CN109153839A

CN109153839A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element

Info

Publication number: CN109153839A
Application number: CN201780030684.1A
Authority: CN
Inventors: 根木隆之; 名木达哉; 永井健太郎; 别府功朗; 别府功一朗
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2016-05-18
Filing date: 2017-05-17
Publication date: 2019-01-04
Also published as: KR20190009296A; KR20220048487A; JPWO2017199986A1; KR20210082546A; TW201809878A; WO2017199986A1; JP6992746B2

Abstract

According to the present invention it is possible to provide: providing and have been assigned the novel polymer composition that tropism control ability, after image characteristic are excellent, the driving liquid crystal of transverse electric field indicates element liquid crystal orientation film with high efficiency；With use the driving liquid crystal of its transverse electric field to indicate element liquid crystal orientation film.The present invention relates to a kind of polymer compositions, it contains: (A) side chain type macromolecule, and (B) organic solvent, (A) the side chain type macromolecule have: the side chain (a1) with photoreactivity position shown in following formula (a), the side chain (a2) with the photoreactivity position different from photoreactivity position shown in following formula (a) and the side chain (a3) for showing liquid crystal liquid crystal property.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element

Technical field

The present invention relates to aligning agent for liquid crystal, liquid crystal orientation film and using its liquid crystal indicate element, be suitable for manufacture phase Poor film, polarization diffraction device etc. control the macromolecule membrane of the optical element of molecularly oriented.

Background technique

Liquid crystal indicate element as light weight, slim and low power consumption expression device be it is known, be used in recent years greatly Type television applications etc. realize significant development.Liquid crystal indicates that element is, for example, to press from both sides using a pair of of the transparent substrate for having electrode It holds liquid crystal layer and constitutes.Also, it indicates to be used as liquid crystal aligning by the organic film that organic material is formed in element in liquid crystal Film, so that expectation state of orientation is presented in liquid crystal between the substrates.

That is, liquid crystal orientation film be liquid crystal indicate element component parts, 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 making liquid crystal be orientated this effect along specific directions such as the directions for being for example parallel to substrate, also require sometimes The pre-tilt angle of liquid crystal is carried out controlling this effect.The ability of the control liquid crystal aligning of this liquid crystal orientation film (hereinafter referred to as takes To control ability.) be endowed and 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, it has been known that there is brushings all the time Method.Brushing method refers to following method: for the organic film of polyvinyl alcohol, polyamide, polyimides on substrate etc., using cotton The cloth of flower, nylon, polyester etc. is along constant direction friction (brushing) its surface, to make liquid crystal along frictional direction (brushing side To) orientation.The brushing method can easily realize more stable liquid crystal aligning state, therefore be used in previous liquid crystal expression member In the manufacturing process of part.It is main to select the reliabilities such as heat resistance, electricity special also, as organic film used in liquid crystal orientation film The excellent polyimides system organic film of property.

However, the brushing method to rub to the surface of the liquid crystal orientation film by formation such as polyimides there are dust, produce The problem of raw electrostatic.In addition, since liquid crystal in recent years indicates that the high-definition of element, the electrode on corresponding substrate or liquid crystal drive Employ bumps caused by switching active component, therefore, the surface for the liquid crystal orientation film that can not equably be rubbed with cloth sometimes, can not Realize uniform liquid crystal aligning.

Thus, as other method for orientation treatment of the liquid crystal orientation film without brushing, energetically have studied light orientation Method.

Optical alignment method has various methods, is constituting the organic of liquid crystal orientation film by rectilinearly polarized light or collimated light Anisotropy is formed in film, is orientated liquid crystal according to the anisotropy.As main optical alignment method, it is known to: it is logical Polarized UV rays irradiation is crossed, generates " photolysis type " of anisotropic decomposition in the molecular structure；Use poly- cinnamic acid ethylene Ester irradiates polarized UV rays, makes to generate dimerization (cross-linking reaction) in the double bond part of 2 side chains parallel with polarised light " dimerization type " (referring for example to patent document 1)；Using in the high molecular situation of side chain type on side chain with azobenzene, shine Polarized UV rays are penetrated, isomerization reaction is generated in the azobenzene portion of the side chain parallel with polarised light, makes liquid crystal edge and polarization direction " isomerization type " (referring for example to the non-patent literature 2) of orthogonal direction orientation.

On the other hand, in recent years, to using the high molecular new light of the photosensitive side chain type that can show liquid crystal liquid crystal property to take It is studied to method (hereinafter also referred to as orientation amplifying method).It refers to: to the photosensitive side that can show liquid crystal liquid crystal property The high molecular film of chain carries out orientation process by polarizing light irradiation and heats later to the side chain type polymeric membrane, passes through These processes obtain the film for having been assigned tropism control ability.At this point, being shown by polarizing light irradiation a small amount of respectively to different Property become driving force, side chain type macromolecule of liquid crystal liquid crystal property itself passes through self assembly effectively reorientation.As a result, available work Efficient orientation process is realized for liquid crystal orientation film, the liquid crystal orientation film that has been assigned high tropism control ability (such as is joined According to patent document 2).

In turn, birefringence is shown according to molecularly oriented by the macromolecule membrane that the orientation amplifying method obtains, because This can also be used as the various optical elements such as phase-contrast film and utilize in addition to the purposes of liquid crystal orientation film.

Existing technical literature

Patent document

Patent document 1: No. 3893659 bulletins of Japanese Patent No.

Patent document 2: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)

Summary of the invention

Problems to be solved by the invention

Optimal polarization is purple for expeditiously importing anisotropy to the liquid crystal orientation film for being orientated amplifying method The exposure of outside line reaches the irradiation of optimal polarized UV rays with the amount of photonasty group generation light reaction is made in the film It measures corresponding.Polarized UV rays are irradiated for liquid crystal orientation film used in orientation amplifying method, as a result, the side chain of light reaction occurs If photonasty group it is few, not will form sufficient light reaction amount.Under above situation, even if being heated later, also not Carry out sufficient self assembly.On the other hand, if the photonasty group that the side chain of light reaction occurs becomes excessive, gained film becomes Obtain upright and outspoken, the progress of self assembly brought by the heating after interfering sometimes.

Currently, being orientated in liquid crystal orientation film used in amplifying method, the photoreactive group in polymer used sometimes High sensitivity or above-mentioned optimal polarized UV rays exposure region it is narrow.As a result, liquid crystal indicates the manufacture of element The reduction of efficiency becomes problem.

In turn, in the case that the firing temperature of liquid crystal orientation film is low, due to residual solvent etc. influence and have liquid crystal expression A possibility that reliability of element reduces, but be orientated aligning agent for liquid crystal that amplifying method obtains its in nature, can not be in high score It is burnt at a temperature of more than the liquid crystal performance temperature of sub- liquid crystal, therefore, low, residual solvent of firing temperature etc., which becomes, in a word makes reliably Property one of the factor that reduces.

Therefore, the object of the present invention is to provide: tropism control ability is imparted with high efficiency and can be adjusted to best Polarized UV rays exposure, optimal firing temperature the wide liquid crystal orientation film of process allowance.

The solution to the problem

The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that following invention.

<1>a kind of polymer composition, contains:

(A) side chain type macromolecule, and (B) organic solvent, (A) the side chain type macromolecule have: having following formula (a) institute The side chain (a1) at the photoreactivity position shown has the photoreactivity portion different from photoreactivity position shown in following formula (a) The side chain (a2) of position and the side chain (a3) for showing liquid crystal liquid crystal property.

<2>in above-mentioned<1>, above-mentioned side chain (a2) can be the sense of generation photo-crosslinking, photoisomerization or light fries' rearrangement Photosensitiveness side chain.

<3>in above-mentioned<1>or<2>, above-mentioned side chain (a2) can be in the group being made of following formula (1)~(6) Wantonly a kind of photonasty side chain and be the side with the photoreactivity position different from photoreactivity position shown in above-mentioned formula (a) Chain.

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 monovalence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 Ring, or identical or different 2~6 ring in these substituent groups is by group made of binding groups B bonding, Their hydrogen atom is bonded to 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 take Generation,；

Y₂For selected from the ester ring type hydrocarbon and their group by the phenyl ring of divalent, naphthalene nucleus, furan nucleus, pyrrole ring, carbon number 5~8 The group in 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 number 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 of q1 and q2 are 1, another one 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 their combination 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 number of P becomes 2 or more, P is optionally mutually the same or not Together, when the number 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 phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and their combination selected from divalent In group.

<4>in any one of above-mentioned<1>~<3>, above-mentioned side chain (a3) can be for selected from by following formula (21)~(31) group At group in wantonly a kind of liquid crystal liquid crystal property side chain.

In formula, A and B have definition same as described above；

Y₃For selected from by the phenyl ring of monovalence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and carbon number 5~8 ester ring type hydrocarbon Group in the group of their combination composition, is bonded to their hydrogen atom each independently optionally by-NO₂,-CN, halogen The alkyl oxy of 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, Cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or carbon number 1~12 alcoxyl Base；

One of q1 and q2 are 1, another one 0；

L indicate 1~12 integer, m indicate 0~2 integer, wherein in formula (23)~(24), whole m add up to 2 with On, in formula (25)~(26), 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, the phenyl ring of monovalence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle, With the ester ring type hydrocarbon and alkyl or alkyl oxy of carbon number 5~8；

Z₁、Z₂Indicate singly-bound ,-CO- ,-CH₂O- ,-CH=N- ,-CF₂-。

<5>a kind of manufacturing method for the substrate that element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field, Obtain having been assigned the liquid crystal orientation film of tropism control ability and having following process,

The composition of any one of above-mentioned<1>~<4>is coated on the base of the conductive film with transverse electric field driving by [I] The process of film is formed on plate；

The process of [II] to the irradiation polarized UV rays of film obtained in [I]；With,

The process that [III] heats film obtained in [II].

<6>a kind of substrate that element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field, be by it is above-mentioned< 5 > method manufacture.

<7>a kind of driving liquid crystal of transverse electric field indicates element, the substrate with above-mentioned<6>.

<8>a kind of driving liquid crystal of transverse electric field indicates the manufacturing method of element, is obtained and having following process The liquid crystal indicates element:

Prepare the process of the substrate (the 1st substrate) of above-mentioned<6>；

The process for obtaining the 2nd substrate with liquid crystal orientation film, by having following [I '], [II '], [III '] process And obtain having been assigned the liquid crystal orientation film of tropism control ability；And

[IV] is oppositely disposed the 1st substrate in such a way that the liquid crystal orientation film of the 1st substrate and the 2nd substrate is across liquid crystalline phase pair With the 2nd substrate, thus obtain liquid crystal indicate element process,

[I '] is coated with the polymer composition of any one of above-mentioned<1>~<17>on the 2nd substrate and forms the work of film Sequence；

The process of [II '] to the irradiation polarized UV rays of film obtained in [I ']；With

The process that [III '] heats film obtained in [II '].

<9>a kind of driving liquid crystal of transverse electric field indicates element, is manufactured by above-mentioned<8>.

The effect of invention

According to the present invention it is possible to obtain the polymer with specific structural unit, resulting polymers form liquid crystal aligning When film, with previous polymer phase ratio, good orientation is shown under the UV exposure of wider range.As a result, for reality Existing liquid crystal indicates various characteristics required by element, can be with more than ever before kind of various polarization when carrying out light orientation processing Light UV exposure carries out, and productivity improves.As a result, can be provided well with yield rate: having and have been assigned orientation with high efficiency Control ability, after image characteristic are excellent, the driving liquid crystal of transverse electric field indicates the substrate of element liquid crystal orientation film and have this The driving liquid crystal of the transverse electric field of substrate indicates element.

Specific embodiment

Present inventor has performed further investigations, as a result obtain following opinion, so as to complete the present invention.

Polymer composition of the invention has the photonasty side chain type macromolecule that can show liquid crystal liquid crystal property (hereinafter, also simple Referred to as side chain type macromolecule), it the use of the film that foregoing polymer compositions obtain is with the photonasty that can show liquid crystal liquid crystal property The high molecular film of side chain type.The film carries out orientation process by polarizing light irradiation without brushing processing.Also, After irradiating polarised light, the film for having been assigned tropism control ability is formed via the process for heating the side chain type polymeric membrane (hereinafter also referred to as liquid crystal orientation film).At this point, becoming driving by the small anisotropy that polarizing light irradiation is shown Reorientation is effectively performed by self assembly in the side chain type macromolecule itself of power, liquid crystal liquid crystal property.It is taken as a result, can be used as liquid crystal Efficient orientation process is realized to film, obtains the liquid crystal orientation film for having been assigned highly oriented control ability.

In addition, the side chain type macromolecule as (A) ingredient contains above-mentioned formula (a) in polymer composition in the present invention Shown in side chain.UV exposure meter when the liquid crystal orientation film obtained as a result, by polymer composition of the invention is to manufacture, Good orientation is shown under the UV exposure of wider range.About the phenomenon, it is believed that: light reaction shown in above-mentioned formula (a) Property position due to long conjugated system and have fluorescent characteristic, thus absorb ultraviolet light.Therefore, make that there is above-mentioned formula by utilizing (a) polymer obtained from the monomer copolymerization at photoreactivity position shown in, to expand irradiation surplus.It should be noted that These include being related to the opinion of the present inventor of mechanism of the invention, do not limit the present invention.

In addition, in polymer composition in the present invention, as (A) ingredient side chain type macromolecule and as (B) at It on the basis of the organic solvent divided, can also contain: tetracarboxylic acid derivatives being made to carry out polymerization reaction with diamine compound and manufacture Polyamic acid or make polyamic acid carry out imidizate and manufacture polyimides, make diisocyanate cpd and diamines Compound carry out polymerization reaction and manufacture polyureas, make diisocyanate cpd and tetracarboxylic acid derivatives and diamine compound into Row polymerization reaction and manufacture polyureas polyamic acid, so that polyureas polyamic acid is carried out imidizate and the polyureas polyimides that manufactures As (C) ingredient.

Hereinafter, embodiments of the present invention are described in detail.

< polymer composition >

Coated polymeric composition on the substrate of the conductive film with transverse electric field driving, particularly on conductive film.

Used in the manufacturing method of the present invention, the polymer composition be characterized in that, contain:

(A) side chain type macromolecule and (B) organic solvent, (A) the side chain type macromolecule are in defined temperature range The photosensitive side chain type macromolecule of liquid crystal liquid crystal property is inside shown, and is had:

Side chain (a1) with photoreactivity position shown in following formula (a),

Side chain (a2) with the photoreactivity position different from photoreactivity position shown in following formula (a) and

Show the side chain (a3) of liquid crystal liquid crystal property.

< < (A) side chain type macromolecule > >

(A) the side chain type macromolecule of ingredient is the photosensitive side chain type for showing liquid crystal liquid crystal property within the specified temperature range Macromolecule, and have:

Side chain (a1) with photoreactivity position shown in above-mentioned formula (a),

Side chain (a2) with the photoreactivity position different from photoreactivity position shown in above-mentioned formula (a) and

Show the side chain (a3) of liquid crystal liquid crystal property.

(A) the side chain type macromolecule of ingredient can react under the light of the wave-length coverage of 250nm~400nm and Liquid crystal liquid crystal property is shown within the temperature range of 100 DEG C~300 DEG C.

(A) the side chain type macromolecule of ingredient preferably has reacts photosensitive under the light of the wave-length coverage of 250nm~400nm Property side chain.

In order to show liquid crystal liquid crystal property within the temperature range of 100 DEG C~300 DEG C, the side chain type macromolecule of (A) ingredient is preferred Has the side chain (a3) for showing liquid crystal liquid crystal property.

< < < side chain (a2): the side chain with the photoreactivity position different from photoreactivity position shown in formula (a) > > >

(A) the side chain type macromolecule of ingredient has: having the photoreactivity different from photoreactivity position shown in formula (a) The side chain (a2) at position.Herein, " there is the photoreactivity position different from photoreactivity position shown in formula (a) " and refers to have There is photoreactivity position, but does not have photoreactivity position shown in formula (a).That is, side chain (a2) refers to, there is induction light and send out The position of raw cross-linking reaction, isomerization reaction or light fries' rearrangement, and do not have photoreactivity position shown in formula (a) Side chain.

(A) the side chain type macromolecule of ingredient is bonded with photosensitive side chain on main chain, is incuded light and can be occurred Cross-linking reaction, isomerization reaction or light fries' rearrangement.At this point, if exposed to outside stimulus such as heat, it also can be steady for a long time It is fixed to keep realized tropism control ability.As long as the high molecular structure of photonasty side chain type that can show liquid crystal liquid crystal property meets this Kind characteristic is just not particularly limited, with the mesomorphic ingredient of upright and outspoken (rigid) preferably in side-chain structure.At this point, by the side chain When liquid crystal orientation film is made in 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 The induction light in portion and carry out cross-linking reaction, isomerization reaction photonasty group structure；With main chain and the side for being bonded to it Chain, the side chain have the also structure as mesomorphic ingredient and the phenylamino benzoic acid ester group of progress light Fries rearrangement.

More specific example as the high molecular structure of photonasty side chain type that can show liquid crystal liquid crystal property, it is however preferred to have By selected from by (methyl) acrylate, itaconate, fumarate, maleate, alpha-methylene-gamma-butyrolactone, styrene, The radically polymerizable group of vinyl, maleimide, norbornene etc. is rolled into a ball and at least one of the group of siloxanes composition structure At main chain and the side chain formed by least one of following formula (1)~(6) structure.

In above-mentioned formula (1)~(6), A, B, D each independently represent singly-bound ,-O- ,-CH₂-、-COO-、-OCO-、- CONH- ,-NH-CO- ,-CH=CH-CO-O- or-O-CO-CH=CH-；

Y₁In the ester ring type hydrocarbon for indicating phenyl ring selected from monovalence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 Ring, or identical or different 2~6 ring in these substituent groups is by group made of binding groups B bonding, Their hydrogen atom is bonded to 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 take Generation；

Y₂For selected from by the phenyl ring of divalent, naphthalene nucleus, furan nucleus, pyrrole ring, carbon number 5~8 ester ring type hydrocarbon and they The group in group that group is combined into is bonded to their hydrogen atom each independently optionally by-NO₂,-CN ,-CH=C (CN)₂、- The alkyl oxy substitution of CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5；

One of q1 and q2 are 1, another one 0；

Q3 is 0 or 1；

L1 is 0 or 1；

The integer that l2 is 0~2；

When l1 is 1, B also illustrates that singly-bound when T is singly-bound；

Preferred embodiment according to the present invention, side chain (a2) are wantonly a kind in the group being made of above-mentioned formula (1)~(6) Photonasty side chain, and be the side chain with the photoreactivity position different from photoreactivity position shown in above-mentioned formula (a).

Side chain (a2) can be wantonly a kind of the photonasty side chain in 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, when n=0, B is singly-bound).

Side chain (a2) can be wantonly a kind of the photonasty side chain in the group being made of following formula (11)~(13).

In formula, A, X, l, m, m1 and R have definition same as described above.

Side chain (a2) can be photonasty side chain shown in following formula (14) or (15).

In formula, A, Y₁, l, m1 and m2 have definition same as described above.

Side chain (a2) can be photonasty side chain shown in following formula (16) or (17).

In formula, A, X, l and m have definition same as described above.

In addition, side chain (a2) can be photonasty side chain shown in following formula (18) or (19).

In formula, A, B, Y1, q1, q2, m1 and m2 have definition same as described above.

R₁Indicate hydrogen atom ,-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.

Side chain (a2) can be photonasty side chain shown in following formula (20).

In formula, A, Y₁, X, l and m have definition same as described above.

< < < side chain (a1): the side chain > > > with photoreactivity position shown in formula (a)

In addition, the side chain type macromolecule of (A) ingredient contains the side chain with photoreactivity position shown in following formula (a) (a1)。

As side chain (a1), such as side chain shown in preferred following formula (a1-1).

In formula (a1-1), L is the alkylidene of the linear chain or branched chain of carbon number 1~16.

In formula (a1-1), X indicates singly-bound ,-O- ,-C (=O)-O- or-O-C (=O)-.

< < < side chain (a3): the side chain > > > of liquid crystal liquid crystal property is shown

In turn, the side chain type macromolecule of (A) ingredient contains the side chain (a3) for showing liquid crystal liquid crystal property.Side chain (a3) is herein Refer to, show the side chain of liquid crystal liquid crystal property, and be itself can show mesomorphism side chain or for hydrogen bond etc. progress dimerization from And the side chain of mesomorphism can be shown.

That is, as the side chain (a3) for showing liquid crystal liquid crystal property in the side chain type macromolecule of (A) ingredient, for example, be preferably 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, B, q1 and q2 have definition same as described above；

Z₁、Z₂Indicate singly-bound ,-CO- ,-CH₂O- ,-CH=N- ,-CF₂-。

The high molecular preparation method > > of the photosensitive side chain type of < <

The above-mentioned photosensitive side chain type macromolecule that can show liquid crystal liquid crystal property can be by that will have structure shown in formula (a) The monomer of unit, the photoreactivity side chain with the photoreactivity position different from photoreactivity position shown in above-mentioned formula (a) Monomer (M1) and liquid crystal liquid crystal property side chain monomer (M2) polymerization obtain.

[monomer with structural unit shown in formula (a)]

As the monomer with structural unit shown in formula (a), following formula (am1-1) compound represented can be enumerated.

In formula (am1-1), L is the alkylidene of the linear chain or branched chain of carbon number 1~16.

In formula (am1-1), X indicates singly-bound ,-O- ,-C (=O)-O- or-O-C (=O)-.

In formula (am1-1), PL is the group that can polymerize, and indicates poly- in the group being made of following formula PL-1~PL-5 Conjunction property group.In formula PL-1~PL-5, R¹、R²And R³Indicate the alkyl of the linear chain or branched chain of hydrogen atom, carbon number 1~10 or by halogen The alkyl of the linear chain or branched chain for the carbon number 1~10 that element replaces (* indicates the bonding position with L).

In these monomers, some is commercially available, and what is had can be manufactured by known substance with well known manufacturing method.

[photoreactivity side chain monomer (M1)]

Photoreactivity side chain monomer refers to, when forming macromolecule, can be formed in high molecular side chain position with aforementioned The high molecular monomer of photonasty side chain (a2).

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 photonasty The structure of side chain, that is, the polymerizable group is by selected from by (methyl) acrylate, itaconate, fumarate, maleic acid The radically polymerizable group of ester, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene etc. roll into a ball and At least one of the group of siloxanes composition is constituted, and the photonasty side chain is to be formed by least one of above-mentioned formula (1)~(6) Photonasty side chain, preferably for example by the photonasty side chain of at least one formation in above-mentioned formula (7)~(10), by above-mentioned formula (11) photonasty side chain, above-mentioned formula shown in the photonasty side chain of at least one formation in~(13), above-mentioned formula (14) or (15) (16) or photonasty side chain shown in (17), shown in photonasty side chain, above-mentioned formula (20) shown in above-mentioned formula (18) or (19) Photonasty side chain.

More specific example as monomer (M1), it is however preferred to have following polymerizable group and the knot such as flowering structure Structure, that is, the polymerizable group is by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, α-Asia The radically polymerizable group of methyl-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene etc. is rolled into a ball and siloxanes At least one kind of composition in the group of composition, the structure be by least one kind of formation in above-mentioned formula (1)~(6) to show light anti- The structure of answering property and liquid crystal liquid crystal property, preferably for example by least one kind of formation in above-mentioned formula (7)~(10) show photoreactivity and The structure of liquid crystal liquid crystal property, by least one kind of formation in above-mentioned formula (11)~(13) the structure for showing photoreactivity and liquid crystal liquid crystal property, It shows to show shown in the structure, above-mentioned formula (16) or (17) of photoreactivity and liquid crystal liquid crystal property shown in above-mentioned formula (14) or (15) Out the structure of photoreactivity and liquid crystal liquid crystal property, photoreactivity and liquid crystal liquid crystal property are shown shown in above-mentioned formula (18) or (19) structure, The structure of photoreactivity and liquid crystal liquid crystal property is shown shown in above-mentioned formula (20).

Monomer (M1) can for from following formula MA1, MA3, MA4, MA5, MA14, MA16~MA23, MA25, MA28~ MA30, MA32, MA34, MA36, MA38~MA42, MA44 and MA46 and among these compounds as polymerizable group have There is the polymerizable group of the compound of methacrylate to be replaced by selected from by acrylate, itaconate, fumarate, horse Come in the group of acid esters, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxanes composition Polymerizable group made of at least one that selects in compound.Especially monomer (M1) can have (methyl) acrylate As polymerizable group, it is preferred that the end of such as side chain can be COOH.

It should be noted that MA1~MA46 can be synthesized as follows.

MA1 can be synthesized with the synthetic method recorded in patent document (WO2011-084546).

MA2 can be synthesized with the synthetic method recorded in patent document (Japanese Unexamined Patent Publication 9-118717).

MA3 can be carried out with the synthetic method recorded in non-patent literature (Macromolecules 2002,35,706-713) Synthesis.

MA4 can be synthesized with the synthetic method recorded in patent document (WO2014/054785).

MA5 can be synthesized with the synthetic method recorded in patent document (Japanese Unexamined Patent Publication 2010-18807).

MA6~MA9 can be synthesized with the synthetic method recorded in patent document (WO2014/054785).

MA10 can be used can the commercially available M6BC (Midori Kagaku Co., Ltd. system) bought.

MA11~13 can be synthesized with the synthetic method recorded in patent document (WO2014/054785).

It MA14~18 can be respectively using commercially available buy, M4CA, M4BA, M2CA, M3CA and M5CA (all of which of energy For Midori Kagaku Co., Ltd. system).

MA19~23 can be synthesized with the synthetic method recorded in patent document (WO2014/054785).

MA24 can be with note in non-patent literature (Polymer Journal, Vol.29, No.4, pp303-308 (1997)) The synthetic method of load is synthesized.

MA25 can be synthesized with the synthetic method recorded in patent document (WO2014/054785).

MA26 and MA27 can be respectively with non-patent literature (Macromolecules (2012), 45 (21), 8547- 8554), the synthetic method recorded in non-patent literature (Liquid Crystals (1995), 19 (4), 433-40) is synthesized.

MA28~33 can be synthesized with the synthetic method recorded in patent document (WO2014/054785).

MA34~39 can be synthesized with the synthetic method recorded in patent document (WO2014/054785).

MA40 and 41 can be closed with the synthetic method recorded in patent document (Japanese Unexamined Patent Application Publication 2009-511431) At.

MA42 can be synthesized with the synthetic method recorded in patent document (WO2014/054785).

MA43 can be synthesized with the synthetic method recorded in patent document (WO2012-115129).

MA44 can be synthesized with the synthetic method recorded in patent document (WO2013-133078).

MA45 can be synthesized with the synthetic method recorded in patent document (WO2008-072652).

MA46 can be synthesized with the synthetic method recorded in patent document (WO2014/054785).

[monomer (M2) and its manufacturing method with the structure for only showing liquid crystal liquid crystal property]

Monomer (M2) with the structure for only showing liquid crystal liquid crystal property refers to that the polymer from the monomer shows liquid crystal Property, and the polymer can form the monomer of mesomorphic group at side chain position.

It can be with biphenyl, phenol benzoate etc. individually as mesomorphic structure as mesomorphic group possessed by side chain Group, or as benzoic acid etc., side chain carries out Hydrogenbond each other and becomes the group of mesomorphic structure.As side chain Possessed mesomorphic group, preferably following structures.

More specific example as the monomer (M2) with the structure for only showing liquid crystal liquid crystal property, it is however preferred to have following poly- The structure of conjunction property group and the structure by least one kind of formation in above-mentioned formula (21)~(31): the polymerizable group is by being selected from By hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, alpha-methylene-gamma-butyrolactone, styrene, ethylene At least one kind of composition in group that the radically polymerizable group of base, maleimide, norbornene etc. is rolled into a ball and siloxanes forms.

Monomer (M2) can for from above-mentioned formula MA2, MA9~MA13, MA15, MA24, MA26, MA27, MA31, MA35, MA37, MA43 and MA45 and the among these compounds compound as polymerizable group with methacrylate gather Close property group be replaced by selected from by acrylate, itaconate, fumarate, maleate, alpha-methylene-gamma-butyrolactone, In compound made of the polymerizable group in group that styrene, vinyl, maleimide, norbornene and siloxanes form At least one of selection.Monomer (M2) can have (methyl) acrylate as polymerizable group, it is therefore particularly preferred that for example The end of side chain can be COOH.

[monomer (M3) with crosslinkable groups]

Macromolecule as (A) ingredient can have following monomer and be formed: (M-3) have crosslinkable groups monomer, Specifically there is the monomer of at least one kind of group in the group being made of following formula (G-1), (G-2), (G-3) and (G-4) (M3), the monomer more specifically with structure shown in following formula (0).

(in formula (0), S, A, P, X, Q, B, T, l1 and l2 indicate meaning identical with the definition in previously described formula (1), and G is indicated Group in above-mentioned (G-1), (G-2), (G-3) and (G-4), dotted line indicate atom key, R⁵⁰It indicates to be selected from hydrogen atom, halogen Atom, the alkyl of carbon number 1~3, the group in phenyl, R⁵⁰When having multiple, optionally it is same or different to each other, the integer that t is 1~7, J indicates O, S, NH or NR⁵¹, R⁵¹Indicate the group in alkyl and phenyl selected from carbon number 1~3.)

[monomer with structure shown in formula (0)]

As the more specific example of the above-mentioned monomer with structure shown in formula (0), preferably have by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, alpha-methylene-gamma-butyrolactone, styrene, vinyl, horse Carry out the polymerism of the radically polymerizable group group of acid imide, norbornene etc. and at least one kind of composition in the group of siloxanes composition Structure shown in group and above-mentioned formula (0).

In such monomer, as the monomer with epoxy group, specifically, for example, (methyl) acrylic acid contracts The compounds such as water glyceride, (methyl) acrylic acid (3,4- epoxycyclohexyl) methyl esters, allyl glycidyl ether, wherein can be with It is double to enumerate (methyl) glycidyl acrylate, (methyl) acrylic acid (3,4- epoxycyclohexyl) methyl esters, 3- vinyl -7- oxa- Ring [4.1.0] heptane, 1,2- epoxy -5- hexene, 1,7- octadiene monoepoxide etc..

As the monomer with thiirane, specifically, for example, the above-mentioned monomer with epoxy group Epoxy construction is replaced by monomer made of thiirane etc..

As the monomer with aziridine, specifically, for example, the epoxy of the above-mentioned monomer with epoxy group Structure is replaced by monomer made of aziridine or 1- methylaziridine etc..

As the monomer with oxetanyl, for example, (methyl) acrylic acid with oxetanyl Ester etc..In such monomer, preferably 3- (methacryloxymethyl) oxetanes, 3- (acryloyloxymethyl) oxa- Cyclobutane, 3- (methacryloxymethyl) -3- methvl-oxetan, 3- (acryloyloxymethyl) -3- methyl-oxygen Azetidine, 3- (methacryloxymethyl) -3- ethyl-oxetane, 3- (acryloyloxymethyl) -3- ethyl - Oxetanes, 3- (methacryloxymethyl) -2- trifluoromethyl oxetanes, 3- (acryloyloxymethyl) -2- Trifluoromethyl oxetanes, 3- (methacryloxymethyl) -2- phenyl-oxetanes, 3- (acryloxy first Base) -2- phenyl-oxetanes, 2- (methacryloxymethyl) oxetanes, 2- (acryloyloxymethyl) oxa- Cyclobutane, 2- (methacryloxymethyl) -4- trifluoromethyl oxetanes, 2- (acryloyloxymethyl) -4- trifluoro Methy oxetane can enumerate 3- (methacryloxymethyl) -3- ethyl-oxetane, 3- (acryloxy Methyl) -3- ethyl-oxetane etc..

As the monomer with Thietane base, such as the oxetanes of the preferably monomer with oxetanyl Base is replaced by monomer made of Thietane base.

As the monomer with azetidinyl, such as the oxetanes of the preferably monomer with oxetanyl Base is replaced by monomer made of azetidinyl.

Among the above, from availability etc., the monomer preferably with epoxy group and the list with oxetanyl Body, more preferably with the monomer of epoxy group.Wherein, from availability aspect, preferred (methyl) glycidyl acrylate.

[monomer (M4) with nitrogenous aromatic heterocycle etc.]

Polymer (A1) and/or polymer (A2) can have following monomer according to expectation and be formed: (M-4), which has, to be selected from The monomer (M4) of at least one kind of group in group be made of nitrogenous aromatic heterocycle, amide groups and carbamate groups.

Nitrogenous heteroaromatic can for containing at least one, preferably 1~4 selected from by following formulas [20a], formula [20b] and formula [20c] (in formula, Z₂For the linear or branched alkyl group of carbon number 1~5) composition group in structure aromatic series ring type Hydrocarbon.

Specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline can be enumerated Quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine Ring, triazole ring, pyridine ring, benzimidazole ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzo thiophene Azoles ring, phenthazine ring, oxadiazoles ring, acridine ring etc..In turn, it can have on the carbon atom of these nitrogenous heteroaromatics and include Heteroatomic substituent group.

Wherein, such as preferred pyridine ring.

May is that has since the macromolecule as (A) ingredient passes through selected from nitrogenous aromatic heterocycle, amide groups and ammonia Group in carbamate base, so that ion can be reduced when liquid crystal orientation film is made in polymer composition of the invention Property impurity dissolution, and promote the friendship of the cross-linking reaction of above-mentioned crosslinkable groups, more specifically group shown in above-mentioned formula (0) Connection reaction, therefore the higher liquid crystal orientation film of available durability.Have to manufacture selected from nitrogenous aromatic heterocycle, acyl The polymer of group in amido and carbamate groups can make monomer (M4) and above-mentioned monomer (M1), have shown in formula (a) Structural unit monomer and monomer (M2), according to desired monomer (M3) be copolymerized.

It as monomer (M4), is preferably provided with: by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, horse Carry out the radically polymerizable group of acid esters, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene etc. Group is with the polymerizable group of at least one kind of composition in the group of siloxanes composition and with nitrogenous aromatic heterocycle, amide groups With the structure of carbamate groups.The NH of amide groups and carbamate groups is optionally substituted or unsubstituted.As optionally quilt Substituent group when substitution can enumerate alkyl, the protecting group of amino, benzyl etc..

In such monomer, as the monomer with nitrogenous aromatic heterocycle, specifically, for example, (first Base) acrylic acid 2- (2- pyridylcarbonyl oxygroup) ethyl ester, (methyl) acrylic acid 2- (3- pyridylcarbonyl oxygroup) ethyl ester, (methyl) Acrylic acid 2- (4- pyridylcarbonyl oxygroup) ethyl ester etc..

As the monomer with amide groups or carbamate groups, specifically, for example, (methyl) acrylic acid 2- (4- methyl piperidine -1- base carbonylamino) ethyl ester, 4- (6- Methacryloxyhexyl oxygroup) benzoic acid N- (tert-butyl oxygen Base carbonyl) piperidin-4-yl ester, 4- (6- Methacryloxyhexyl oxygroup) benzoic acid 2- (t-butyloxycarbonyl amino) second Base ester etc..

(M-4) there is at least 1 in the group being made of nitrogenous aromatic heterocycle, amide groups and carbamate groups The monomer (M4) of kind group can be for from above-mentioned formula MA6~MA8 and MA33 and among these compounds as polymerism base There is the polymerizable group of the compound of methacrylate to be replaced by selected from by acrylate, itaconate, fumaric acid for group Ester, maleate, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxanes composition Group in polymerizable group made of select in compound it is at least one kind of.

It, can be total with other monomers in the range of not damaging the expressive ability of photoreactivity and/or liquid crystal liquid crystal property as above-mentioned It is poly-.As other monomers, for example, the monomer that can be carried out Raolical polymerizable that can industrially obtain.

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, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, third Olefin(e) acid benzyl ester, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, acrylic acid 2,2,2- trifluoro second Ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2- methoxy acrylate, methoxy triethylene Acrylate, acrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxybutyl, acrylic acid 2- methyl -2- Buddha's warrior attendant alkyl ester, acrylic acid 2- propyl -2- Buddha's warrior attendant alkyl ester, acrylic acid 8- methyl -8- tricyclodecyl and acrylic acid 8- ethyl -8- three Ring last of the ten Heavenly stems ester etc..

As methacrylate compound, for example, methyl methacrylate, ethyl methacrylate, methyl Isopropyl acrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthrylmethyl, Phenyl methacrylate, methacrylic acid 2,2,2- trifluoro ethyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, first Base isobornyl acrylate, methacrylic acid 2- methoxy acrylate, methoxy triethylene methacrylate, methacrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxybutyl, methacrylic acid 2- methyl -2- gold Rigid alkyl ester, methacrylic acid 2- propyl -2- Buddha's warrior attendant alkyl ester, methacrylic acid 8- methyl -8- tricyclodecyl and methacrylic acid 8- Ethyl -8- tricyclodecyl etc..

As vinyl compound, for example, vinyl ethers, methyl vinyl ether, benzyl vinyl ether, 2- hydroxyl Base ethyl vinyl ether, Vinyl phenyl ether and propyl vinyl ether etc..

As distyryl compound, for example, styrene, methyl styrene, chlorostyrene, bromstyrol etc..

As maleimide compound, for example, maleimide, N- methylmaleimido, N- phenyl horse Come acid imide and N- N-cyclohexylmaleimide etc..

For the manufacturing method of at least two kinds of polymer of the invention, it is not particularly limited, can use industrial processing General method.Specifically, can by monomer with structural unit shown in above-mentioned formula (a), have and above-mentioned formula (a) Shown in the different photoreactivity position in photoreactivity position photoreactivity side chain monomer (M1) and liquid crystal liquid crystal property side chain monomer (M2) using the cationic polymerization of vinyl, free radical polymerization, anionic polymerisation and manufacture.Wherein, from the appearance of reaction controlling The viewpoints such as easy property are set out, particularly preferred free radical polymerization.

As the polymerization initiator of free radical polymerization, radical polymerization initiator, reversible addition-breaking type chain can be used Shift compound well known to (RAFT) polymerization agent etc..

Free radical thermal polymerization is the compound generated free radicals and being heated to decomposition temperature or more.As this Kind of free radical thermal polymerization, for example, can enumerate peroxidating ketone (methyl ethyl ketone peroxide, Cyclohexanone peroxides etc.), Diacyl peroxide class (acetyl peroxide, benzoyl peroxide etc.), hydroperoxide kind (hydrogen peroxide, tertiary fourth Base hydrogen peroxide, cumene hydroperoxide etc.), dialkyl peroxide class (di-tert-butyl peroxide, dicumyl peroxide, Dilauroyl peroxide etc.), ketal peroxide class (dibutyl cyclohexane peroxide etc.), alkyl super-acid ester class (peroxidating The neodecanoic acid tert-butyl ester, tert-Butyl peroxypivalate, peroxidating 2- cyclohexyl alkanoic acid-tert-pentyl ester etc.), persulfuric acid salt (mistake Potassium sulfate, sodium peroxydisulfate, ammonium persulfate etc.), (azodiisobutyronitrile and 2,2 '-two (2- hydroxyethyls) are even for azo compound Nitrogen bis-isobutyronitrile etc.).This free radical thermal polymerization can be used alone, or can also be applied in combination 2 kinds with On.

Radical photopolymerization initiator does not limit especially as long as irradiating the compound for causing free radical polymerization by light It is fixed.As such radical photopolymerization initiator, benzophenone, Michler's keton, 4,4 '-bis- (diethylaminos) two can be enumerated Benzophenone, xanthone, thioxanthones, isopropyl xanthone, 2,4- diethyl thioxanthone, 2- ethyl hydrazine, acetophenone, 2- hydroxyl Base -2- methyl phenyl ketone, 2- hydroxy-2-methyl -4 '-cumene acetone, 1- hydroxycyclohexylphenylketone, cumene acyloin Ether, isobutyl benzoin ether, 2,2- diethoxy acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, camphorquinone, benzanthracene Ketone, 2- methyl-1-[4- (methyl thio) phenyl]-2- morpholinopropane-1- ketone, 2- benzyl-2- dimethylamino-1- (4- Quinoline base phenyl)-butanone -1,4- dimethyl amino benzoate, 4- dimethylaminobenzoic acid isopentyl ester, 4,4 '-two (tertiary fourths Base crosses oxygen carbonyl) benzophenone, 3,4,4 '-three (t-butyl peroxy carbonyl) benzophenone, 2,4,6- trimethylbenzoyl two Phenyl phosphine oxide, bis- (the trichloromethyl)-s-triazine of 2- (4 '-methoxyl-styrene) -4,6-, 2- (3 ', 4 '-dimethoxy benzenes Vinyl) bis- (the trichloromethyl)-s-triazine of -4,6-, 2- (2 ', 4 '-dimethoxy-styryl) -4,6- be bis- (trichloromethyl) - S-triazine, bis- (the trichloromethyl)-s-triazine of 2- (2 '-methoxyl-styrene) -4,6-, 2- (4 '-amyl oxygroup styryl) - Bis- (the trichloromethyl)-s-triazine of 4,6-, 4- [p- N, N- bis- (ethoxy carbonyl methyl)] -2,6- two (trichloromethyl)-equal three Bis- (trichloromethyl) -5- (2 '-the chlorphenyl)-s-triazine of piperazine, 1,3-, bis- (the trichloromethyl) -5- (4 '-methoxyphenyl)-of 1,3- S-triazine, 2- (to dimethylaminostyryl) benzoxazoles, 2- (to dimethylaminostyryl) benzothiazole, 2- mercapto Base benzothiazole, 3,3 '-carbonyls bis- (7- diethyl amino coumarins), -4,4 ', 5,5 '-tetraphenyl -1 2- (Chloro-O-Phenyl), 2 '-bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (4- carboethoxyphenyl) -1,2 '-bisglyoxalines, 2,2 ' - Bis- (2,4 dichloro benzene base) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines, 2,2 ' bis- (2,4- dibromo phenyls) -4,4 ', 5,5 ' - Tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4,6- trichlorophenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines, 3- (2- Methyl -2- dimethylamino propiono) carbazole, bis- (2- methyl -2- morpholinyl the propiono) -9- dodecyl carbazoles of 3,6-, 1- hydroxycyclohexylphenylketone, bis- (5-2,4- cyclopentadiene -1- bases)-are bis- (the fluoro- 3- of 2,6- bis- (1H- pyrroles -1- base)-phenyl) Titanium, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary hexyl crosses oxygen carbonyl) benzophenone, 3,3 '-two (methoxycarbonyl) -4,4 '-two (t-butyl peroxy carbonyl) benzophenone, 3,4 '-two (methoxycarbonyls) -4,3 ' - Two (t-butyl peroxy carbonyl) benzophenone, 4,4 '-two (methoxycarbonyl) -3,3 '-two (t-butyl peroxy carbonyl) hexichol first Ketone, 2- (3- methyl -3H- benzothiazole -2- subunit) -1- naphthalene -2- base-ethyl ketone or 2- (3- methyl-1,3- benzothiazole -2 (3H)-subunit) -1- (2- benzoyl) ethyl ketone etc..These compounds can be used alone, and can also mix two or more use.

Radical polymerization is not particularly limited, and emulsion polymerization can be used, suspension polymerization, dispersion copolymerization method, sink Shallow lake polymerization, mass polymerization, solution polymerization process etc..

As make with show photoreactivity and liquid crystal liquid crystal property structure monomer (M1)；It is only shown with (M-2) The monomer (M2) of the structure of liquid crystal liquid crystal property is copolymerized and respectively obtains organic molten used in the reaction of at least two kinds of polymer of the invention Agent is not particularly limited as long as that can dissolve high molecular solvent generated.Its concrete example is enumerated below.

It can enumerate: N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl- 2-Pyrrolidone, N- methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-fourth Lactone, isopropanol, methoxy amylalcohol, cinene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, Methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl card must Alcohol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyl acetic acid Ester, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, fourth Acid butyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, dioxanes, n-hexane, pentane, normal octane, diethyl The positive fourth of ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid Ester, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-c acid methyl Ethyl ester, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxypropionic acid Butyl ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanone, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide etc..

These organic solvents can be used alone, and can also be used in mixed way.In turn, even not dissolving polymerization generated The solvent of object, as long as can also mix in the range of polymer generated will not be precipitated to above-mentioned organic solvent It uses.

In addition, the oxygen in organic solvent can become the reason of hindering polymerization reaction, therefore organic molten in free radical polymerization Agent uses after preferably deaerating as much as possible.

Polymerization temperature when free radical polymerization can choose 30 DEG C~150 DEG C of arbitrary temp, and 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 %.Initial reaction stage is carried out with high concentration, can add organic solvent later.

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]

When recycling polymer generated from the reaction solution obtained using above-mentioned reaction, reaction solution is put into bad Precipitate these polymer in solvent.As the poor solvent for precipitating, methanol, acetone, hexane, heptan can be enumerated Alkane, butyl cellosolve, heptane, methyl ethyl ketone, methylisobutylketone, ethyl alcohol, toluene, benzene, ether, ethyl methyl ether, water etc..It puts into bad The polymer precipitated in solvent can carry out air drying under normal or reduced pressure or heating is dry after being recovered by filtration It is dry.In addition, repeating the operation that the polymer that 2 times~10 times recycle precipitating is re-dissolved in organic solvent and reprecipitation recycling When, the impurity in polymer can be reduced.As poor solvent at this time, such as alcohols, ketone, hydrocarbon can be enumerated etc., it uses When 3 kinds or more poor solvents among these, purification efficiency is further increased, so it is preferred that.

About the high molecular molecular weight of (A) side chain type of the invention, behaviour when gained applies film strength, film formation is considered In the case where the property made and the uniformity of film, GPC (gel permeation chromatography (Gel Permeation is utilized Chromatography the)) weight average molecular weight preferably 2000~2000000, more preferable 5000~150000 of method measurement.Alternatively, Foresaid weight average molecular weight preferably 2000~1000000, more preferable 5000~200000.

< < (B) organic solvent > >

As long as capableing of having for dissolving resin ingredient for the organic solvent in polymer composition used in the present invention Solvent is just not particularly limited.It is exemplified below out its specific example.

Can enumerate: N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- methyl oneself Lactams, 2-Pyrrolidone, N- ethyl pyrrolidone, n-vinyl pyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, two Methyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- dimethyl propionyl Amine, 3- butoxy-N, N- dimethylpropionamide, 1,3- dimethyl-2-imidazolidinone, ethylpentyl ketone, methyl nonyl ketone, first and second Ketone, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4- hydroxyl Base -4-methyl-2 pentanone, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethyl Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, two Dihydroxypropane single-ether, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- Methyl -3- methoxybutyl acetic acid esters, tripropylene glycol methyl ether etc..These can be used alone, and can also be used in mixed way.

< < any ingredient > >

Polymer composition used in the present invention can contain the ingredient in addition to above-mentioned (A), (B) and (C) ingredient.Make For its example, can enumerate for improving film thickness uniformity, the solvent of surface smoothness, chemical combination in coated polymeric composition Object, compound of adaptation for improving liquid crystal orientation film and substrate etc., but not limited thereto.

As the concrete example of the solvent (poor solvent) for improving film thickness uniformity, surface smoothness, can enumerate with Lower solvent.

Such as isopropanol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, first can be enumerated Base cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, second two Alcohol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol list Methyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, two Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate list ether, two Propylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3- Methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, two isobutyls Ketone, methylcyclohexene, propyl ether, two hexyl ethers, 1- hexanol, n-hexane, pentane, normal octane, diethyl ether, methyl lactate, lactic acid second Ester, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3- first Oxygroup methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, 1- methoxy-2-propanol, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- Propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- monomethyl ether -2- acetic acid esters, Propylene glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-c oxygroup) propyl alcohol, methyl lactate, ethyl lactate, cream Sour n-propyl, n-butyl lactate, isoamyl lactate etc. have the solvent etc. of low surface tension.

These poor solvents can be used a kind, can also be used in mixed way a variety of.When using solvent as described above, it is The dissolubility of the solvent for including in polymer composition entirety is significantly reduced, preferably 5 mass % of solvent entirety~ 80 mass %, 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 system), Megafac (registered trademark) F171, F173, R-30 (DICCORPORATION system), Fluorad FC430, FC431 (Sumitomo 3M Limited system), AsahiGuard (registered trademark) AG710 (Asahi Glass Co., Ltd System), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC SEIMI CHEMICALCO., LTD. system) etc..The use ratio of these surfactants is relative to the resin contained in polymer composition 100 mass parts of ingredient are preferably 0.01 mass parts~2 mass parts, more preferably 0.01 mass parts~1 mass parts.

The concrete example of compound as the adaptation for improving liquid crystal orientation film and substrate can enumerate described below Siliceous hydride compounds of functionality etc..

Such as 3- TSL 8330,3-aminopropyltriethoxysilane, 2- aminopropyl can be enumerated Trimethoxy silane, 2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- TSL 8330, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- ureido-propyl trimethoxy silane, three second of 3- ureido-propyl Oxysilane, N- ethoxy carbonyl -3- TSL 8330, N- ethoxy carbonyl -3- aminopropyl triethoxy Silane, N- triethoxysilylpropyltetrasulfide diethylenetriamine, N- trimethoxy-silylpropyl diethylenetriamine, Three azepine decane of 10- trimethoxysilyl -1,4,7-, three azepine decane of 10- triethoxysilyl -1,4,7-, 9- Trimethoxysilyl -3,6- diaza nonyl acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyl acetic acid Ester, N- benzyl -3- TSL 8330, N- benzyl -3-aminopropyltriethoxysilane, N- phenyl -3- amino Bis- (oxygen the ethylidene) -3- aminopropyl front threes of propyl trimethoxy silicane, N- phenyl -3-aminopropyltriethoxysilane, N- Bis- (oxygen ethylidene) -3-aminopropyltriethoxysilane of oxysilane, N- etc..

By backlight when in turn, in order to improve the adaptation of substrate and liquid crystal orientation film and prevent from constituting liquid crystal expression element Caused electrical characteristics reduction etc., can contain phenoplasts system as following, chemical combination containing epoxy group in polymer composition The additive of object.Specific phenoplasts system additive described below, but it is not limited to the structure.

As specific contains epoxides, it is sweet that ethylene glycol diglycidylether, polyethylene glycol diglycidyl can be exemplified Oily ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol two Glycidol ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycol 2-glycidyl Ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycol, N, N, N ', N '-four glycidyl group m-xylene diamine, 1,3- it is bis- (N, N- diglycidyl amino methyl) hexamethylene, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl-methane etc..

When using improving the compound with the adaptation of substrate, dosage is relative to the resin contained in polymer composition 100 mass parts of ingredient are preferably 0.1 mass parts~30 mass parts, more preferably 1 mass parts~20 mass parts.Dosage is lower than 0.1 When mass parts, the effect for improving adaptation can not be expected, when being more than 30 mass parts, the orientation of liquid crystal is deteriorated sometimes.

As additive, photosensitizer also can be used.Preferably colourless sensitizer and triplet sensitizer.

As photosensitizer, there are aromatic nitro compound, cumarin (7- lignocaine -4- methylcoumarin, 7- hydroxyl Base -4- methylcoumarin), coumarin ketone, carbonyl bicoumarin, aromatic series -2- hydroxy-ketone and the fragrance replaced by amino (2- dihydroxy benaophenonel, single pair (dimethylamino) -2- dihydroxy benaophenonel or two are to (dimethylamino) -2- hydroxyl for race's -2- hydroxy-ketone Base benzophenone), acetophenone, anthraquinone, xanthone, thioxanthones, benzanthrone, thiazoline (2- benzoyl methylene -3- first Base-β-aphthothiazoles quinoline, 2- (β-naphthoyl methylene) -3- methylbenzothiazole quinoline, 2- (α-naphthoyl methylene) -3- methyl Benzothiazoline, 2- (4- biphenyl Acylmethylene) -3- methylbenzothiazole quinoline, 2- (β-naphthoyl methylene) -3- methyl-β - Aphthothiazoles quinoline, 2- (4- biphenyl Acylmethylene) -3- methyl-β-aphthothiazoles quinoline, 2- (to fluorobenzoyl methylene) -3- Methyl-β-aphthothiazoles quinoline), ((β-naphthoyl is sub- by 2- benzoyl methylene -3- methyl-β-aphthoxazoles quinoline, 2- for oxazoline Methyl) -3- methylbenzoxazole quinoline, 2- (α-naphthoyl methylene) -3- methylbenzoxazole quinoline, 2- (4- biphenyl acyl group methylene Base) -3- methylbenzoxazole quinoline, 2- (β-naphthoyl methylene) -3- methyl-β-aphthoxazoles quinoline, 2- (4- biphenyl acyl group methylene Base) -3- methyl-β-aphthoxazoles quinoline, 2- (to fluorobenzoyl methylene) -3- methyl-β-aphthoxazoles quinoline), benzothiazole, Nitroaniline (meta nitro aniline or paranitroanilinum, 2,4,6- trinitroaniline) or nitro acenaphthene (5- nitro acenaphthene), (2- [(hydroxyl Base is to methoxyl group) styryl] benzothiazole, benzoin alkylether, N- alkylation phthalein ketone (N-alkyl phthalone), benzene Ethyl ketone ketal (2,2- Dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2- naphthalene methanol, 2- naphthalene-carboxylic acid, 9- anthryl carbinol and 9- anthracene carboxylic acid), benzene And pyrans, azo indolizine, methylcoumarin etc..

Preferably aromatic series -2- hydroxy-ketone (benzophenone), cumarin, coumarin ketone, carbonyl bicoumarin, acetophenone, Anthraquinone, xanthone, thioxanthones and acetophenone ketal.

In polymer composition, apart from the above, as long as the range that does not impair the effect of the present invention, so that it may for changing Become the purposes of electrical characteristics such as dielectric constant, the electric conductivity of liquid crystal orientation film and add dielectric, conductive materials, and then for raising The hardness of film when liquid crystal orientation film is made, the purpose of consistency and add cross-linked compound.

[preparation of polymer composition]

Polymer composition used in the present invention is preferably in a manner of being suitable for forming liquid crystal orientation film with coating fluid Form preparation.That is, polymer composition used in the present invention is preferably prepared as a solution, the solution is in organic solvent In dissolved with above-mentioned (A) ingredient and it is above-mentioned for improve film thickness uniformity, the solvent of surface smoothness, compound, for improving The compound etc. of the adaptation of liquid crystal orientation film and substrate.Herein, the content of (A) ingredient preferably 1 mass of mass %~20 %, more It is preferred that 3 mass of mass %~15 %, the particularly preferred 3 mass mass of %~10 %.

In the polymer composition of present embodiment, in addition to (A) ingredient, liquid crystal expressive ability and photonasty are not being damaged Other polymers can be mixed in the range of energy.At this point, the content of the other polymers in resin component be 0.5 mass %~ 80 mass %, preferably 1 mass of mass %~50 %.

Such other polymers are for example formed by poly- (methyl) acrylate, polyamic acid, polyimides etc., Ke Yiju It is not that can show high molecular polymer of photonasty side chain type of liquid crystal liquid crystal property etc. out.

The manufacturing method > that there is < manufacturing method > and the < liquid crystal of the substrate of liquid crystal orientation film to indicate element

The manufacturing method of substrate with liquid crystal orientation film of the invention has following process:

Polymer composition is coated on the substrate of the conductive film with transverse electric field driving and forms film by [I] Process, the polymer composition are characterized in that, contain (A) side chain type macromolecule and (B) organic solvent, (A) side chain Type macromolecule has: side chain (a1) with photoreactivity position shown in above-mentioned formula (a), have with shown in above-mentioned formula (a) The side chain (a2) at the different photoreactivity position in photoreactivity position and the side chain (a3) for showing liquid crystal liquid crystal property；

The process that [III] heats film obtained in [II].

By above-mentioned operation, the available driving liquid crystal of transverse electric field for having been assigned tropism control ability indicates element With liquid crystal orientation film, the available substrate with the liquid crystal orientation film.

In the 2nd mode of the invention, the manufacturing method of the substrate with liquid crystal orientation film of the invention has following process:

The process that [III] heats film obtained in [II].

In addition, preparing the 2nd substrate in addition to substrate obtained above (the 1st substrate), driven so as to obtain transverse electric field Ejector half liquid crystal indicates element.

2nd substrate is replaced using the substrate of the conductive film without transverse electric field driving with transverse electric field driving The substrate of conductive film, in addition to this, by (not having transverse electric field driving use due to using using above-mentioned operation [I]~[III] Conductive film substrate, therefore, it is convenient for the sake of brief note makees process [I ']~[III '] sometimes in the application), it is available to have Have been assigned the 2nd substrate of the liquid crystal orientation film of tropism control ability.

The driving liquid crystal of transverse electric field indicates that the manufacturing method of element has following process:

[IV] in such a way that the liquid crystal orientation film of the 1st substrate and the 2nd substrate is across liquid crystalline phase pair, relative configuration obtains among the above The 1st substrate arrived and the 2nd substrate, to obtain the process that liquid crystal indicates element.

Thus, it is possible to which obtaining the driving liquid crystal of transverse electric field indicates element.

Hereinafter, being illustrated for each process of [I]~[III] and [IV] that the manufacturing method of the present invention has.

< process [I] >

In process [I], coating is containing in defined temperature model on the substrate of the conductive film with transverse electric field driving It shows the photonasty side chain type macromolecule of liquid crystal liquid crystal property and the polymer composition of organic solvent in enclosing and forms film.

< substrate >

It is not particularly limited for substrate, the liquid crystal to be manufactured indicates when element is transmission-type, it is preferable to use the transparency is high Substrate.It is not particularly limited at this time, the plastic bases such as glass substrate or acrylic compounds substrate, polycarbonate substrate can be used Deng.

Additionally, it is contemplated that the liquid crystal in reflection-type indicates the application in element, the opaque base such as Silicon Wafer also can be used Plate.

The conductive film > of < transverse electric field driving

Substrate has the conductive film of transverse electric field driving.

As the conductive film, in the case that liquid crystal indicates that element is transmission-type, ITO (Indium Tin can be enumerated Oxide: tin indium oxide), IZO (Indium Zinc Oxide: indium zinc oxide) etc., but be not limited to these.

In addition, in the case that the liquid crystal of reflection-type indicates element, as conductive film, the material of the reflected lights such as aluminium can be enumerated Deng, but it is not limited to these.

The method that conductive film is formed on substrate can use known method.

The method above-mentioned polymer composition being coated on the substrate of the conductive film with transverse electric field driving does not have It is particularly limited to.

About coating method, industrial is usually to be carried out using silk-screen printing, hectographic printing, flexible printing or ink-jet method etc. 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 of the conductive film with transverse electric field driving after coated polymeric composition, can use hot plate, The heating meanss such as thermal cycle type baking oven or IR (infrared ray) type baking oven, steam solvent at 50~200 DEG C, preferably 50~150 DEG C It sends out and obtains film.Drying temperature at this time is preferably shorter than the high molecular liquid crystalline phase performance temperature of side chain type.

When the thickness of film is blocked up, liquid crystal indicate element power consumption in terms of be it is unfavorable, 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, can also be arranged will be formed with the substrate of film after [I] process, before next [II] process The process being cooled to room temperature.

< process [II] >

In process [II], polarized UV rays are irradiated to film obtained in process [I].It is purple to the film surface irradiation polarization of film When outside line, polarized UV rays are irradiated to substrate from certain orientation across polarizing film.As the ultraviolet light used, wavelength can be used For the ultraviolet light of 100nm~400nm range.Preferably, it according to the film type used, is selected by filter etc. optimal Wavelength.Also, such as can choose using wavelength be 290nm~400nm range ultraviolet light, so as to selectively induce Photo-crosslinking.As ultraviolet light, the light issued by high-pressure sodium lamp can be used for example.

For the exposure of polarized UV rays, depending on the film used.About exposure, it is preferably set to realize as follows In the range of the 1%~70% of the amount of the polarized UV rays of the maximum value (hereinafter also referred to Δ Amax) of Δ A, more preferably it is set as In the range of 1%~50%, the Δ A be the film, be parallel to polarized UV rays polarization direction direction ultraviolet light Absorbance and perpendicular to polarized UV rays polarization direction direction ultraviolet absorbance difference.

< process [III] >

In process [III], the film of polarized UV rays has been irradiated in heating in process [II].Painting can be assigned by heating Film tropism control ability.

The heating meanss such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven can be used in heating.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 temperature (the hereinafter referred to as liquid crystal sex expression temperature that side chain type macromolecule can show liquid crystal liquid crystal property Degree) within the temperature range of.In the case where film surface as film, it is contemplated that the liquid crystal sex expression temperature of film coated surface is lower than Liquid crystal when observation can show the photonasty side chain type macromolecule of liquid crystal liquid crystal property in body phase (bulk) shows temperature.Therefore, it heats Temperature is more preferably within the temperature range of the liquid crystal sex expression temperature of film coated surface.That is, the heating temperature after irradiation polarized UV rays The temperature range of degree is preferred are as follows: the lower limit of the temperature range of liquid crystal sex expression temperature more high molecular than used side chain type is low 10 DEG C of temperature as lower limit, using low 10 DEG C of the temperature of the upper limit than the liquid crystal temperature range as the temperature of the range of the upper limit. When heating temperature is lower than above-mentioned temperature range, there are being increased in film by hot bring anisotropy, effect is insufficient to incline To in addition, when heating temperature is excessively high compared with above-mentioned temperature range, there are film states close to isotropic liquid condition The tendency of (isotropic phase), at this point, 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 are from the opposite liquid crystal of solid The glass transition temperature (Tg) of phase transition or more mutually occurs and from the opposite isotropic phase of liquid crystal (isotropic phase) Isotropic phase transition temperature (Tiso) temperature below of phase transition occurs.

By with process as above, in the manufacturing method of the present invention, can be realized film is efficiently imported it is each to different Property.Further, it is possible to efficiently manufacture the substrate with liquid crystal orientation film.

< process [IV] >

[IV] process is following process: will have liquid obtained in [III] on the conductive film of transverse electric field driving The substrate (the 1st substrate) of brilliant alignment films, the band liquid without conductive film obtained in above-mentioned [I ']~[III '] in the same manner as The substrate (the 2nd substrate) of brilliant alignment films is oppositely disposed across liquid crystal, in the opposite mode of the liquid crystal orientation film of the two, using known Method make liquid crystal cells, the driving liquid crystal of production transverse electric field indicates element.It should be noted that for process [I ']~ [III '] replaces that there is the transverse electric field to drive in process [I] using the substrate without transverse electric field driving conductive film In addition to this substrate of conductive film can be carried out similarly with process [I]~[III].Process [I]~[III] and process [I ']~[III's '] the difference is that only the presence or absence of above-mentioned conductive film, therefore, omit the explanation of process [I ']~[III '].

If enumerating liquid crystal cells or liquid crystal indicates a production example of element, following method can be exemplified: in preparation The 1st substrate stated and the 2nd substrate spread spacer on the liquid crystal orientation film of a substrate, so that liquid crystal alignment film surface becomes The method of another substrate, decompression injection liquid crystal and sealing is pasted in inside；Alternatively, to the liquid crystal orientation film for being scattered with spacer After liquid crystal is added dropwise in face, adhesive substrate and the method etc. being sealed.At this time, it is preferred that unilateral substrate, which uses, to be had laterally The substrate of the electrode of structure as the comb teeth of electric field driven.The diameter of spacer at this time is preferably 1 μm~30 μm, more excellent It is selected as 2 μm~10 μm.The spacer diameter can determine the thickness of the spacing of a pair of of substrate of clamping liquid crystal layer, i.e. liquid crystal layer.

In the manufacturing method of substrate with film of the invention, polymer composition is coated on substrate and forms film Afterwards, polarized UV rays are irradiated.Then, it by being heated, realizes to side chain type polymeric membrane and efficiently imports anisotropy, from And manufacture the substrate with the liquid crystal orientation film for having liquid crystal aligning control ability.

In the film that the present invention uses, the molecule that the light reaction using side chain and the self assembly based on liquid crystal liquid crystal property are induced is again The principle of orientation, realization efficiently import anisotropy to film.In the manufacturing method of the present invention, have in side chain type macromolecule In the case where 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, production liquid crystal indicates element.

Therefore, film used in method of the invention irradiates at polarized UV rays and heating film by successively carrying out Reason, can efficiently import anisotropy and the excellent liquid crystal orientation film of tropism control ability is made.

In addition, to film used in method of the invention, optimize the exposures of the polarized UV rays that film irradiate with The heating temperature of heat treatment.Thus, it is possible to realize efficiently to import anisotropy to film.

The irradiation of optimal polarized UV rays for efficiently importing anisotropy to film used in the present invention Photo-crosslinking, photoisomerization reacts or the amount of light Fries rearrangement reaches with occurring photonasty group in the film for amount It is corresponding to optimal polarized UV rays exposure.To the irradiation polarized UV rays of film used in the present invention as a result, carrying out When the photonasty group of the side chain of photo-crosslinking, photoisomerization reaction or light Fries rearrangement is few, it is not achieved enough Light reaction amount.At this point, sufficient self assembly will not be carried out being heated later.On the other hand, for making in the present invention For film, to the structured illumination polarized UV rays with photocrosslinking reaction group as a result, carrying out the side chain of cross-linking reaction Photonasty group excess when, the cross-linking reaction between side chain can be carried out excessively.At this point, resulting film becomes upright and outspoken, hamper sometimes The progress of self assembly brought by heating after hindering.In addition, for the film used in the present invention, to not sharp with light This reset group structured illumination polarized UV rays as a result, carry out light Fries rearrangement side chain photonasty group become When obtaining excessive, the liquid crystal liquid crystal property of film can be reduced excessively.At this point, the liquid crystal liquid crystal property of resulting film also reduces, after sometimes interfering with The progress of self assembly brought by heating.When in turn, to the structured illumination polarized UV rays with light fries' rearrangement group, if Ultraviolet irradiation amount is excessive, then photodegradation occurs for side chain type macromolecule, from group brought by the heating after sometimes interfering with The progress of dress.

Therefore, in film used in the present invention, the photonasty group of side chain occurs because of the irradiation of polarized UV rays The optimised quantity of photo-crosslinking, photoisomerization reaction or light Fries rearrangement, which is preferably set to the side chain type polymeric membrane, to be had 0.1 mole of %~40 mole % of some photonasty groups, is more preferably set as 0.1 mole of %~20 mole %.By making to occur The amount of the photonasty group of the side chain of light reaction is such range, and the self assembly in heat treatment later efficiently carries out, The anisotropy in film can be efficiently formed.

In film used in method of the invention, optimize side chain type high score by optimizing the exposure of polarized UV rays Photo-crosslinking, the photoisomerization of photonasty group in the side chain of sub- film react or the amount of light Fries rearrangement.Also, It is realized together with heat treatment later and efficiently imports anisotropy into film used in the present invention.At this point, for suitable The polarized UV rays amount of conjunction can be carried out based on the evaluation of the UV absorption of film used in the present invention.

That is, for the present invention used in film, measure respectively polarized UV rays irradiation after, be parallel to polarized UV The ultraviolet radiation absorption in the direction of the polarization direction of line and perpendicular to polarized UV rays polarization direction direction ultraviolet radiation absorption. Δ A is evaluated by the measurement result of UV absorption, the Δ A is the side of the polarization direction for being parallel to polarized UV rays in the film To ultraviolet absorbance and perpendicular to polarized UV rays polarization direction direction ultraviolet absorbance difference.Also, it asks The maximum value (Δ Amax) of the Δ A realized in film used in the present invention out and realize its polarized UV rays exposure. In the manufacturing method of the present invention, using the polarized UV rays exposure of realization Δ Amax as benchmark, it can determine and taken in liquid crystal The polarized UV rays amount for the preferred amounts irradiated into the manufacture of film.

In the manufacturing method of the present invention, preferably by the exposure for the polarized UV rays irradiated to film used in the present invention It is set as in the range of realize the amount of the polarized UV rays of Δ Amax 1%~70%, is more preferably set as 1%~50% range It is interior.In film used in the present invention, the polarization in the range of the 1%~50% of the amount of the polarized UV rays of Δ Amax is realized Ultraviolet irradiation amount, which is equivalent to, makes 0.1 mole of %~20 of the entirety of photonasty group possessed by the side chain type polymeric membrane rub The amount of the polarized UV rays of photo-crosslinking occurs for your %.

As described above, in the manufacturing method of the present invention, anisotropy is efficiently imported to film to realize, with the side The high molecular liquid crystal temperature range of chain determines suitable heating temperature as described above as benchmark.Thus, for example this hair Heating when the high molecular liquid crystal temperature range of side chain type used in bright is 100 DEG C~200 DEG C, after irradiating polarized UV rays It is ideal that temperature, which is 90 DEG C~190 DEG C,.It sets, in film used in the present invention, imparts bigger each in this way Anisotropy.

Operate in this way, liquid crystal provided by the present invention indicate element to the outside stimulus such as light, heat show it is high can By property.

Operation as above, the driving liquid crystal of the transverse electric field manufactured by means of the present invention indicate component substrate or The driving liquid crystal of transverse electric field with the substrate indicates that the reliability of element becomes excellent, can be suitable for big picture and height Clearly LCD TV etc..

Hereinafter, illustrating the present invention using embodiment, but the present invention is not limited to the embodiments.

Embodiment

Below as the monomer used in embodiment with photoreactive group, M1, M2 are shown, as with liquid crystal liquid crystal property The monomer of group, shows M3, as the monomer of crosslinked group, shows HBAGE, and as the monomer with amide groups, show A1。

M1, M2, M3 following synthesis respectively.That is, M1 is closed with the synthetic method recorded in patent document (WO2011-084546) At.Synthetic method synthesis of the M2 to be recorded in patent document (WO2014/054785 pamphlet).(Japan is special with patent document by M3 Open flat 9-118717) in record synthetic method synthesis.It should be noted that there is light reaction using the polymer that M1 is formed as monomer Property and liquid crystal liquid crystal property, only have liquid crystal liquid crystal property using the polymer that M3 is formed as monomer.

Synthetic method synthesis of the monomer A1 of copolymerization to be recorded in patent document (WO2014/054785 pamphlet).

HBAGE (hydroxybutyl acrylate glycidol ether) uses the commercially available product bought of energy.

In addition, the abbreviation of reagent used in the present embodiment described below.

(Diisocyanate component)

ISPDA: isophorone diisocyanate

(diamine component)

DDM:4,4 '-diaminodiphenyl-methane

Me-4APhA:N- methyl -2- (4- aminophenyl) ethylamine

Me-DADPA:4,4 '-diamino-diphenyl (N- methyl) amine

(tetracarboxylic dianhydride)

TDA:3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dianhydride

(organic solvent)

THF: tetrahydrofuran

NMP:N- ethyl-2-pyrrolidone

BCS: butyl cellosolve

(polymerization initiator)

AIBN:2,2 '-azodiisobutyronitrile

< light orientation Macroscopic single crystal example P1 >

It is dissolved in M1 (2.99g:0.15mol%), M2 (1.31g:0.05mol%), M3 (14.71g:0.80mol%) In NMP (79.21g), after being de-gassed with diaphragm pump, AIBN (0.30g) is added and is de-gassed again.Later, with 60 DEG C of reactions 8 Hour, obtain the polymer solution of methacrylate.The polymer solution is added dropwise in methanol (450ml), gained is precipitated Object filtering.The sediment is cleaned with methanol, is dried under reduced pressure, obtains methacrylate polymer powder P1.

< light orientation Macroscopic single crystal example P2~P3 >

It is formed using shown in table 1, in addition to this, utilizes method same as light orientation Macroscopic single crystal example P1, synthesis Methacrylate polymer powder P2~P3.

[table 1]

< Macroscopic single crystal example closes L1 >

TDA 4.85g used as tetracarboxylic dianhydride's ingredient, the ISPDA3.67g as Diisocyanate component, conduct DDM 5.89g, Me-DADPA 0.35g, the Me-4APhA 0.25 of diamine component react 18 in NMP85.06g at room temperature Hour, the concentration for obtaining polyamic acid (L1) is the solution of 15wt%.

1 > of < embodiment

Methacrylate polymer powder obtained in light orientation Macroscopic single crystal example P1 is added in NMP (12.8g) P1 (1.2g) is stirred at room temperature 1 hour and makes it dissolve.Later, BCS (6.0g) is added and stirs, so that it is molten to obtain polymer Liquid T1.Polymer solution T1 is directly as the aligning agent for liquid crystal for being used to form liquid crystal orientation film.

2 > of < embodiment

Methacrylate polymer powder obtained in light orientation Macroscopic single crystal example P1 is added in NMP (8.04g) P1 (0.36g) is stirred at room temperature 1 hour and makes it dissolve.Polyamides obtained in Macroscopic single crystal example L1 is added in the solution Amino acid solution L1 (5.6g) and BCS (6.0g) is simultaneously stirred, to obtain polymer solution T2.Polymer solution T2 directly makees For the aligning agent for liquid crystal for being used to form liquid crystal orientation film.

< compares 1 >

Methacrylate polymer powder obtained in light orientation Macroscopic single crystal example P2 is added in NMP (12.8g) P2 (1.2g) is stirred at room temperature 1 hour and makes it dissolve.Later, BCS (6.0g) is added and stirs, so that it is molten to obtain polymer Liquid CT1.Polymer solution CT1 is directly as the aligning agent for liquid crystal for being used to form liquid crystal orientation film.

< compares 2 >

Methacrylate polymer powder obtained in light orientation Macroscopic single crystal example P3 is added in NMP (12.8g) P3 (1.2g) is stirred at room temperature 1 hour and makes it dissolve.Later, BCS (6.0g) is added and stirs, so that it is molten to obtain polymer Liquid CT2.Polymer solution CT2 is directly as the aligning agent for liquid crystal for being used to form liquid crystal orientation film.

< compares 3 >

Methacrylate polymer powder obtained in light orientation Macroscopic single crystal example P2 is added in NMP (8.04g) P2 (0.36g) is stirred at room temperature 1 hour and makes it dissolve.Polyamides obtained in Macroscopic single crystal example L1 is added in the solution Amino acid solution L1 (5.6g) and BCS (6.0g) is simultaneously stirred, to obtain polymer solution CT3.Polymer solution CT3 is direct As the aligning agent for liquid crystal for being used to form liquid crystal orientation film.

< compares 4 >

Methacrylate polymer powder obtained in light orientation Macroscopic single crystal example P3 is added in NMP (8.04g) P3 (0.36g) is stirred at room temperature 1 hour and makes it dissolve.Polyamides obtained in Macroscopic single crystal example L1 is added in the solution Amino acid solution L1 (5.6g) and BCS (6.0g) is simultaneously stirred, to obtain polymer solution CT4.Polymer solution CT4 is direct As the aligning agent for liquid crystal for being used to form liquid crystal orientation film.

Aligning agent for liquid crystal T1~2 for Examples 1 to 2 and compare 1~4 aligning agent for liquid crystal CT1~CT4, it is below The type of polymer and its content, the content of other polymers and solvent and its content used is summarized in table 2.

[table 2]

The production > of < liquid crystal cells

After 0.45 μm of filter filtering of aligning agent for liquid crystal obtained in embodiment 1 (T1), it is spun on transparent electricity On the glass substrate of pole, after 90 seconds dry on 70 DEG C of hot plate, the liquid crystal orientation film of film thickness 100nm is formed.Then, to film Ultraviolet light 5~30mJ/cm of the face across polarization plate irradiation 313nm²Afterwards, it is heated 10 minutes on 150 DEG C of hot plate, obtains band The substrate of liquid crystal orientation film.Substrate with liquid crystal orientation film as preparing 2, sets in the liquid crystal alignment film surface of a substrate After setting 6 μm of spacer, with the brushing direction of 2 substrates become parallel mode combine, make liquid crystal injecting port remain and will be all Enclose sealing, the dummy cell that production unit gap is 4 μm.Liquid crystal MLC-3019 is injected in the dummy cell by depressurizing injection method (Merck Co. Ltd. system), inlet is sealed, and obtains the parallel-oriented liquid crystal cells of liquid crystal.

It is used in the same manner aligning agent for liquid crystal CT1 obtained in aligning agent for liquid crystal T2 obtained in embodiment 2 and control 1~4 ~4, make liquid crystal cells.

< orientation evaluates >

The liquid crystal cells made in Examples 1 to 2, control 1~4 are become orthogonal mode with polarizing axis to configure at 2 Between polarization plate, backlight is lighted in the state that no-voltage applies, least way is become with the brightness of transmitted light, adjusted The arrangement angles of whole liquid crystal cells.With the visual confirmation liquid crystal cells.If the liquid crystal cells are well orientated and stream are not confirmed Dynamic orientation is then denoted as "○", is denoted as " △ " if having carried out orientation but having confirmed flow orientation, is denoted as if if it is No yield point “×”。

< voltage retention (VHR) evaluates >

Using the liquid crystal cells made among the above, at a temperature of 70 DEG C, apply the 60 μ s of voltage of 5V, after measuring 16.67ms Voltage, calculate voltage and how much be able to maintain as voltage retention (VHR).It should be noted that in the measurement of voltage retention Use the voltage retention measurement device VHR-1 of TOYO Corporation.

By the result and light orientation polymer of Examples 1 to 2 and result and < orientation the evaluation > of the VHR of control 1~4 " total photoreactive group amount " in ingredient is shown in table 3 together.

[table 3]

As shown in Table 2, in embodiment 1,2, make the monomer copolymerization with 2 kinds of different photoreactive groups, thus with its point is made Polymer phase ratio obtained from not being copolymerized not individually, shows good orientation, and then will gather under the UV exposure of wide scope Amic acid is blended, so that VHR is improved.

Claims

1. a kind of polymer composition, contains:

(A) side chain type macromolecule, and (B) organic solvent,

(A) the side chain type macromolecule has: side chain (a1) with photoreactivity position shown in following formula (a), have with The side chain (a2) at the different photoreactivity position in photoreactivity position shown in following formula (a) and the side chain for showing liquid crystal liquid crystal property (a3),

2. composition according to claim 1, wherein the side chain (a2) is that photo-crosslinking, photoisomerization or light occurs not The photonasty side chain that Li Si is reset.

3. composition according to claim 1 or 2, wherein the side chain (a2) is selected from by following formula (1)~(6) group At group in wantonly a kind of photonasty side chain and for the light reaction different from photoreactivity position shown in the formula (a) The side chain at property position,

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 monovalence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, Identical or different 2~6 ring either in these substituent groups is by group made of binding groups B bonding, 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；

Y₂For selected from by the phenyl ring of divalent, naphthalene nucleus, furan nucleus, pyrrole ring, the ester ring type hydrocarbon of carbon number 5~8 and their combination group At group in group, be bonded to their hydrogen atom each independently optionally by-NO₂,-CN ,-CH=C (CN)₂,-CH=CH- The alkyl oxy substitution of CN, halogen group, the alkyl of carbon number 1~5 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 number 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 replace；

One of q1 and q2 are 1, another one 0；

Q3 is 0 or 1；

P and Q be each independently selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 alicyclic ring Group in the group of formula hydrocarbon and their combination composition；Wherein, the case where X is-CH=CH-CO-O- ,-O-CO-CH=CH- Under, the P or Q for the side that-CH=CH- is bonded are aromatic rings, and when the number of P becomes 2 or more, P is optionally same or different to each other, When the number 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 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 their combination Group.

4. composition described in any one of claim 1 to 3, wherein the side chain (a3) is selected from by following formula (21)~(31) wantonly a kind of the liquid crystal liquid crystal property side chain in group formed,

In formula, A and B have definition same as described above；

Y₃For selected from by the phenyl ring of monovalence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and 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, halogen group, The alkyl of carbon number 1~5 or the alkyl oxy of carbon number 1~5 replace；

R₃Indicate hydrogen atom ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, the phenyl ring of monovalence, naphthalene nucleus, biphenyl Ring, furan nucleus, nitrogen-containing heterocycle, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or carbon number 1~12 alkoxy；

One of q1 and q2 are 1, another one 0；

L indicates that 1~12 integer, m indicate 0~2 integer, wherein in formula (23)~(24), whole m's adds up to 2 or more, In formula (25)~(26), 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, the phenyl ring of monovalence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and carbon The ester ring type hydrocarbon and alkyl or alkyl oxy of number 5~8；

Z₁、Z₂Indicate singly-bound ,-CO- ,-CH₂O- ,-CH=N- ,-CF₂-。

5. a kind of manufacturing method for the substrate for indicating element liquid crystal orientation film with the driving liquid crystal of transverse electric field, passes through tool Obtain having been assigned the liquid crystal orientation film of tropism control ability for following process,

Composition according to any one of claims 1 to 4 is coated on the base of the conductive film with transverse electric field driving by [I] The process of film is formed on plate；

The process that [III] heats film obtained in [II].

6. a kind of substrate for indicating element liquid crystal orientation film with the driving liquid crystal of transverse electric field, is by claim 5 The method manufacture.

7. a kind of driving liquid crystal of transverse electric field indicates element, with substrate as claimed in claim 6.

8. a kind of driving liquid crystal of transverse electric field indicates the manufacturing method of element, the liquid crystal is obtained and having following process Indicate element:

Prepare the process of substrate as claimed in claim 6 (the 1st substrate)；

The process for obtaining the 2nd substrate with liquid crystal orientation film, by having following [I '], [II '], [III '] process to obtain To the liquid crystal orientation film for having been assigned tropism control ability；And

[IV] is oppositely disposed the described 1st in such a way that the liquid crystal orientation film of the 1st substrate and the 2nd substrate is across liquid crystalline phase pair Substrate and the 2nd substrate, so that the process that liquid crystal indicates element is obtained,

[I '] is coated with polymer composition described in any one of claim 1~17 on the 2nd substrate and forms the work of film Sequence；

The process that [III '] heats film obtained in [II '].

It 9. a kind of driving liquid crystal of transverse electric field indicates element, is manufactured by method according to any one of claims 8.