is typically to utilize the progress such as silk-screen printing, hectographic printing, flexible printing or ink-jet method Method.As other coating methods, there are infusion process, rolling method, slot coated method, spin-coating method (method of spin coating) or spray coating method Deng, can according to purpose use they.
On the substrate with conductive film after coating composition, hot plate, thermal cycle type baking oven or IR (infrared ray) type are utilized The heating meanss such as baking oven make evaporation of the solvent with 50~200 DEG C, preferably with 50~150 DEG C, so as to obtain film.At this time dry Dry temperature is preferably shorter than the high molecular liquid crystalline phase performance temperature of side chain type.
It is unfavorable in terms of the power consumption that liquid crystal indicates element when the thickness of film is blocked up, when the thickness of film is excessively thin, liquid Crystalline substance indicates that the reliability of element reduces sometimes, therefore preferably 5nm~300nm, more preferably 10nm~150nm.
In addition, after process [I] and before subsequent processing [II], can also be arranged will be formed with the substrate cooling of film To the process of room temperature.
＜ processes [II] ＞
In process [II], polarized UV rays are irradiated to the film obtained by process [I].It is inclined to the film surface irradiation of film Shake ultraviolet light when, from specific direction across polarization plates to substrate irradiate polarized UV rays.As ultraviolet light to be used, can make With the ultraviolet light that wavelength is 100nm~400nm ranges.Preferably, according to film type to be used, by choosings such as filters Select best wavelength.Also, such as can select using wavelength for 290nm~400nm ranges ultraviolet light, so as to select Induce photo-crosslinking to property.As ultraviolet light, the light for example sent out by high-pressure sodium lamp can be used.
The exposure of polarized UV rays depends on film to be used.About exposure, it is preferably set to realize the maximum of Δ A In the range of the 1%~70% of the amount of the polarized UV rays of value (hereinafter also referred to Δ Amax), more preferably it is set as 1%~50% In range, the Δ A is the film, be parallel to polarized UV rays polarization direction direction ultraviolet absorbance with it is vertical In the difference of the ultraviolet absorbance in the direction of the polarization direction of polarized UV rays.
＜ processes [III] ＞
In process [III], the film of polarized UV rays has been irradiated in heating in process [II].It can be to applying by heating Film assigns tropism control ability.
Heating can use the heating meanss such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven.Heating temperature can It is determined with considering that film used is made to show the temperature of liquid crystal liquid crystal property.
Heating temperature is preferably the temperature (hereinafter referred to as liquid crystal sex expression temperature) that side chain type high molecular form reveals liquid crystal liquid crystal property Within the temperature range of.In the case of film surface as film, it is contemplated that the liquid crystal sex expression temperature of film coated surface is less than whole Liquid crystal sex expression temperature when can show the photosensitive side chain type macromolecule of liquid crystal liquid crystal property is observed on body.Therefore, heating temperature More preferably within the temperature range of the liquid crystal sex expression temperature of film coated surface.That is, the heating temperature after polarized UV rays irradiation Temperature range is preferably：The lower limit of the temperature range of liquid crystal sex expression temperature more high molecular than used side chain type is 10 DEG C low Temperature as lower limit, using 10 DEG C of temperature lower than the upper limit of the liquid crystal temperature range as the temperature of the range of the upper limit.Heating When temperature is less than above-mentioned temperature range, there are in film by the torrid zone Lai the insufficient tendency of anisotropy amplification effect, separately Outside, when heating temperature is excessively high compared with above-mentioned temperature range, there are film state close to isotropic liquid condition (respectively to Same sex phase) tendency, at this point, self assembly (self-assembly) is difficult to be utilized sometimes and carries out reorientation in one direction.
It should be noted that liquid crystal sex expression temperature refers to side chain type macromolecule or film coated surface from the opposite liquid crystalline phase of solid Occur phase transition glass transition temperature (Tg) more than and from the opposite homogenieity phase of liquid crystal (Isotropic phase, respectively to Same sex phase) occur phase transition isotropic phase transition temperature (Tiso) temperature below.
By the process with more than, in the manufacturing method of the present invention, can realize film is efficiently imported it is each to It is anisotropic.Further, it is possible to efficiently manufacture the substrate with liquid crystal orientation film.
＜ processes [IV] ＞
[IV] process be will by substrate (first substrate) with liquid crystal orientation film on conductive film that [III] is obtained with it is same The substrate (second substrate) with liquid crystal orientation film without conductive film obtained by above-mentioned [I ']~[III '] to sample across Liquid crystal is oppositely disposed in the opposite mode of the liquid crystal orientation film of the two, liquid crystal cells is made using well known method, to make The process that the driving liquid crystal of transverse electric field indicates element.It should be noted that about process [I ']~[III '], in addition in process The substrate with conductive film is replaced in [I] and is used except the substrate without the conductive film, it can be with process [I]~[III] It is carried out similarly.Process [I]~[III] and process [I ']~[III's '] only difference is that whether there is or not above-mentioned conductive films, therefore Omit the explanation of process [I ']~[III '].
If enumerating liquid crystal cells or liquid crystal indicating a making example of element, following method can be exemplified：In preparation The first substrate and second substrate stated, are spread spacer on the liquid crystal orientation film of a substrate, are become with liquid crystal alignment film surface The method that the mode of inside pastes another substrate, decompression injection liquid crystal and sealing；Alternatively, being taken to the liquid crystal for being scattered with spacer After liquid crystal is added dropwise to film surface, adhesive substrate and the method etc. being sealed.At this time, it is preferred that unilateral substrate uses laterally The substrate of the electrode with structure as broach of electric field driven.The diameter of spacer at this time is preferably 1 μm~30 μm, More preferably 2 μm~10 μm.The spacer diameter can determine a pair of of base distance between plates of clamping liquid crystal layer, the i.e. thickness of liquid crystal layer Degree.
The manufacturing method of the substrate with film of the present invention is irradiated after forming film composition to be coated on substrate Polarized UV rays.Then, by being heated, anisotropy, manufacture are imported to realize to side chain type polymeric membrane high efficiency The substrate of liquid crystal orientation film with the tropism control ability for having liquid crystal.
Point that film used in the present invention is caused using the light reaction of side chain and by the self assembly based on liquid crystal liquid crystal property The principle of sub- reorientation is realized to film high efficiency and imports anisotropy.The manufacturing method of the present invention has in side chain type macromolecule In the case of having structure of the photocrosslinking reaction group as photoreactive group, film is formed on substrate using side chain type macromolecule Afterwards, polarized UV rays are irradiated, after then being heated, liquid crystal is made and indicates element.
It should be noted that about using with photocrosslinking reaction group, the group of generation light fries' rearrangement or isomerization Side chain type high molecular optical alignment method of the group as the structure of photoreactive group, WO2014/054785 (document Content is integrally comprised in the application as reference) in be described in detail, it is also the same in the application.
As previously discussed, using the present invention composition or the present invention method manufacture liquid crystal indicate component substrate, Especially the driving liquid crystal of transverse electric field indicates that component substrate or the liquid crystal with the substrate indicate element, particularly laterally electricity The driving liquid crystal in field indicates the excellent in reliability of element.
In addition, composition through the invention or generating taking for liquid crystal orientation film method of the invention, it is possible to expand to stablize To the range (so-called " exposure boundary ") of the light irradiation amount of control ability, therefore, in the manufacturing process of liquid crystal orientation film i.e. So that time of polarizing light irradiation etc. is slightly deviateed from controlling value, can also obtain the constant liquid crystal orientation film of quality, can improve The manufacture efficiency of liquid crystal orientation film.Therefore, element is indicated using the liquid crystal of the method manufacture of the composition of the present invention or the present invention Indicate that component substrate or liquid crystal with the substrate indicate element, especially with substrate, particularly the driving liquid crystal of transverse electric field It is that the driving liquid crystal of transverse electric field indicates that element can be suitably used for large screen and the LCD TV of high-resolution etc..
Hereinafter, illustrating the present invention using embodiment, the present invention is not limited to the embodiments.
Embodiment
The abbreviation of (methyl) acrylate compounds and additive that are used in embodiment and its structure are shown in following.
＜ (methyl) acrylate compounds ＞
MA-1 is synthesized by the synthetic method described in patent document (WO2011-084546).
MA-2 is synthesized by the synthetic method described in patent document (Japanese Unexamined Patent Publication 9-118717).
＜ additives ＞
T-1~T-8 uses commercially available product (Tokyo Chemical Industry Co., Ltd's system).
T-1：Benzanthrone
T-2：Acridine
T-3：Pyrene
T-4：9-Fluorenone
T-5：Benzil
T-6：2- acetonaphthones
T-7：1,10- phenanthroline
T-8：2 methyl benzophenone
The abbreviation of the organic solvent used in embodiment etc. is as described below.
NEP：N- ethyl-2-pyrrolidones
PB：Propylene glycol monobutyl ether
THF：Tetrahydrofuran
(polymerization example 1)
MA-1 (13.3g, 40.0mmol) and MA-2 (18.4g, 60.0mmol) are dissolved in THF (182.3g), with every After membrane pump is de-gassed, 2,2 '-azodiisobutyronitriles (0.82g, 5.0mmol) are added, are de-gassed again.Later, with 50 DEG C Reaction 30 hours, obtains the polymer solution of methacrylate.
The polymer solution is added dropwise in diethyl ether (1500ml), gained sediment is filtered.By the sediment diethyl Ether cleans, and is dried under reduced pressure in 40 DEG C of baking oven, obtains methacrylate polymers powder.
NEP (127g) is added in gained powder 10.0g, is stirred at room temperature 16 hours and makes it dissolve.In the solution PB (113g) is added and stirs, to obtain methacrylate polymers solution PMA-1.
(embodiment 1)
Additive T-1 is added in the methacrylate polymers solution PMA-1 (5.00g) obtained among the above (0.010g) is stirred at room temperature 1 hour, to obtain aligning agent for liquid crystal A-1.
(embodiment 2~5 and comparative example 1~4)
To be formed shown in table 1, with method similarly to Example 1, obtain the aligning agent for liquid crystal A-2 of embodiment 2~5~ A-5。
In addition, comparative example 1~4 also prepares aligning agent for liquid crystal B-1~B-4 with same method.
[table 1]
Aligning agent for liquid crystal A-1~A-5's of 1. Examples 1 to 5 of table and aligning agent for liquid crystal B-1~B-4 of comparative example 1~4 Composition
<Light reaction rate measurement substrate is made>
Using the aligning agent for liquid crystal A-1 obtained among the above, light reaction rate measurement substrate is carried out with step shown in following Making.Substrate is the quartz base plate of 1.0mm using size 40mm × 40mm and thickness.
After the filter filtering of 1.0 μm of the filter pore sizes the aligning agent for liquid crystal A-1 obtained in embodiment 1, it is spun on On quartz base plate, after 90 seconds dry on 70 DEG C of hot plate, the liquid crystal orientation film of film thickness 100nm is formed.Then, to coated surface Across polarization plates to become 30mJ/cm2Mode irradiate the ultraviolet light of 313nm, obtain with the liquid crystal aligning Jing Guo light reaction The substrate of film.
About the aligning agent for liquid crystal A-2~A-5 and B-1~B-4 obtained in embodiment 2~5 and comparative example 1~4, also with Light reaction rate measurement substrate is made in the same methods of aligning agent for liquid crystal A-1.
The measurement ＞ of ＜ light reaction rates
The light reaction rate of the liquid crystal orientation film by light reaction made by aforesaid operations is calculated with absorbance and following formula.
It should be noted that using the visible near-infrared analysis luminosity of ultraviolet light of Shimadzu Seisakusho Ltd. in the measurement of absorbance Count U-3100PC.
Herein, A (initial) indicates that the absorbance of UV pre-irradiations, A (exposed) indicate the absorbance after UV irradiations.This When, for light reaction rate closer to 0, expression does not generate light reaction.
＞ is made in the degree of orientation (In-plane order parameter) measurement substrate in the faces ＜
In turn, in order to confirm the optical anisotropy of liquid crystal orientation film, using the aligning agent for liquid crystal A-1 obtained among the above, The making of degree of orientation measurement substrate in carry out face.Substrate is the quartzy base of 1.0mm using size 40mm × 40mm and thickness Plate.
After 1.0 μm of filter filterings of the aligning agent for liquid crystal A-1 obtained in embodiment 1, it is spun on quartz base plate, After being dried 90 seconds on 70 DEG C of hot plate, the liquid crystal orientation film of film thickness 100nm is formed.Then, to coated surface across polarization plates To become 30mJ/cm2Mode irradiate the ultraviolet light of 313nm after, heated 10 minutes on 140 DEG C of hot plate, obtain band liquid crystal The substrate of alignment films.
About the aligning agent for liquid crystal A-2~A-5 and B-1~B-4 obtained in embodiment 2~5 and comparative example 1~4, also use Degree of orientation measurement substrate in face is made in method same as aligning agent for liquid crystal A-1.
The measurement ＞ of the degree of orientation in the faces ＜
Using the substrate with liquid crystal orientation film made among the above, in order to measure the optical anisotropy of liquid crystal orientation film, It is calculated as the S of the degree of orientation in face using following formula by the absorbance of polarised light.
It should be noted that using the UV, visible light near-infrared analysis photometer of Shimadzu Seisakusho Ltd. in the measurement of absorbance U-3100PC。
Herein, AparaIndicate the absorbance in the direction parallel with the polarization directions UV irradiated, AperIt indicates and is irradiated Polarize the absorbance in the vertical direction in the directions UV.AlargeExpression parallel direction is compared with the absorbance of vertical direction, value compared with The absorbance of a big side, AsmallExpression compares parallel direction with the absorbance of vertical direction, is worth the absorbance of a smaller side. For the absolute value of the degree of orientation closer to 1, identical state of orientation is more presented in expression in face.
The absolute value of degree of orientation S in the light reaction rate knead dough of calculating is shown in table 2.It should be noted that for being taken in face Xiang Du is indicated using following benchmark.
◎：The absolute value of S is 0.6 or more
○：The absolute value of S be 0.5 or more~be less than 0.6
△：The absolute value of S be 0.4 or more~be less than 0.5
[table 2]
Table 2.
Using the liquid crystal duty of Examples 1 to 5 and comparative example 1~4 into the light reaction rate knead dough when agent degree of orientation
It should be noted that in table 2, the values of minimum triplet energies be chemical new range photochemistry (skirt China room), Handbook of Photochemistry,Third Edition(CRC Press)、Photochem.Photobiol.Sci., Value described in 2011,10,1902-1909 etc..
In addition, the value of the minimum triplet energies of comparative example 1 indicates the photoreactive group, that is, Chinese cassia tree being originated from polymer The minimum triplet energies of the cinnamic acid of acid groups.
As shown in table 2 like that, it is thus identified that, be added to the present invention additive Examples 1 to 5 aligning agent for liquid crystal with it is complete The aligning agent for liquid crystal of complete un-added comparative example 1 is compared, and light reaction rate reduces.
In addition it confirmed, under conditions of light reaction rate reduces, show the increasing of degree of orientation S in optically anisotropic face Greatly.
And then it is found that the minimum triplet energies value that the value of the minimum triplet energies of additive is more less than cinnamic acid is " 240 ", light reaction rate more reduces and degree of orientation S is worth i.e. 1 closer to desired in face.
Show, in the presence of the additive of the present invention, the sensitivity passivation of photoreactive group, therefore even if place Best UV irradiation areas can be also adjusted under the conditions of ultraviolet irradiation amount is excessive.
Best UV irradiation areas can be also adjusted to by being irradiated under conditions of excess even at ultraviolet light, as a result UV irradiation process In processing boundary expand, can expect to be conducive to fabrication yield raising.In turn, the type by adjusting additive and importing Light reaction rate, can be suppressed to arbitrary ratio by amount.That is, best UV exposures can be finely tuned, being adjusted to anisotropy becomes most Big exposure, so as to obtain the higher liquid crystal orientation film of orientation.
Herein, in Examples 1 to 5, the importing less than the additive of the excited triplet state energy of cinnamic acid is reduced Chinese cassia tree The effect of the light reaction rate of acid, it is therefore, i.e., estimated to play a role as delustering agent.That is, it is believed that, by swashing for cinnamic acid The delustring process that the energy of hair-like state is inactivated since the energy to additive is mobile, the light reaction rate of cinnamic acid reduces. In addition, have the minimum triplet energies difference of additive and cinnamic acid bigger, the tendency that light reaction rate more reduces, therefore imply that, The minimum triplet energies of additive are smaller, more can more advantageously choose delustring process.
It is not limited to as a result, in cinnamic acid, such as chalcone skeleton, coumarin skeleton, Stilbene skeleton, azo benzene skeleton, It carries out shining based on ultraviolet light under the conditions of existing for additive with the minimum triplet energies lower than these photoreactive groups In the case of the light reaction penetrated, a part for photoreactive group also passes through delustring process, thus, it is expected that with there is no additives State compare, light reaction rate is equivalent or reduces.As a result, even if the same liquid for not being cinnamic acid for photoreactive group Brilliant alignment agent can carry out the control of light reaction rate also in the same manner as Examples 1 to 5, be conducive to the processing boundary of UV irradiation process Expand, ultraviolet irradiation amount can be adjusted to anisotropy becomes maximum exposure.

Claims (14)

1. a kind of liquid crystal orientation film manufacture composition, which is characterized in that contain：
(A) side chain type macromolecule, has following side chain, and the side chain shows liquid crystal liquid crystal property and tool within the specified temperature range There is the photoreactive group that photo-crosslinking, photoisomerization or light fries' rearrangement occurs；
(B) organic solvent；With
(C) additive,
The minimum triplet energies of (C) additive are less than the minimum triplet of the compound from the photoreactive group Energy.
2. composition according to claim 1, wherein (A) the side chain type macromolecule has at least one kind of selected from by following Side chain in the group of formula (1)~(6) composition, with photoreactive group,
In formula, A, B, D each independently represent singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH- CO-O- or-O-CO-CH=CH-；
S is the alkylidene of carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
T is the alkylidene of singly-bound or carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
Y1Indicate the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of 2~6 identical or different rings selected from these substituent groups are bonded by linking group B, is bonded to it Hydrogen atom each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon number 1~5 alkyl or the alkyl oxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5；
Y2For selected from the ester ring type hydrocarbon and their group by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 Group in the group being combined into is bonded to their hydrogen atom each independently optionally by-NO2,-CN ,-CH=C (CN)2、-CH The alkyl oxy substitution of=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5；
R indicates the alkoxy of hydroxyl, carbon number 1~6, or expression and Y1Identical definition；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X become 2, X is optionally same or different to each other；
Cou indicates Coumarin-6-base or coumarin-7-base, is bonded to their hydrogen atom each independently optionally by-NO2、- CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy substitution；
One is 1 in q1 and q2 and another one is 0；
Q3 is 0 or 1；
P and Q is each independently selected from the alicyclic ring by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 Group in the group of formula hydrocarbon and combination thereof composition；Wherein, the case where X is-CH=CH-CO-O- ,-O-CO-CH=CH- Under, the P or Q of the side that-CH=CH- is bonded are aromatic rings, and when the quantity of P becomes 2 or more, P is optionally same or different to each other, When the quantity of Q becomes 2 or more, Q is optionally same or different to each other；
L1 is 0 or 1；
The integer that l2 is 0~2；
When l1 and l2 are 0, A also illustrates that singly-bound when T is singly-bound；
When l1 is 1, B also illustrates that singly-bound when T is singly-bound；
H and I is each independently the base in the phenyl ring selected from divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and combination thereof Group.
3. composition according to claim 1, wherein (A) the side chain type macromolecule has at least one kind of selected from by following Side chain in the group of formula (7)~(10) composition, with photoreactive group,
In formula, A, B, D each independently represent singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH- CO-O- or-O-CO-CH=CH-；
Y1Indicate the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of 2~6 identical or different rings selected from these substituent groups are bonded by linking group B, is bonded to it Hydrogen atom each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon number 1~5 alkyl or the alkyl oxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X become 2, X is optionally same or different to each other；
L indicates 1~12 integer；
M indicates that 0~2 integer, m1, m2 indicate 1~3 integer；
N indicates 0~12 integer, wherein B is singly-bound when n=0；
Y2For selected from the ester ring type hydrocarbon and their group by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 Group in the group being combined into is bonded to their hydrogen atom each independently optionally by-NO2,-CN ,-CH=C (CN)2、-CH The alkyl oxy substitution of=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5；
R indicates the alkoxy of hydroxyl, carbon number 1~6, or expression and Y1Identical definition.
4. composition according to claim 1, wherein (A) the side chain type macromolecule has at least one kind of selected from by following Side chain in the group of formula (11)~(13) composition, with photoreactive group,
In formula, A each independently represents singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO- O- or-O-CO-CH=CH-；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X become 2, X is optionally same or different to each other；
L indicates that 1~12 integer, m indicate that 0~2 integer, m2 indicate 1~3 integer；
R indicates the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of 2~6 identical or different rings selected from these substituent groups are bonded by linking group B, is bonded to it Hydrogen atom each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon number 1~5 alkyl or the alkyl oxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5；Or R is indicated The alkoxy of hydroxyl or carbon number 1~6.
5. composition according to claim 1, wherein (A) the side chain type macromolecule has following formula (14) or (15) Shown in photoreactive group side chain,
In formula, A each independently represents singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO- O- or-O-CO-CH=CH-；
Y1Indicate the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of 2~6 identical or different rings selected from these substituent groups are bonded by linking group B, is bonded to it Hydrogen atom each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon number 1~5 alkyl or the alkyl oxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X become 2, X is optionally same or different to each other；
L indicates that 1~12 integer, m1, m2 indicate 1~3 integer.
6. composition according to claim 1, wherein (A) the side chain type macromolecule has following formula (16) or (17) Shown in photoreactive group side chain,
In formula, A indicates singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO-O- or-O-CO- CH=CH-；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X become 2, X is optionally same or different to each other；
L indicates that 1~12 integer, m indicate 0~2 integer.
7. according to composition according to any one of claims 1 to 6, wherein
The high molecular side chain of (A) side chain type has group shown in following formula (A-1),
In formula, Y2For selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 ester ring type hydrocarbon and it The group that is combined into of group in group, be bonded to their hydrogen atom each independently optionally by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy substitution；
R indicates hydroxyl, the alkoxy of carbon number 1~6, the phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5 Ring in~8 ester ring type hydrocarbon, or indicate 2~6 identical or different rings selected from these substituent groups by linking group B keys Group made of conjunction is bonded to their hydrogen atom each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2、-CH The alkyl oxy substitution of=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5, in formula, R0Indicate hydrogen atom or The alkyl of carbon number 1~5；
* group shown in expression (A-1) is a part for the high molecular side chain of described (A) side chain type, is connected at *,
Compound from photoreactive group is formula (A-2) compound represented, in formula, R, Y2Determine with same as described above Justice,
The minimum triplet energies of (C) additive are less than the minimum triplet energies of the formula (A-2) compound represented； Or
The high molecular side chain of (A) side chain type has group shown in following formula (A-3),
In formula, Y1In the ester ring type hydrocarbon for indicating phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 Ring, or be group made of 2~6 identical or different rings selected from these substituent groups are bonded by linking group B, bonding In their hydrogen atom each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, The alkyl of carbon number 1~5 or the alkyl oxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5；
* group shown in expression (A-3) is a part for the high molecular side chain of described (A) side chain type, is connected at *,
Compound from photoreactive group is formula (A-4) compound represented, in formula, Y1With definition same as described above,
The minimum triplet energies of (C) additive are less than the minimum triplet energies of the formula (A-4) compound represented.
8. composition according to claim 7, wherein (C) additive is selected from by following formula (C-1)~(C-27) It is at least one kind of in the group of compound represented composition,
9. according to composition according to any one of claims 1 to 8, wherein (A) the side chain type macromolecule have selected from by Wantonly a kind of liquid crystal liquid crystal property side chain in the group of following formula (21)~(31) composition,
In formula, A and B have definition same as described above；
Y3For selected from by the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring and carbon number 5~8 ester ring type hydrocarbon and they The group that is combined into of group in group, be bonded to their hydrogen atom each independently optionally by-NO2,-CN, halogen group, carbon The alkyl oxy substitution of the alkyl or carbon number 1~5 of number 1~5；
R3Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, phenyl ring, naphthalene nucleus, the biphenyl of 1 valence The ester ring type hydrocarbon of ring, furan nucleus, nitrogen heterocyclic ring, carbon number 5~8, the alkyl of carbon number 1~12 or the alkoxy of carbon number 1~12；
One is 1 in q1 and q2 and another one is 0；
L indicates that 1~12 integer, m indicate 0 to 2 integer, wherein in formula (25)~(26), whole m's adds up to 2 or more, In formula (27)~(28), whole m's adds up to 1 or more, and m1, m2 and m3 each independently represent 1~3 integer；
R2Indicate hydrogen atom ,-NO2,-CN, halogen group, phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring and the carbon of 1 valence The ester ring type hydrocarbon and alkyl or alkyl oxy of number 5~8；
Z1、Z2Indicate singly-bound ,-CO- ,-CH2O- ,-CH=N- ,-CF2-。
10. a kind of manufacturing method of the substrate with liquid crystal orientation film, orientation is imparted by being obtained with following process The liquid crystal orientation film of control ability：
Composition according to any one of claims 1 to 9 is coated on the substrate with conductive film and forms film by [I] Process；
The process that [II] irradiates the film obtained in [I] polarized UV rays；With
The process that [III] heats the film obtained in [II].
11. a kind of substrate with liquid crystal orientation film, is manufactured by method according to any one of claims 10.
12. a kind of liquid crystal indicates element, with substrate according to any one of claims 10.
13. a kind of liquid crystal indicates the manufacturing method of element, element is indicated to obtain the liquid crystal with following process：
Prepare the substrate according to any one of claims 10 i.e. process of the 1st substrate；
The process for obtaining the 2nd substrate with liquid crystal orientation film, have following [I '], [II '], [III '] process and obtain To the liquid crystal orientation film for imparting tropism control ability；With
[IV] across liquid crystal in such a way that the liquid crystal orientation film of the 1st substrate and the 2nd substrate is opposite, by the 1st substrate and 2nd substrate is oppositely disposed and obtains the process that liquid crystal indicates element,
[I '] be coated with composition according to any one of claims 1 to 9 on the 2nd substrate and formed film process,
[II '] to the film that is obtained in [I '] irradiate polarized UV rays process and
The process that [III '] heats the film obtained in [II '].
It is manufactured 14. a kind of liquid crystal indicates element, by be the method described in the claim 13.
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