CN105452370B

CN105452370B - The manufacturing method of the substrate of element liquid crystal orientation film is represented with the driving liquid crystal of transverse electric field

Info

Publication number: CN105452370B
Application number: CN201480044003.3A
Authority: CN
Inventors: 名木达哉; 川月喜弘; 近藤瑞穂
Original assignee: Nissan Chemical Corp; University of Hyogo
Current assignee: Nissan Chemical Corp; University of Hyogo
Priority date: 2013-06-05
Filing date: 2014-06-05
Publication date: 2018-06-01
Anticipated expiration: 2034-06-05

Abstract

The present invention, which is provided, to be endowed tropism control ability, ghost excellent and the high driving liquid crystal of transverse electric field of reliability with high efficiency and represents element.The present invention provides a kind of manufacturing method for the substrate that element liquid crystal orientation film is represented with the driving liquid crystal of transverse electric field, obtains having been assigned the foregoing liquid crystal alignment films of tropism control ability by possessing following process：Polymer composition is coated on the process for forming film on the substrate with transverse electric field driving conductive film by [I], the polymer composition contains (A) side chain type macromolecule and (B) organic solvent, the side chain type macromolecule is the photonasty side chain type macromolecule that liquid crystal liquid crystal property is shown within the scope of specific temperature, it has selected from one or more of annular amine structure repetitive unit, it is described ring-type amine structure 2 adjacent with nitrogen-atoms carbon atom be respectively provided with 2 following formula (S) (in formula, R¹¹For singly-bound etc., X is singly-bound, R¹²For alkyl.) shown in substituent group；The process of [II] to the film irradiation polarized UV rays obtained in [I]；And the process that [III] heats the film obtained in [II].‑R¹¹‑X‑R¹²(S)。

Description

The system of the substrate of element liquid crystal orientation film is represented with the driving liquid crystal of transverse electric field Make method

Technical field

The present invention relates to the manufacturing methods for the substrate that element liquid crystal orientation film is represented with the driving liquid crystal of transverse electric field. More specifically, it is related to the new method for the liquid crystal expression element for manufacturing ghost excellent.

Background technology

It is known that liquid crystal, which represents element as light weight, the expression device that section is thin and power consumption is low, is used in recent years Large-scale tv purposes etc. realizes significant development.Liquid crystal represents that element is, for example, to utilize a pair of of the transparent substrate for possessing electrode It clamps liquid crystal layer and forms.Also, in liquid crystal represents element, the organic film comprising organic material is used as liquid crystal orientation film Make liquid crystal that expectation state of orientation be presented between the substrates.

That is, liquid crystal orientation film is the component parts that liquid crystal represents element, is formed in the substrate and liquid crystal of clamping 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, except liquid crystal is made also to be required sometimes along in addition to being for example orientated this effect parallel to specific directions such as the directions of substrate Liquid crystal pretilt angle is carried out to control this effect.The ability of the control liquid crystal aligning of this liquid crystal orientation film (is hereinafter referred to as orientated Control ability.) be endowed by carrying out orientation process to the organic film for forming liquid crystal orientation film.

As for assigning the method for orientation treatment of the liquid crystal orientation film of 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, the polyimides on substrate etc., cotton is used The cloth of flower, nylon, polyester etc. is along constant direction friction (brushing) its surface, so that liquid crystal is along frictional direction (brushing side To) orientation.The brushing method can easily realize relatively stable liquid crystal aligning state, therefore can be used in previous liquid crystal and represent The manufacturing process of element.It is main to select the reliabilities such as heat resistance, electricity special also, as the organic film used in liquid crystal orientation film The excellent polyimides system organic film of property.

However, to the brushing method that the surface of the liquid crystal orientation film comprising polyimides etc. rubs, there are dust, generations The problem of electrostatic.Further, since liquid crystal in recent years represents high-definition, the electrode or liquid crystal drive on corresponding substrate of element With switching active element caused by bumps, therefore, it is impossible to the surface for the liquid crystal orientation film that equably rubbed with cloth, can not realize Even 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, and the organic of liquid crystal orientation film is being formed 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 the optical alignment method of breakdown type.For example, it is purple to irradiate polarization to polyimide film Using the polarization direction dependence of the ultraviolet radiation absorption of molecular structure anisotropic decomposition occurs for outside line.Also, by not Decompose and remaining polyimides makes liquid crystal be orientated (referring for example to patent document 1.).

In addition, it is also known that have photo-crosslinking type, the optical alignment method of photoisomerization type.Such as it using poly- vinyl cinnamate, shines Polarized UV rays are penetrated, make the double bond part parallel to 2 side chains of polarised light that dimerization reaction (cross-linking reaction) occur.Also, make Liquid crystal is orientated along the direction vertical with polarization direction (referring for example to non-patent literature 1.).In addition, have using in side chain When having the side chain type macromolecule of azobenzene, polarized UV rays are irradiated, make the azobenzene part generation parallel to the side chain of polarised light Isomerization reaction makes liquid crystal be orientated along the direction vertical with polarization direction (referring for example to non-patent literature 2.).

As above-mentioned example, using optical alignment method to liquid crystal orientation film carry out orientation process method in, without into Row brushing, without worrying dust, generating electrostatic.Also, has the substrate of irregular liquid crystal expression element even if for surface It can implement orientation process, so as to become the method for orientation treatment for the liquid crystal orientation film for being suitable for industrial manufacture process.

Prior art literature

Patent document

Patent document 1：No. 3893659 publications of Japanese Patent Publication No.

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).

The content of the invention

Problems to be solved by the invention

As described above, the brushing of industrial utilization is carried out all the time with representing the method for orientation treatment of element as liquid crystal Method is compared, and optical alignment method possesses clear advantage without this process of brushing process.Also, with brushing caused by take The brushing method substantially stationary to control ability is compared, and optical alignment method can change the exposure of polarised light to control tropism control energy Power.However, in the case of wanting to realize the tropism control ability identical with utilizing degree during brushing method in optical alignment method, sometimes It needs substantial amounts of polarizing light irradiation amount or can not realize stable liquid crystal aligning.

For example, it is necessary to be irradiated 60 minutes to polyimide film in the breakdown type optical alignment method described in above patent document 1 The ultraviolet light sent by the high-pressure sodium lamp of power 500W etc., it is necessary to for a long time and substantial amounts of ultraviolet light irradiation.In addition, in dimerization In the case of type, photoisomerization type optical alignment method, it is sometimes desirable to a large amount of ultraviolet lights irradiation of number J (joule)~tens of J or so.Into And in the case of photo-crosslinking type, photoisomerization type optical alignment method, the thermal stability of liquid crystal aligning, photostability are poor, therefore make When representing element into liquid crystal, there are problems that occurring to be orientated bad, expression ghost.Especially, the driving liquid crystal of transverse electric field It represents in element, liquid crystal molecule is switched in face, therefore the liquid crystal aligning offset after liquid crystal drive easily occurs, by AC Represent that ghost is considered apparent problem caused by driving.

Therefore, for optical alignment method, it is desirable that realize high efficiency, the liquid crystal aligning of stabilization of orientation process, it is desirable that Liquid crystal orientation film, the aligning agent for liquid crystal of highly oriented control ability can be efficiently assigned to liquid crystal orientation film.

It is an object of the present invention to provide with high efficiency be endowed tropism control ability, ghost excellent, have horizontal stroke The substrate of element liquid crystal orientation film is represented to electric field drive liquid crystal and there is the driving liquid crystal of transverse electric field of the substrate Represent element.

In addition, it is an object of the present invention to provide on the basis of above-mentioned purpose, even if harsh in high temperature, high humidity etc. Under the conditions of, the characteristics such as voltage retention will not reduce, possess the driving liquid crystal cell of transverse electric field and use of high reliability In the liquid crystal orientation film of the element.

The solution to the problem

The inventors of the present invention have made intensive studies to realize the above subject, it turns out that following invention.

<1>The driving liquid crystal of a kind of polymer composition, especially transverse electric field represents that element is manufactured with liquid crystal orientation film With composition, contain：(A) the photonasty side chain type macromolecule and (B) of liquid crystal liquid crystal property are shown within the scope of specific temperature Organic solvent,

(A) side chain type macromolecule is somebody's turn to do to possess selected from by the 1st repetitive unit with annular amine structure and with phenol structure The 2nd repetitive unit composition group at least one kind of repetitive unit,

2 adjacent with the nitrogen-atoms carbon atom of aforementioned cyclic amine structure is respectively provided with the substitution shown in 2 following formula (S) Base (in formula, R¹¹For singly-bound or optionally substituted alkyl,

X be singly-bound, oxygen atom, sulphur atom ,-CO- ,-CO-O- or-O-CO-,

R¹²For optionally substituted alkyl.Wherein, when X is not singly-bound, R¹¹And R¹²Optionally bond together and form ring knot Structure.)

At least one carbon atom among the ortho position carbon atom of the hydroxyl of foregoing phenol structure has shown in following formula (S) Substituent group.

-R¹¹-X-R¹² (S)

<2>It is above-mentioned<1>In, (A) ingredient can have the photosensitive of photo-crosslinking, photoisomerization or light fries' rearrangement can occur Property side chain.

<3>It is above-mentioned<1>Or<2>In, foregoing 1st repetitive unit can use following formula (1-1), and (in formula (1-1), R is former for hydrogen Son or methyl, R¹¹Optionally each it is identical or different, have definition same as described above, X optionally each it is identical or different, have with Above-mentioned identical definition, R¹²It is optionally each identical or different, there is definition same as described above, B¹For hydrogen atom, oxygen atom, halogen The organic group of plain atom, hydroxyl or 1 valency, m are 0~4 integer) it represents,

Foregoing 2nd repetitive unit can use following formula (1-2) (in formula (1-2), R be hydrogen atom or methyl, R¹¹Optionally each It is identical or different, there is definition same as described above, X is optionally each identical or different, has definition same as described above, R¹²Appoint Choosing is each identical or different, has definition same as described above, and n is 0~3 integer) it represents.

<4>It is above-mentioned<1>~<3>Any one in, foregoing 1st repetitive unit can use following formula (1-1-1) (formula (1-1- 1) in, R be hydrogen atom or methyl, A¹For singly-bound or the connection group of divalent, R¹³It is optionally same or different to each other, is carbon number 1~5 Alkyl, B¹For the organic group of hydrogen atom, oxygen atom, halogen atom, hydroxyl or 1 valency) it represents,

Foregoing 2nd repetitive unit can use following formula (1-2-1) (in formula (1-2-1), R be hydrogen atom or methyl, A¹For list The connection group of key or divalent, R¹³For the alkyl of carbon number 1~5, R¹⁴For hydrogen atom or the alkyl of carbon number 1~5) it represents.

<5>It is above-mentioned<1>~<4>Any one in, (A) ingredient can have selected from the group that is made of following formula (1)~(6) Any one of photonasty side 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 substituted 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 substituted by halogen group；

Y₁In the ester ring type hydrocarbon for representing the phenyl ring selected from 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 The group that ring or identical or different 2~6 ring in these substituent groups are formed by binding groups B bondings, key Together in their hydrogen atom independently optionally by-COOR₀(in formula, R₀Represent 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 alkoxy substitution；

Y₂For be selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 ester ring type hydrocarbon and it Combination composition group in group, be bonded to their hydrogen atom 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 alkoxy substitution；

R⁵¹Represent hydroxyl, the alkoxy of carbon number 1~6 or expression and Y₁Identical definition；

X represents singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH =CH-, when the quantity of X reaches 2, X is optionally same or different to each other；

Cou represents Coumarin-6-base or coumarin-7-base, be bonded to their hydrogen atom 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 alkoxy substitution；

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 combination thereof composition；Wherein, when X is-CH=CH-CO-O- ,-O-CO-CH=CH- ,- The P or Q for the one side that CH=CH- is bonded are aromatic rings, and when the quantity of P reaches more than 2, P is optionally same or different to each other, Q's When quantity reaches more than 2, Q is optionally same or different to each other；

L1 is 0 or 1；

L2 is 0~2 integer；

When l1 and l2 are 0, A also illustrates that singly-bound when T is singly-bound；

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

H and I is each independently in the phenyl ring selected from divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and combination thereof Group.

<6>It is above-mentioned<1>~<4>Any one in, (A) ingredient can have selected from being made of following formula (7)~(10) Any one of group photonasty side chain.

In formula, A, B, D, Y₁、X、Y₂And R⁵¹With definition same as described above；

L represents 1~12 integer；

M represents 0~2 integer, and m1, m2 represent 1~3 integer；

N represents 0~12 integer (wherein, during n=0, B is singly-bound).

<7>It is above-mentioned<1>~<4>Any one in, (A) ingredient can have selected from being made of following formula (11)~(13) Any one of group photonasty side chain.

In formula, A, X, l, m, m1 and R⁵¹With definition same as described above.

<8>It is above-mentioned<1>~<4>Any one in, (A) ingredient can have following formula (14) or the photonasty shown in (15) Side chain.

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

<9>It is above-mentioned<1>~<4>Any one in, (A) ingredient can have following formula (16) or the photonasty shown in (17) Side chain.

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

<10>It is above-mentioned<1>~<4>Any one in, (A) ingredient can have following formula (18) or photosensitive shown in (19) Property side chain.

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

R₁Represent hydrogen atom ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, carbon number 1~5 alkyl, Or the alkoxy of carbon number 1~5.

<11>It is above-mentioned<1>~<4>Any one in, (A) ingredient can have following formula (20) shown in photonasty side chain.

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

<12>It is above-mentioned<1>~<11>Any one in, (A) ingredient can have selected from being made of following formula (21)~(31) Any one of group liquid crystal liquid crystal property side chain.

In formula, A, B, q1 and q2 have definition same as described above；

Y₃For be selected from by the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring and carbon number 5~8 ester ring type hydrocarbon, And the group in the group of combination thereof composition, their hydrogen atom is bonded to independently optionally by-NO₂,-CN, halogen The alkoxy substitution of plain group, the alkyl of carbon number 1~5 or carbon number 1~5；

R₃Represent hydrogen atom ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, the phenyl ring of 1 valency, naphthalene nucleus, Cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or the alcoxyl of carbon number 1~12 Base；

L represents 1~12 integer, and m represents 0~2 integer, wherein, in formula (23)~(24), the summation of all m is 2 More than, in formula (25)~(26), the summation of all m is more than 1, and m1, m2 and m3 each independently represent 1~3 integer；

R₂Represent hydrogen atom ,-NO₂,-CN, halogen group, the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring, With the ester ring type hydrocarbon and alkyl or alkoxy of carbon number 5~8；

Z₁、Z₂Represent singly-bound ,-CO- ,-CH₂O- ,-CH=N- ,-CF₂-。

<13>A kind of manufacturing method for the substrate that element liquid crystal orientation film is represented with the driving liquid crystal of transverse electric field, Obtain having been assigned the foregoing liquid crystal alignment films of tropism control ability by possessing following process：

[I] will be above-mentioned<1>~<12>Any one of composition be coated on transverse electric field driving conductive film Substrate on and the process that forms film；

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

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

<14>A kind of substrate that element liquid crystal orientation film is represented with the driving liquid crystal of transverse electric field, is by above-mentioned <13>Method and manufacture.

<15>A kind of driving liquid crystal of transverse electric field represents element, with above-mentioned<14>Substrate.

<16>A kind of driving liquid crystal of transverse electric field represents the manufacturing method of element, is obtained by possessing following process The liquid crystal represents element：

Prepare above-mentioned<14>Substrate (the 1st substrate) process；

Obtain with following liquid crystal orientation films the 2nd substrate process, by possess following processes [I '], [II '] and [III '] and obtain having been assigned the liquid crystal orientation film of tropism control ability；And

[IV] is oppositely disposed foregoing in a manner that the liquid crystal orientation film of foregoing 1st substrate and the 2nd substrate is across liquid crystalline phase pair 1st substrate and the 2nd substrate, so as to obtain the process that liquid crystal represents element,

The process [I '], [II '] and [III '] is：

[I '] coated polymeric composition and the process that forms film, described polymer composition on the 2nd substrate contains： (A) the photonasty side chain type macromolecule of liquid crystal liquid crystal property and (B) organic solvent are shown within the scope of specific temperature；

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

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

In addition, following invention is found that as another side.

<P1>A kind of manufacturing method for the substrate that element liquid crystal orientation film is represented with the driving liquid crystal of transverse electric field, Obtain having been assigned the foregoing liquid crystal alignment films of tropism control ability by possessing following process：

Polymer composition is coated on the substrate with transverse electric field driving conductive film and forms the work of film by [I] Sequence, the polymer composition contain (A) side chain type macromolecule and (B) organic solvent, and (A) the side chain type macromolecule is in spy The photonasty side chain type macromolecule of liquid crystal liquid crystal property is shown within the scope of fixed temperature, is had selected from annular amine structure or phenol structure One or more of repetitive unit, it is described ring-type amine structure 2 adjacent with nitrogen-atoms carbon atom be respectively provided with 2 following formula (S) substituent group shown in, at least one carbon atom among the ortho position carbon atom of the hydroxyl of the phenol structure have following formula (S) (in formula, R¹¹For singly-bound or optionally substituted alkyl, X is singly-bound, oxygen atom, sulphur atom ,-CO- ,-CO-O- or-O- CO-, R¹²For optionally substituted alkyl.Wherein, when X is not singly-bound, R¹¹And R¹²Optionally bond together and form ring structure.) institute The substituent group shown；

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

-R¹¹-X-R¹² (S)

<P2>It is above-mentioned<P1>In, (A) ingredient can have the sense that photo-crosslinking, photoisomerization or light fries' rearrangement can occur Photosensitiveness side chain.

<P3>A kind of manufacturing method, which is characterized in that above-mentioned<P1>In, foregoing repetitive unit following formula (1-1) or (1- 2) (in formula (1-1) and formula (1-2), R be hydrogen atom or methyl, A¹For singly-bound or the connection group of divalent, R¹¹Respectively singly-bound or Optionally substituted alkyl, X are respectively singly-bound, oxygen atom, sulphur atom ,-CO- ,-CO-O- or-O-CO-, R¹²Respectively optional quilt Substituted alkyl.Wherein, when X is not singly-bound, R¹¹And R¹²Optionally bond together and form ring structure.In formula (1-1), B¹It is former for hydrogen Son, oxygen atom, halogen atom, the organic group of hydroxyl or 1 valency, m are 0~4 integer.In formula (1-2), n be 0~3 it is whole Number.) represent.

<P4>A kind of manufacturing method, which is characterized in that above-mentioned<P1>In, foregoing repetitive unit with following formula (1-1-1) or (1-2-1) (in formula (1-1-1) and formula (1-2-1), R be hydrogen atom or methyl, A¹For singly-bound or the connection group of divalent, R¹³Respectively For the alkyl of carbon number 1~5, R¹⁴For hydrogen atom or the alkyl of carbon number 1~5.In formula (1-1-1), B¹For hydrogen atom, oxygen atom, halogen The organic group of plain atom, hydroxyl or 1 valency.) represent.

<P5>It is above-mentioned<P1>Or<P2>In, (A) ingredient can have in the group for being selected from and being made of following formula (1)~(6) Any photonasty side chain.

X represents singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH =CH-；

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

Q3 is 0 or 1；

P and Q is each independently selected from by singly-bound, the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5 Group in the group of~8 ester ring type hydrocarbon and combination thereof composition.Wherein, X is-CH=CH-CO-O- ,-O-CO-CH=CH- When, the P or Q of the one side that-CH=CH- is bonded are aromatic rings；

<P6>It is above-mentioned<P1>Or<P2>In, (A) ingredient can have in the group for being selected from and being made of following formula (7)~(10) Any photonasty side chain.

L represents 1~12 integer；

M represents 0~2 integer, and m1, m2 represent 1~3 integer；

N represents 0~12 integer (wherein, during n=0, B is singly-bound).

<P7>It is above-mentioned<P1>Or<P2>In, (A) ingredient can have in the group for being selected from and being made of following formula (11)~(13) Any photonasty side chain.

In formula, A, X, l, m and R⁵¹With definition same as described above.

<P8>It is above-mentioned<P1>Or<P2>In, (A) ingredient can be with the photonasty side chain shown in following formula (14) or (15).

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

<P9>It is above-mentioned<P1>Or<P2>In, (A) ingredient can be with the photonasty side chain shown in following formula (16) or (17).

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

<P10>It is above-mentioned<P1>Or<P2>In, (A) ingredient can be with the photonasty side shown in following formula (18) or (19) Chain.

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

<P11>It is above-mentioned<P1>Or<P2>In, (A) ingredient can have the photonasty side chain shown in following formula (20).

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

<P12>It is above-mentioned<P1>~<P11>Any one in, (A) ingredient can have be selected from by following formula (21)~(31) Any one of group of composition liquid crystal liquid crystal property side chain.

In formula, A, B, q1 and q2 have definition same as described above；

L represents 1~12 integer, and m represents 0~2 integer, wherein, in formula (25)~(26), the summation of all m is 2 More than, in formula (27)~(28), the summation of all m is more than 1, and m1, m2 and m3 each independently represent 1~3 integer；

Z₁、Z₂Represent singly-bound ,-CO- ,-CH₂O- ,-CH=N- ,-CF₂-。

<P13>A kind of substrate that element liquid crystal orientation film is represented with the driving liquid crystal of transverse electric field, is by upper It states<P1>~<P12>Any one of and manufacture.

<P14>A kind of driving liquid crystal of transverse electric field represents element, with above-mentioned<P13>Substrate.

<P15>A kind of driving liquid crystal of transverse electric field represents the manufacturing method of element, is obtained by possessing following process Element is represented to the liquid crystal：

Prepare above-mentioned<P13>Substrate (the 1st substrate) process；

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

[IV] in a manner that the liquid crystal orientation film of the 1st substrate and the 2nd substrate is across liquid crystalline phase pair, oppositely disposed 1st substrate With the 2nd substrate, so as to obtain liquid crystal represent element process,

The process [I '], [II '] and [III '] is：

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

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

<P16>A kind of driving liquid crystal of transverse electric field represents element, is by above-mentioned<P15>And manufacture.

<P17>A kind of driving liquid crystal of transverse electric field represents that element is manufactured with liquid crystal orientation film with composition, contains (A) Side chain type macromolecule and (B) organic solvent,

(A) the side chain type macromolecule is the photonasty side chain type high score that liquid crystal liquid crystal property is shown within the scope of specific temperature Son has selected from annular one or more of amine structure or phenol structure repetitive unit,

It is described ring-type amine structure 2 adjacent with nitrogen-atoms carbon atom be respectively provided with 2 following formula (S) (in formula, R¹¹For Singly-bound or optionally substituted alkyl, X are singly-bound, oxygen atom, sulphur atom ,-CO- ,-CO-O- or-O-CO-, R¹²Optionally to be taken The alkyl in generation.Wherein, when X is not singly-bound, R¹¹And R¹²Optionally bond together and form ring structure.) shown in substituent group,

At least one carbon atom among the ortho position carbon atom of the hydroxyl of the phenol structure has shown in following formula (S) Substituent group.

-R¹¹-X-R¹² (S)

<P18>A kind of composition, which is characterized in that above-mentioned<P17>In, foregoing repetitive unit following formula (1-1) or (1- 2) represent.

In formula (1-1) and formula (1-2), R be hydrogen atom or methyl, A¹For singly-bound or the connection group of divalent, R¹¹It is respectively single Key or optionally substituted alkyl, X are respectively singly-bound, oxygen atom, sulphur atom ,-CO- ,-CO-O- or-O-CO-, R¹²Respectively appoint Select substituted alkyl.Wherein, when X is not singly-bound, R¹¹And R¹²Optionally bond together and form ring structure.In formula (1-1), B¹For Hydrogen atom, oxygen atom, halogen atom, the organic group of hydroxyl or 1 valency, m are 0~4 integer.In formula (1-2), n is 0~3 Integer.

<P19>A kind of composition, which is characterized in that above-mentioned<P17>In, foregoing repetitive unit with following formula (1-1-1) or (1-2-1) is represented.

In formula (1-1-1) and formula (1-2-1), R be hydrogen atom or methyl, A¹For singly-bound or the connection group of divalent, R¹³Respectively For the alkyl of carbon number 1~5, R¹⁴For hydrogen atom or the alkyl of carbon number 1~5.In formula (1-1-1), B¹For hydrogen atom, oxygen atom, halogen The organic group of plain atom, hydroxyl or 1 valency.

The effect of invention

By means of the invention it is possible to provide with high efficiency be endowed tropism control ability, ghost excellent, have laterally Electric field drive liquid crystal represents the substrate of element liquid crystal orientation film and the driving liquid crystal watch of transverse electric field with the substrate Show element.

The driving liquid crystal of transverse electric field manufactured by the method for the present invention represents that element is efficiently imparted orientation Control ability, therefore even if long-time Continuous Drive will not damage characterization.

In addition, it by means of the invention it is possible to provides on the basis of the above effect, even if in the harsh item such as high temperature, high humidity Under part, the characteristics such as voltage retention will not reduce, possess the driving liquid crystal cell of transverse electric field of high reliability and be used for The liquid crystal orientation film of the element.

Description of the drawings

Fig. 1 is the anisotropy importing processing in the manufacturing method for schematically illustrate the liquid crystal orientation film used in the present invention An example figure, figure when being photosensitive side chain using bridging property organic group and the small anisotropy that is imported.

Fig. 2 is the anisotropy importing processing in the manufacturing method for schematically illustrate the liquid crystal orientation film used in the present invention An example figure, figure when being photosensitive side chain using bridging property organic group and the big anisotropy that is imported.

Fig. 3 is the anisotropy importing processing in the manufacturing method for schematically illustrate the liquid crystal orientation film used in the present invention An example figure, be photosensitive side chain using the organic group of fries' rearrangement or isomerization can occur and imported Figure when anisotropy is small.

Fig. 4 is the anisotropy importing processing in the manufacturing method for schematically illustrate the liquid crystal orientation film used in the present invention An example figure, be photosensitive side chain using the organic group of fries' rearrangement or isomerization can occur and imported Figure when anisotropy is big.

Specific embodiment

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

The polymer composition used in the manufacturing method of the present invention has the photonasty side chain that can show liquid crystal liquid crystal property Type macromolecule (hereinafter also referred to as side chain type macromolecule), the film obtained using foregoing polymer compositions be have being capable of table Reveal the high molecular film of photonasty side chain type of liquid crystal liquid crystal property.The film need not carry out brushing processing, by polarizing light irradiation and into Row orientation process.Also, after polarizing light irradiation is carried out, via the process for heating the side chain type polymeric membrane, so as to as quilt Impart the film (hereinafter also referred to liquid crystal orientation film) of tropism control ability.At this point, shown by polarizing light irradiation Small anisotropy becomes driving force, the side chain type macromolecule itself of liquid crystal liquid crystal property effectively reorientation due to self assembly.It is tied Fruit can realize efficient orientation process as liquid crystal orientation film, and the liquid crystal for obtaining having been assigned highly oriented control ability takes To film

Hereinafter, it is described in detail for embodiments of the present invention.

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

The driving liquid crystal of polymer composition, especially transverse electric field is represented that element manufactures use with liquid crystal orientation film by [I] Composition is coated on the process for forming film on the substrate with transverse electric field driving conductive film, the combination of polymers The driving liquid crystal of object, especially transverse electric field represents that element is manufactured with liquid crystal orientation film and is contained with composition：(A) in specific temperature The photonasty side chain type macromolecule of liquid crystal liquid crystal property and (B) organic solvent are shown in the range of degree, it should (A) side chain type macromolecule tool Alternatively in the group of the 1st repetitive unit freely with annular amine structure and the 2nd repetitive unit composition with phenol structure extremely Few a kind of repetitive unit, 2 adjacent with the nitrogen-atoms carbon atom of aforementioned cyclic amine structure are respectively provided with 2 following formula (S) (formulas In, R¹¹For singly-bound or optionally substituted alkyl, X is singly-bound, oxygen atom, sulphur atom ,-CO- ,-CO-O- or-O-CO-, R¹²For Optionally substituted alkyl.Wherein, when X is not singly-bound, R¹¹And R¹²Optionally bond together and form ring structure.) shown in substitution Base, at least one carbon atom among the ortho position carbon atom of the hydroxyl of foregoing phenol structure have the substitution shown in following formula (S) Base；

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

-R¹¹-X-R¹² (S)

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

In addition, in addition to substrate obtained above (the 1st substrate), by preparing the 2nd substrate, transverse electric field can be obtained Driving liquid crystal represents element.

2nd substrate is except using without transverse electric field driving with the substrate of conductive film come instead of having transverse electric field to drive Outside the substrate of conductive film, by using above-mentioned operation [I]~[III] (due to the use of without transverse electric field driving with leading The substrate of electrolemma, therefore for convenience, in this application sometimes referred to simply as process [I ']~[III ']), it can obtain with quilt Impart the 2nd substrate of the liquid crystal orientation film of tropism control ability.

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

[IV] is by the 1st substrate obtained above and the 2nd substrate with the liquid crystal orientation film of the 1st substrate and the 2nd substrate across liquid The mode of crystalline phase pair carry out it is oppositely disposed, so as to obtain liquid crystal represent element process.Thereby, it is possible to obtain transverse electric field driving Type liquid crystal represents element.

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

In process [I], the coated polymeric composition on the substrate with transverse electric field driving conductive film and form painting Film, the polymer composition contain：Shown within the scope of specific temperature liquid crystal liquid crystal property photonasty side chain type macromolecule, with And organic solvent.

It is not particularly limited for substrate, when the liquid crystal to be manufactured expression element is infiltration type, it is preferable to use transparent 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.

Furthermore, it is contemplated that the application in reflective liquid crystal represents element, can also use the opaque bases such as silicon wafer Plate.

Substrate has transverse electric field driving conductive film.

As the conductive film, when liquid crystal expression element is infiltration type, ITO (Indium Tin Oxide can be included：Oxidation Indium tin), IZO (Indium Zinc Oxide：Indium zinc oxide) etc., it is not limited to these.

In addition, in the case where reflective liquid crystal represents element, as conductive film, the material that aluminium etc. understands reflected light can be included Material etc., is not limited to these.

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

Coated polymeric composition, especially applies on conductive film on the substrate with transverse electric field driving conductive film Cloth polymer composition.

The polymer composition used in the manufacturing method of the present invention contains：(A) showed within the scope of specific temperature Go out the photonasty side chain type macromolecule of liquid crystal liquid crystal property and (B) organic solvent.

<<(A) side chain type macromolecule>>

(A) ingredient is the photonasty side chain type macromolecule that liquid crystal liquid crystal property is shown within the scope of specific temperature.

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

(A) side chain type macromolecule preferably has the photonasty side to react with the light of the wave-length coverage of 250nm~400nm Chain.

(A) side chain type macromolecule shows liquid crystal liquid crystal property within the temperature range of 100 DEG C~250 DEG C, therefore preferably has liquid crystal Former base group.

[repetitive unit]

(A) side chain type macromolecule is somebody's turn to do to possess selected from by the 1st repetitive unit with annular amine structure and with phenol structure The 2nd repetitive unit composition group at least one kind of repetitive unit.

2 adjacent with the nitrogen-atoms carbon atom of annular amine structure is respectively provided with the substituent group shown in 2 above-mentioned formulas (S).

At least one carbon atom among the ortho position carbon atom of the hydroxyl of phenol structure has the substitution shown in above-mentioned formula (S) Base.

As above-mentioned annular amine structure, the quantity for forming the carbon atom of its ring structure is preferably 2 or more and less than 7, More preferably 5.

In addition, as above-mentioned phenol structure, the bonding position of the hydroxyl in phenyl ring is arbitrary, is preferably in the phenyl ring The contraposition of the carbon atom closed with main chain side switch.

It is with hindered amine knot when there is annular amine structure more specifically as the preferred structure of repetitive unit (a1) The structure of structure is the structure shown in following formula (1-1).

On the other hand, when there is phenol structure, it is the structure with hindered phenol structure, is the knot shown in following formula (1-2) Structure.

In formula (1-1) and formula (1-2), R be hydrogen atom or methyl, A¹For singly-bound or the connection group of divalent, in formula (1-1), B¹For the organic group of hydrogen atom, oxygen atom, halogen atom, hydroxyl or 1 valency, m is 0~4 integer.In formula (1-2), n for 0~ 3 integer.R¹¹, X and R¹²Definition it is identical with above-mentioned formula (S).

In above-mentioned formula (S), above-mentioned formula (1-1) and above-mentioned formula (1-2), as R¹¹Alkyl, specifically, carbon can be included Divalent chain alkyl, the divalent alicyclic type hydrocarbon of carbon number 3~15 and the divalent aromatic hydrocarbyl of carbon number 6~20 of number 1~10.This It is preferably the alkylidene of methylene or carbon number 2~5 among a little.As the alkylidene of carbon number 2~5, specifically, can include Ethylidene, propylidene, butylidene, pentylidene etc., they can be straight-chain and any one of branched.It should in addition, being used as The substituent group that alkyl optionally has can include halogen atom, hydroxyl etc. such as fluorine atom, chlorine atom.

In above-mentioned formula (S), above-mentioned formula (1-1) and above-mentioned formula (1-2) ,-R¹¹When-X- is not singly-bound, preferably-CO-O- ,- CH₂- CO- or-CH₂-CH(OH)-。

In above-mentioned formula (S), above-mentioned formula (1-1) and above-mentioned formula (1-2), as R¹², specifically, carbon number 1~6 can be included Alkyl, the aryl of carbon number 6~12 or the aralkyl of carbon number 7~13.At this point, benzene ring hydrogen possessed by aryl and aralkyl Atom is optionally substituted by the alkoxy of formoxyl or carbon number 1~4.

As R¹²Carbon number 1~6 alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, 2- can be included Butyl, isobutyl group, tertiary butyl etc.；

As the aryl of carbon number 6~12, such as phenyl, 4- Fonnylphenyls, 3,4,5- trimethoxyphenyls can be included Deng；

As the aralkyl of carbon number 7~13, benzyl etc. can be included.

As R¹¹And R¹²The ring structure for bonding together and being formed, can include for example from furans, thiophene, 2H- pyrans and Group obtained from removing 1 hydrogen atom in 4H- pyrans etc..

In above-mentioned formula (S), above-mentioned formula (1-1) and above-mentioned formula (1-2), as-R¹¹-X-R¹², it is preferable to it includes for example Methyl, ethyl, n-propyl, isopropyl, normal-butyl, 2- butyl, isobutyl group, tertiary butyl, phenyl, benzyl, benzoyl, 4- formyls Base benzoyl, 2- hydroxyl -2- phenethyls, 2- oxa-s -2- (3,4,5- trimethoxyphenyls) ethyl etc..In addition, conduct-R¹¹- X-R¹², the more preferably alkyl of carbon number 1~5, if above-mentioned formula (1-1), then particularly preferably methyl or ethyl, if upper Formula (1-2) is stated, then particularly preferably methyl or tertiary butyl.

It is preferably 0 as m in above-mentioned formula (1-1)；It is preferably 0 or 1 as n in above-mentioned formula (1-2).These m's and n Relation and with above-mentioned-R¹¹-X-R¹²Relation in, as above-mentioned formula (1-1) and above-mentioned formula (1-2), preferably with following formula (1- 1-1) represented with following formula (1-2-1).

In formula (1-1-1) and formula (1-2-1), R¹³The respectively alkyl of carbon number 1~5；In formula (1-2-1), R¹⁴For hydrogen atom Or the alkyl of carbon number 1~5.R、A¹And B¹Definition it is identical with above-mentioned formula (1-1) and above-mentioned formula (1-2).)

In above-mentioned formula (1-1), above-mentioned formula (1-2), above-mentioned formula (1-1-1) and above-mentioned formula (1-2-1), as A¹, it is preferably 2 The connection group of valency.As A¹Divalent connection group, the group shown in following formula (A1) can be included.

-A¹¹-A¹²-A¹³-A¹⁴-*1 (A1)

In formula, A¹¹For singly-bound, methylene, carbon number 2~5 alkylidene or phenylene, A¹²For singly-bound ,-O- ,-CO- ,-CO- O- or-O-CO-, A¹³For singly-bound or the alkylidene of optionally substituted methylene or carbon number 2~5, A¹⁴For singly-bound ,-O- ,- CO- ,-CO-O- ,-O-CO- ,-NR '-or alkyl that-NR '-CO-O-, R ' are hydrogen atom or carbon number 1~6.Wherein, not including A¹¹、 A¹²、A¹³And A¹⁴The situation of all singly-bounds.* 1 represents and the carbon atom bonding of the carbon atom of annular amine structure or phenol structure Connecting key.

In above-mentioned formula (A1), as A¹¹And A¹³Carbon number 2~5 alkylidene, above-mentioned R can be included¹¹In the Asia that exemplifies Alkyl.In addition, as A¹³Methylene or carbon number 2~5 the substituent group that optionally has of alkylidene, above-mentioned R can be included¹¹In The substituent group of illustration.In addition, the alkyl of the carbon number 1~6 as R ', can include above-mentioned R¹²In the alkyl that exemplifies.

As the connection group of the divalent shown in above-mentioned formula (A1), can include shown in such as formula (A1-1)~formula (A1-17) Group, but be not limited to these.

In formula (A1-1)~formula (A1-17), * 1 represents key on the carbon atom of the carbon atom of annular amine structure or phenol structure The connecting key of conjunction.

In above-mentioned formula (A1-1)~formula (A1-17), in terms of the durability for being suitable for realizing improving gained liquid crystal orientation film It sets out, as A¹Divalent connection group, be preferably formula (A1-2), formula (A1-5), formula (A1-8), formula (A1-10), formula (A1- 11), the group shown in any one of formula (A1-16) and formula (A1-17), more preferably formula (A1-2), formula (A1-5) and formula Any one of (A1-10) group shown in.

In above-mentioned formula (1-1) and above-mentioned formula (1-1-1), as B¹Halogen atom, fluorine atom, chlorine atom can be included Deng.

In above-mentioned formula (1-1) and above-mentioned formula (1-1-1), as B¹1 valency organic group, following formula (B1) institute can be included The group shown.

-B¹¹-B¹² (B1)

In formula, B¹¹For singly-bound ,-O- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-NR "-or-CO-NR "-, R " is hydrogen atom Or the alkyl of carbon number 1~6.B¹²Alkyl, the aryl of carbon number 6~12, the aralkyl of carbon number 7~13, carbon number 3 for carbon number 1~15 The heterocycle of~10 1 valency or the alicyclic type hydrocarbon of carbon number 3~15, hydrogen atom possessed by these groups are optionally substituted.

In above-mentioned formula (B1), the alkyl of the carbon number 1~6 as R " can include above-mentioned R¹²In the alkyl that exemplifies.

In above-mentioned formula (B1), as B¹²Carbon number 1~15 alkyl, can be straight-chain or branched, can arrange Enumerate for example methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, Tridecyl, myristyl, pentadecyl etc.；

As the aryl of carbon number 6~12, such as phenyl, tolyl, 4- ethylphenyls, 3,5-dimethylphenyl, 2 can be included, 4,6- trimethylphenyls, naphthalene, anthryl etc.；

As the aralkyl of carbon number 7~13, can include such as benzyl, phenethyl, α-methylbenzyl, naphthyl methyl；

As 1 valency heterocycle of carbon number 3~10, nitrogen-containing heterocycle compound can be included, can include such as piperidines, Quinoline, pyridine, pyrazine etc.；

As the alicyclic type hydrocarbon of carbon number 3~15, can include such as cyclopenta, cyclohexyl, 4- methylcyclohexyls.

In addition, as B¹²The substituent group that optionally has of above-mentioned each group, the halogen such as fluorine atom, chlorine atom can be included Plain atom, hydroxyl, nitro, cyano etc..

As 1 valency organic group (- B shown in above-mentioned formula (B1)¹¹-B¹²), such as methyl, normal-butyl, positive penta can be included Base, tertiary pentyl, n-octyl, benzyl, 4- ethylphenyls, 4- methylcyclohexyls, methoxyl group, octyloxy, cyclohexyloxy, acetyl group, Acetoxyl group, 14 carbonic acyl radicals, Alpha-Methyl benzyloxy, piperidines for carbonyl, morpholino carbonyl, 2- hydroxy-2-methyls propoxyl group ,- O-CONH-C₆H₅Deng.

In above-mentioned formula (1-1) and above-mentioned formula (1-1-1), from the side for the durability for being suitable for realizing improving gained liquid crystal orientation film Face is set out, as B¹, it is preferably hydrogen atom, oxygen atom, chlorine atom, methyl, normal-butyl, n-pentyl, tertiary pentyl, benzyl, methoxy Any one of base, octyloxy, acetyl group, acetoxyl group, cyclohexyloxy, more preferably hydrogen atom, oxygen atom, methyl, benzyl, Any one of octyloxy.

As the repetitive unit (a1) with the structure of hindered amine, specifically, can include following formula (a1-1-1)~ (a1-1-20) repetitive unit shown in (in formula, R is hydrogen atom or methyl).

Assign the repetitive unit (a1) of above-mentioned the structure of hindered amine monomer can by combine the conventional method of organic chemistry come It is easily synthesized.For example, if the monomer for the repetitive unit for assigning above-mentioned formula (a1-1-1)~formula (a1-1-16), can pass through Make halogenated (methyl) acryloyl group and following formula (C-1) (in formula, A¹³、A¹⁴、B¹And R¹³Definition and the definition phase that has been described above Together.) compound represented reacts to obtain according to well known esterification.In addition, if the above-mentioned formula (a1-1-17) of imparting Or the monomer of the repetitive unit of formula (a1-1-18), it can be by making halogenated 2- acrylic or halogenated 9- decyls and following formula (C-1) Compound represented reacts to obtain according to well known etherification reaction.In addition, if the above-mentioned formula (a1-1-19) of imparting or formula (a1-1-20) monomer of repetitive unit, can be by making halogenated (methyl) acryloyl group and the OH-A in following formula (C-1)¹³- A¹⁴- it is substituted for NH₂- compound react to obtain according to well known amidation process.

In addition, above-mentioned each monomer can also use commercially available product, for example, 2,2,6,6- tetramethyl -4- piperidines of methacrylic acid Ester and methacrylic acid 1,2,2,6,6- pentamethyl -4- piperidine esters are respectively in the form of FA-712HM, FA-711MM by Hitachi Into Industrial Co., Ltd's list marketing.

As the repetitive unit (a1) with hindered phenol structure, specifically, following formula (a1-2-1)~formula can be included (a1-2-10) (in formula, R is hydrogen atom or methyl.) shown in repetitive unit.

The monomer for assigning the repetitive unit (a1) of above-mentioned hindered phenol structure can be by combining the conventional method of organic chemistry To be easily synthesized.

As repetitive unit (a1), from the durability aspect for being suitable for realizing improving gained liquid crystal orientation film, with tool The repetitive unit for having hindered phenol structure is compared, it is however preferred to have the repetitive unit of the structure of hindered amine.

In polymer [A], repetitive unit (a1) can individually have a kind, can also combine with two or more.Its mechanism It is still not clear, can speculate：By making polymer [A] that there is repetitive unit (a1), by the ultraviolet light of the irradiations such as backlight by polymer [A] properly absorbs, which is not easy to influence to be selected from as making tetracarboxylic dianhydride and polyamic acid obtained from diamine reactant And its at least one of group of imide amination polymer composition polymer.As a result, liquid crystal is also able to maintain that even if long-time service Orientation characteristic, can obtain having the liquid crystal of long durability to represent element.In addition, from improve the effect aspect, The content ratio (or assigning the copolymerization ratios of the monomer of repetitive unit (a1)) of repetitive unit (a1) in polymer [A] is polymerizeing It is preferably more than 1 weight % among the total weight (or total weight of the monomer used during synthetic polymer [A]) of object [A], more Preferably more than 1 weight % and below 50 weight %, further preferably more than 1 weight % and below 30 weight %, it is especially excellent It elects as more than 1 weight % and below 20 weight %.

(A) the high molecular main chain of side chain type has been bonded with photosensitive side chain, and sensing can crosslink in light Reaction, isomerization reaction or light fries' rearrangement.It is not particularly limited with photosensitive side-chain structure, is contemplated to be sensing in light And crosslink the structure of reaction or light fries' rearrangement, it more desirable to be the structure for crosslinking reaction.At this point, if exposed to The external stresses such as heat can also keep the tropism control ability realized steadily in the long term.It can show the photonasty of liquid crystal liquid crystal property It as long as the structure of side chain type polymeric membrane meets this characteristic, is just not particularly limited, preferably has in side-chain structure upright and outspoken Liquid crystal ultimate constituent.At this point, when the side chain type macromolecule is made liquid crystal orientation film, stable liquid crystal aligning can be obtained.

The high molecular structure can be for example made such as lower structure：With main chain and the side chain for being bonded to it, side chain tool There are the liquid crystal ultimate constituents such as xenyl, terphenyl, phenylcyclohexyl, phenylamino benzoic acid ester group, azobenzene and be bonded to front end The sensing light in portion and crosslink the photonasty group of reaction, isomerization reaction；With main chain and the side chain for being bonded to it, the side Chain has and both for liquid crystal ultimate constituent or the phenylamino benzoic acid ester group of light Fries rearrangement can occur.

The more specific example of structure as the photonasty side chain type polymeric membrane that can show liquid crystal liquid crystal property, it is however preferred to have The structure of following main chain and following side chain, the main chain is by being selected from hydrocarbon, acrylate, methacrylate, maleimide, drop At least one kind of composition in the group that bornylene and siloxanes are formed, the side chain include at least 1 in following formula (1)~(6) Kind.

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

Q3 is 0 or 1；

L1 is 0 or 1；

L2 is 0~2 integer；

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

Side chain can be selected from any one of the group being made of following formula (7)~(10) photonasty side chain.

L represents 1~12 integer；

M represents 0~2 integer, and m1, m2 represent 1~3 integer；

N represents 0~12 integer (wherein, during n=0, B is singly-bound).

Side chain can be selected from any one of the group being made of following formula (11)~(13) photonasty side chain.

In formula, A, X, l, m, m1 and R⁵¹With definition same as described above.

Side chain can be the 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 can be the 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 can be the photonasty side chain shown in following formula (18) or (19).

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

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

In addition, (A) side chain type macromolecule can have any one of group for being selected from and being made of following formula (21)~(31) Liquid crystal liquid crystal property side chain.

In formula, A, B, q1 and q2 have definition same as described above；

Z₁、Z₂Represent singly-bound ,-CO- ,-CH₂O- ,-CH=N- ,-CF₂-。

In the application, as photoreactivity and/or liquid crystal liquid crystal property side chain monomer, provide shown in following formula (1)~(11) Compound (1)~(11)；And following formula (12)~(17) compound represented (12)~(17).

In formula, R represents hydrogen atom or methyl；S represents the alkylidene of carbon number 2~10；R¹⁰Represent Br or CN；S represents carbon number 2 ~10 alkylidene；U is expressed as 0 or 1；And Py represents 2- pyridyl groups, 3- pyridyl groups or 4- pyridyl groups.In addition, v represent 1 or 2。

<<The high molecular preparation method of photonasty side chain type>>

The above-mentioned photonasty side chain type macromolecule that can show liquid crystal liquid crystal property can be by having photonasty side chain by above-mentioned Photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer polymerize to obtain.

[liquid crystal liquid crystal property side chain monomer]

Liquid crystal liquid crystal property side chain monomer refers to：High molecular form from the monomer reveals liquid crystal liquid crystal property, and the macromolecule is at side chain position The monomer of mesogenic group can be formed.

Can be that biphenyl, phenol benzoate etc. individually become liquid crystal original structure as mesogenic group possessed by side chain Group or such ground such as benzoic acid side chain carry out hydrogen bonding each other and as the group of mesogen structure.As side Mesogenic group possessed by chain is preferably following structures.

More specific example as liquid crystal liquid crystal property side chain monomer, it is however preferred to have the structure of following main chain and following side chain, it is described It is at least one kind of in the group that main chain is formed by being selected from hydrocarbon, (methyl) acrylate, maleimide, norbornene and siloxanes It forms, the side chain includes at least one kind of in above-mentioned formula (21)~(31).

(A) side chain type macromolecule can be obtained by the polymerisation of the above-mentioned photoreactivity side chain monomer for showing liquid crystal liquid crystal property .Furthermore it is possible to by the copolymerization of the photoreactivity for not showing liquid crystal liquid crystal property side chain monomer and liquid crystal liquid crystal property side chain monomer, show liquid The photoreactivity side chain monomer of crystalline substance is obtained with the copolymerization of liquid crystal liquid crystal property side chain monomer.And then do not damaging liquid crystal sex expression energy In the range of power, it can be copolymerized with other monomers.

As other monomers, can include for example can the industrial monomer that can carry out Raolical polymerizable obtained.

As the concrete example of other monomers, unsaturated carboxylic acid, acrylate compounds, methacrylated can be included 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 included Deng.

As acrylate compounds, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, third can be included 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 acrylates, methoxy triethylene Acrylate, acrylic acid 2- ethoxy ethyl esters, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxybutyls, acrylic acid 2- methyl -2- Adamantane esters, acrylic acid 2- propyl -2- adamantane esters, acrylic acid 8- methyl -8- tricyclodecyls and acrylic acid 8- second Base -8- tricyclodecyls etc..

As methacrylate compound, such as methyl methacrylate, ethyl methacrylate, methyl can be included Isopropyl acrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthrylmethyl, Phenyl methacrylate, methacrylic acid 2,2,2- trifluoro ethyl esters, Tert-butyl Methacrylate, cyclohexyl methacrylate, first Base isobornyl acrylate, methacrylic acid 2- methoxy acrylates, methoxy triethylene methacrylate, methacrylic acid 2- ethoxy ethyl esters, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxybutyls, methacrylic acid 2- methyl -2- gold Firm Arrcostab, methacrylic acid 2- propyl -2- adamantane esters, methacrylic acid 8- methyl -8- tricyclodecyls and methyl-prop Olefin(e) acid 8- ethyl -8- tricyclodecyls etc..Can also use (methyl) glycidyl acrylate, (methyl) acrylic acid (3- methyl- 3- oxetanyls) methyl esters and (methyl) acrylic acid (3- ethyl -3- oxetanyls) methyl esters etc. have cyclic ether group (methyl) acrylate compounds.

As vinyl compound, such as vinethene, ethylene methacrylic ether, benzyl ethylene ether, 2- hydroxyethyls can be included Vinethene, phenylvinyl ether and propyl vinyl ether etc..

As distyryl compound, can include such as styrene, methyl styrene, chlorostyrene, bromstyrol.

As maleimide compound, such as maleimide, N- methylmaleimidos, N- phenyl horses can be included Come acid imide and N- N-cyclohexylmaleimides etc.

It for the high molecular manufacturing method of side chain type of present embodiment, is not particularly limited, can utilize and industrially should Universal method.It specifically, can be by using liquid crystal liquid crystal property side chain monomer, the sun of the vinyl of photoreactivity side chain monomer Ionic polymerization, free radical polymerization, anionic polymerisation manufacture.Among these, from viewpoints such as reaction controlling easnesses, especially Preferably free radical polymerization.

As the polymerization initiator of free radical polymerization, radical polymerization initiator, invertibity addition-cracking type can be used Compound well known to chain tra nsfer (RAFT) polymerization agent etc..

Free radical thermal polymerization is the compound by being heated to more than decomposition temperature generating free radicals.As this Kind of free radical thermal polymerization, can include such as peroxidating ketone (methyl ethyl ketone peroxide, Cyclohexanone peroxides), Peroxidating two acyl base class (acetyl peroxide, benzoyl peroxide etc.), hydroperoxide kind (hydrogen peroxide, tert-butyl hydroperoxide, Cumene hydroperoxide etc.), dialkyl peroxide class (di-tert-butyl peroxide, dicumyl peroxide, two lauroyl peroxides Compound etc.), ketal peroxide class (dibutyl cyclohexane peroxide etc.), alkyl peroxyesters class (new peroxide tert-butyl caprate, The peroxidating pivalic acid tert-butyl ester, peroxidating 2- cyclohexyl alkanoic acid tert-pentyl esters etc.), persulfuric acid salt (potassium peroxydisulfate, persulfuric acid Sodium, ammonium persulfate etc.), azo compound (azobis isobutyronitrile and 2,2 '-two (2- hydroxyethyls) azobis isobutyronitriles etc.). This free radical thermal polymerization can be used alone, alternatively, two or more can also be applied in combination.

As long as radical photopolymerization initiator triggers the compound of free radical polymerization due to light irradiates, just do not limit especially It is fixed.As this radical photopolymerization initiator, benzophenone, Michler's keton, 4 can be included, 4 '-bis- (lignocaine) hexichol first Ketone, xanthone, thio xanthone, isopropyl xanthone, 2,4- diethyl sulfides are for xanthone, 2- ethyl hydrazine, benzene It is ethyl ketone, 2- hydroxy-2-methyls propiophenone, 2- hydroxy-2-methyls -4 '-cumene acetone, 1- hydroxycyclohexylphenylketones, different Propyl benzoin ether, isobutyl benzoin ether, 2,2- diethoxy acetophenones, 2,2- dimethoxy -2- phenyl acetophenones, camphor Quinone, benzanthrone, 2- methyl-1s-[4- (methyl mercapto) phenyl] -2- morpholino propyl- 1- ketone, 2- benzyl -2- dimethylamino -1- (4- Morphlinophenyl) -1- butanone, 4- dimethyl ethyl aminobenzoates, 4- dimethylaminobenzoic acids isopentyl ester, 4,4 '-two (tertiary butyls Peroxy carbonyl) benzophenone, 3,4,4 '-three (t-butylperoxycarbonyl) benzophenone, 2,4,6- trimethylbenzoyls Diphenyl phosphine oxide, 2- (4 '-methoxyl-styrene) -4,6- double (trichloromethyl) s-triazine, 2- (3 ', 4 '-dimethoxy benzenes Vinyl) double (trichloromethyl) s-triazine of -4,6-, 2- (2 ', 4 '-dimethoxy-styryl) -4,6- double (trichloromethyls) be equal Triazine, 2- (2 '-methoxyl-styrene) -4,6- double (trichloromethyl) s-triazine, 2- (4 '-amyl phenyl ether vinyl) -4,6- Double (trichloromethyl) s-triazine, 4- [p- N, N- bis- (ethoxy carbonyl methyl)] -2,6- two (trichloromethyl) s-triazine, 1,3- Double (trichloromethyl) -5- (2 '-chlorphenyl) s-triazine, 1,3- double (trichloromethyl) -5- (4 '-methoxyphenyl) s-triazine, 2- (to dimethylaminostyryl) benzoxazoles, 2- (to dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3, 3 '-carbonyl double (7- lignocaines cumarin), 2- (Chloro-O-Phenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (4- carboethoxyphenyls) -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4 dichloro benzene bases) - 4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 ' double (2,4- dibromo phenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-connection miaow Azoles, 2,2 '-bis- (2,4,6- trichlorophenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 3- (2- methyl -2- dimethylaminos Propiono) carbazole, 3,6- double (2- methyl -2- morpholinoes propiono) -9- dodecyls carbazole, 1- hydroxycyclohexylphenyls Ketone, double (5-2,4- cyclopentadiene -1- bases)-bis- (bis- fluoro- 3- of 2,6- (1H- pyrroles -1- bases)-phenyl) titanium, 3,3 ', 4,4 '-four (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary hexyl peroxy carbonyl) benzophenone, 3,3 '-two (first Epoxide carbonyl) -4,4 '-two (t-butylperoxycarbonyl) benzophenone, 3,4 '-two (methoxycarbonyl) -4,3 '-two (tertiary fourth Base peroxy carbonyl) benzophenone, 4,4 '-two (methoxycarbonyl) -3,3 '-two (t-butylperoxycarbonyl) benzophenone, 2- (3- methyl -3H- benzothiazole -2- subunits) -1- naphthalenes -2- bases-ethyl ketones or 2- (3- methyl-1s, 3- benzothiazoles -2 (3H)-subunit) -1- (2- benzoyls) ethyl ketone etc..These compounds can be used alone, and can also mix two or more make With.

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

As the organic solvent used in the high molecular polymerisation of photonasty side chain type that can show liquid crystal liquid crystal property, only If the organic solvent that the macromolecule generated can dissolve just is not particularly limited.It is exemplified below out its concrete example.

It can include：N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyls- 2-Pyrrolidone, N- methyl caprolactams, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-fourth Lactone, isopropanol, methoxy amylalcohol, cinene, ethyl pentyl group 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- methoxybutanols, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, fourth Acid butyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ether, 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, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionates, 3- ethoxy-c acid methyl second Ester, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- methoxypropionic acids, 3- methoxy propyls propyl propionate, 3- methoxypropionic acid fourths Ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanones, 3- methoxyl groups-N, N- dimethylpropionamide, 3- ethyoxyls-N, N- Dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide etc..

These organic solvents can be used alone, and can also be used in mixed way.And then even insoluble generated high score The solvent of son, as long as in the range of the macromolecule generated will not be precipitated, then can also mix into above-mentioned organic solvent makes With.

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

Polymerization temperature during free radical polymerization can select 30 DEG C~150 DEG C of arbitrary temp, be preferably 50 DEG C~100 DEG C Scope.In addition, reaction can be carried out with any concentration, it is difficult to obtain the polymer of high molecular weight, concentration mistake when concentration is too low Gao Shi, the viscosity of reaction solution become excessively high and are difficult to equably stir, therefore monomer concentration is preferably the matter of 1 mass %~50 Measure %, more preferably the mass % of 5 mass %~30.Initial reaction stage is carried out with high concentration, can add organic solvent thereafter.

In above-mentioned Raolical polymerizable, when radical polymerization initiator is more compared with the ratio of monomer, gained is high The molecular weight of molecule becomes smaller, radical polymerization initiator compared with monomer ratio less when, the high molecular molecule quantitative change of gained Greatly, therefore radical initiator compared with the ratio of polymerized monomer is preferably 0.1 mole of %~10 mole %.In addition, during polymerization Various monomer components, solvent, initiator etc. can also be added.

[recycling of polymer]

From using it is above-mentioned it is obtained by the reaction, can show in the high molecular reaction solution of photonasty side chain type of liquid crystal liquid crystal property When recycling generated macromolecule, reaction solution is put into poor solvent, precipitates these polymer.As for sinking The poor solvent in shallow lake can include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methylisobutylketone, second Alcohol, toluene, benzene, diethyl ether, ethyl methyl ether, water etc..Putting into the polymer precipitated into poor solvent can filter back After receipts, air drying or heat drying are carried out under normal or reduced pressure.In addition, repeating 2 times~10 times makes what precipitation recycled When polymer is re-dissolved in organic solvent and the operation of reprecipitation recycling, the impurity in polymer can be reduced.As at this time Poor solvent can be included such as alcohols, ketone, hydrocarbon, during using 3 kinds or more poor solvents among these, refined Efficiency further improves, so it is preferred that.

The high molecular molecular weight of (A) side chain type on the present invention, it is contemplated that when gained painting film strength, formation film When workability and the uniformity of film, utilize GPC (Gel Permeation Chromatography, gel permeation chromatography) The weight average molecular weight that method measures is preferably 2000~1000000, more preferably 5000~100000.

[preparation of polymer composition]

The polymer composition used in the present invention is preferably prepared to the form of coating fluid, to suitably form liquid crystal aligning Film.That is, polymer composition used in the present invention preferably for formed resin coating resin component be dissolved in it is organic molten It is prepared by the form of the solution that agent forms.Herein, which refers to that comprising above description liquid crystal liquid crystal property can be shown The high molecular resin component of photonasty side chain type.At this point, the content of resin component be preferably the mass % of 1 mass %~20, it is more excellent Elect the mass % of the mass % of 3 mass %~15, particularly preferably 3 mass %~10 as.

In the polymer composition of present embodiment, it is all that above-mentioned can show liquid that aforementioned resin ingredient, which can be, The photonasty side chain type macromolecule of crystalline substance, in the range of liquid crystal expressive ability and photosensitive property is not damaged, can also mix and remove Other polymer outside this.At this point, the content of other polymer in resin component be the mass % of 0.5 mass %~80, it is excellent Elect the mass % of 1 mass %~50 as.

This other polymer can include such as comprising poly- (methyl) acrylate, polyamic acid, polyimides and It is not that can show high molecular polymer of photonasty side chain type of liquid crystal liquid crystal property etc..

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

It can include：N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- methyl oneself Lactams, 2-Pyrrolidone, N- ethyl pyrrolidones, n-vinyl pyrrolidone, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, two Methyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3- methoxyl groups-N, N- dimethylpropionamide, 3- ethyoxyls-N, N- dimethyl propionyl Amine, 3- butoxy-N, N- dimethylpropionamide, 1,3- dimethyl-imidazolinones, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, Methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4- hydroxyls -4- Methyl -2 pentanone, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, Diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropyl two Alcohol list ether, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl- 3- methoxybutyls acetic acid esters, tripropylene glycol methyl ether etc..They can be used alone, and can also be used in mixed way.

The polymer composition used in the present invention can contain the ingredient outside above-mentioned (A) and (B) ingredient.As its example Son can include and film thickness uniformity, the solvent or compound of surface smoothness are improved in coated polymeric composition, improve liquid Compound of brilliant alignment films and the adaptation of substrate etc., but it is not limited to this.

As the concrete example for the solvent (poor solvent) for improving film thickness uniformity, surface smoothness, can include following molten Agent.

Such as isopropanol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, first can be included 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, propylene glycol mono-n-butyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, two Glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol list Acetic acid esters list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyls acetic acid esters, Tripropylene glycol methyl ether, 3- methyl -3- methoxybutanols, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyric acid fourth Ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, 1- hexanols, n-hexane, pentane, normal octane, diethyl ether, breast Sour methyl esters, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, methyl pyruvate, acetone Acetoacetic ester, 3- methoxy methyl propionates, 3- ethoxy-propionic acids Methylethyl, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- Methoxypropionic acid, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, 1- methoxy-2-propanols, 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- list first Ether -2- acetic acid esters, propylene glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-cs oxygroup) propyl alcohol, lactic acid first Ester, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc. have solvent of low surface tension etc..

These poor solvents can use a kind, can also be used in mixed way a variety of.During using solvent as described above, in order to Do not make the dissolubility of the solvent included in polymer composition entirety significantly reduce, be preferably 5 mass %~80 of solvent entirety Quality %, more preferably the mass % of 20 mass %~60.

As film thickness uniformity, the compound of surface smoothness is improved, fluorine system surfactant, silicon-type can be included Surfactant and nonionic surfactants etc..

More specifically, such as Eftop (registered trademark) 301, EF303, EF352 (Tohkem products can be included Corporation systems)；Megafac (registered trademark) F171, F173, R-30 (DIC CORPORATION systems)；Fluorad FC430, FC431 (Sumitomo 3M Limited systems)；AsahiGuard (registered trademark) AG710 (Asahi Glass Co., Ltds System)；Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC SEIMI CHEMICAL CO., LTD. system) etc..The use ratio of these surfactants is compared with the resin contained in polymer composition 100 mass parts of ingredient are preferably the mass parts of 0.01 mass parts~2, the mass parts of more preferably 0.01 mass parts~1.

The concrete example of compound as the adaptation for improving liquid crystal orientation film and substrate, can include described below contain Compound of functional silanes etc..

Such as 3- TSL 8330s, 3-aminopropyltriethoxysilane, 2- aminopropyls can be included Trimethoxy silane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- TSL 8330s, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, 3- ureas propyl trimethoxy silicane, 3- urea propyl triethoxies Silane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyls -3-aminopropyltriethoxysilane, Three second triamine of N- triethoxysilylpropyltetrasulfides, three second triamine of N- trimethoxy-silylpropyls, 10- trimethoxy first silicon Three azepine decane of alkyl -1,4,7-, three azepine decane of 10- triethoxysilyls -1,4,7-, 9- trimethyoxysilanes Base -3,6- diaza nonyls acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyls acetic acid esters, N- benzyl -3- amino Propyl trimethoxy silicane, N- benzyls -3-aminopropyltriethoxysilane, N- phenyl -3- TSL 8330s, Double (oxygen the ethylidene) -3- TSL 8330s of N- phenyl -3-aminopropyltriethoxysilane, N-, N- are double, and (oxygen is sub- Ethyl) -3-aminopropyltriethoxysilane etc..

And then in order to improve the adaptation of substrate and liquid crystal orientation film and prevent form liquid crystal represent element when by backlight Caused electrical characteristics reduction etc., can contain phenoplasts system as following, the change containing epoxy group in polymer composition Close the additive of object.Specific phenoplasts system additive described below, but it is not limited to the structure.

As the compound specifically containing epoxy group, ethylene glycol diglycidylether, polyethylene glycol diglycidyl can be exemplified Glycerin ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycols two shrink sweet Oily ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycols, N, N, N ', N ',-four glycidyl group m-xylene diamine, 1,3- are double (N, N- diglycidyl amino methyl) hexamethylene, N, N, N ', N ',-four glycidyl group -4,4 '-diamino-diphenyl first Alkane etc..

During using for improving the compound of the adaptation of liquid crystal orientation film and substrate, dosage is compared with combination of polymers 100 mass parts of resin component contained in object are preferably the mass parts of 0.1 mass parts~30, the mass of more preferably 1 mass parts~20 Part.When dosage is less than 0.1 mass parts, it can not expect to improve the effect of adaptation, during more than 30 mass parts, the orientation of liquid crystal has When be deteriorated.

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

As photosensitizer, have aromatic nitro compound, cumarin (7- lignocaine -4- methylcoumarins, 7- hydroxyls - 4- methylcoumarins), coumarin ketone, carbonyl bicoumarin, aromatic series 2- hydroxy-ketones and the aromatic series 2- hydroxyls substituted by amino (2- dihydroxy benaophenonels, single pair (dimethylamino) -2- dihydroxy benaophenonels or two are to (dimethylamino) -2- hydroxyl hexichol for base ketone Ketone), acetophenone, anthraquinone, xanthone, thio xanthone, benzanthrone, thiazoline (2- benzoyl methylene -3- first Base-β-aphthothiazoles quinoline, 2- (β-naphthoyl methylene) -3- methylbenzothiazoles quinoline, 2- (α-naphthoyl methylene) -3- methyl Benzothiazoline, 2- (4- biphenyl Acylmethylene) -3- methylbenzothiazoles quinoline, 2- (β-naphthoyl methylene) -3- methyl-β - Aphthothiazoles quinoline, 2- (4- biphenyl Acylmethylene) -3- methyl-β-aphthothiazoles quinoline, 2- (to fluorobenzoyl methylene) -3- ((β-naphthoyl is sub- by 2- benzoyl methylene -3- methyl-β-Nai Bing oxazolines, 2- by methyl-β-aphthothiazoles quinoline), oxazolines Methyl) -3- first base benzoxazoles quinoline, 2- (α-naphthoyl methylene) -3- first base benzoxazoles quinoline, 2- (4- biphenyl acyl group methylenes Base) -3- first base benzoxazoles quinoline, 2- (β-naphthoyl methylene) -3- methyl-β-naphthalenes and oxazoline, 2- (4- biphenyl acyl group methylenes Base) -3- methyl-β-naphthalene and oxazoline, 2- (to fluorobenzoyl methylene) -3- methyl-β-naphthalene and oxazoline), benzothiazole, Nitroaniline (meta nitro aniline or paranitroanilinum, 2,4,6- trinitroanilines) or nitro acenaphthene (5- nitros acenaphthene), (2- [(hydroxyls Base is to methoxyl group) styryl] benzothiazole, benzoin alkylether, N- alkylations phthalein ketone, acetophenone ketal (2,2- dimethoxies Base Phenyl ethyl ketone), naphthalene, anthracene (2- naphthalenes methanol, 2- naphthalene-carboxylic acids, 9- anthryl carbinols and 9- anthracene carboxylic acids), chromene, azo indolizine, Plum Lip river cumarin etc..

Preferably aromatic series 2- hydroxy-ketones (benzophenone), cumarin, coumarin ketone, carbonyl bicoumarin, acetophenone, anthracene Quinone, xanthone, thio xanthone and acetophenone ketal.

In polymer composition in addition to the foregoing, if within the scope of the effect of the invention, for changing Become the purpose of the electrical characteristics such as dielectric constant, electric conductivity of liquid crystal orientation film, can add dielectric substance, conductive materials, and then for Hardness, the purpose of consistency of film are improved when liquid crystal orientation film is made, cross-linked compound can be added.

Above-mentioned polymer composition is coated on to the method on the substrate with transverse electric field driving conductive film without spy It does not limit.

On coating method, industrial is typically to utilize the progress such as silk-screen printing, hectographic printing, flexible printing or ink-jet method Method.As other coating methods, there are infusion process, rolling method, slot coated method, spin-coating method (method of spin coating) or spraying process Deng, can according to purpose use they.

On the substrate with transverse electric field driving conductive film after coated polymeric composition, hot plate, thermal cycle are utilized The heater means such as type baking oven or IR (infrared ray) type baking oven with 50~200 DEG C, preferably make evaporation of the solvent with 50~150 DEG C, so as to It can obtain film.Drying temperature at this time is preferably shorter than the high molecular liquid crystalline phase performance temperature of side chain type.

It is unfavorable in terms of liquid crystal represents the power consumption of element when the thickness of film is blocked up, when the thickness of film is excessively thin, liquid Crystalline substance represents that the reliability of element reduces sometimes, therefore preferably 5nm~300nm, more preferably 10nm~150nm.

In addition, after [I] process and before next [II] process, it can also set and cool down the substrate for being formed with film To the process of room temperature.

In process [II], polarized UV rays are irradiated to the film obtained in process [I].Polarization is irradiated to the film surface of film During ultraviolet light, from specific direction across polarization plates to the ultraviolet light of substrate irradiation polarization.As ultraviolet light to be used, can make With the ultraviolet light that wavelength is 100nm~400nm scopes.Preferably, according to film species to be used, by choosings such as wave filters Select optimal wavelength.Also, such as can select using wavelength for 290nm~400nm scopes ultraviolet light, so as to select Induce photo-crosslinking to property.As ultraviolet light, the light for example sent by high-pressure sodium lamp can be used.

For the exposure of polarized UV rays, depending on film to be used.On exposure, it is preferably set to realize Δ A Maximum (hereinafter also referred to Δ Amax) polarized UV rays amount 1%~70% in the range of, be more preferably set to 1%~ In the range of 50%, the Δ A be the film, parallel to polarized UV rays polarization direction direction ultraviolet absorbance And the difference of the ultraviolet absorbance perpendicular to the direction of the polarization direction of polarized UV rays.

In process [III], the film that polarized UV rays have been irradiated in process [II] is heated.By heat and can to apply Film assigns tropism control ability.

Heating can use the heater means such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven.Heating temperature can It is determined with considering to make film used to show the temperature of liquid crystal liquid crystal property.

Heating temperature is preferably the temperature (hereinafter referred to as liquid crystal performance temperature) that side chain type macromolecule can show liquid crystal liquid crystal property Within the temperature range of.It can be predicted：In the case of the film surface of film etc, the liquid crystal performance temperature of film coated surface is less than Whole observation can show the liquid crystal performance temperature during photonasty side chain type macromolecule of liquid crystal liquid crystal property.Therefore, heating temperature is more excellent Within the temperature range of the liquid crystal performance temperature for electing film coated surface as.That is, the temperature model of the heating temperature after polarized UV rays is irradiated It encloses preferably using the temperature of low 10 DEG C of the lower limit of the temperature range of liquid crystal more high molecular than side chain type used performance temperature as under It limits and using 10 DEG C lower than the upper limit of the liquid crystal temperature range of temperature as the temperature of the scope of the upper limit.Heating temperature is less than upper When stating temperature range, there are in film by the torrid zone Lai the insufficient tendency of anisotropy amplification effect, in addition, heating temperature When excessively high compared with above-mentioned temperature range, exist and apply membrane stage inclining close to isotropic liquid condition (isotropic phase) To at this point, being difficult to sometimes due to self assembly to a direction reorientation.

It should be noted that liquid crystal performance temperature refers to：Side chain type macromolecule or film coated surface are from the opposite liquid crystalline phase of solid Occur that phase transition occurs more than the glass transition temperature (Tg) of phase transition and from the opposite homogeneous phase (isotropic phase) of liquid crystal The temperature of homogeneous phase transition temperature (Tiso) below.

For with process [I] described in the reasons why it is identical the reasons why, the thickness of the film formed after heating can be preferably 5nm~300nm, more preferably 50nm~150nm.

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

[IV] process is the substrate for having on the transverse electric field driving conductive film that will be obtained in [III] liquid crystal orientation film The substrate with liquid crystal orientation film without conductive film that (the 1st substrate) obtains in the same manner as in above-mentioned [I ']~[III '] (the 2nd substrate) carried out across liquid crystal in a manner that the liquid crystal orientation film of the two is opposite it is oppositely disposed, utilize well known method make Liquid crystal cells, so as to make the process that the driving liquid crystal of transverse electric field represents element.It should be noted that process [I ']~ In [III '], except with the substrate of conductive film replacing that there is the transverse direction using without transverse electric field driving in process [I] Outside the substrate of electric field driven conductive film, it can be carried out in the same manner as process [I]~[III].Process [I]~[III] and process [I ']~[III's '] only difference is that whether there is above-mentioned conductive film, therefore omit the explanation of process [I ']~[III '].

If including liquid crystal cells or liquid crystal representing a making 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, become interior with liquid crystal aligning film surface The mode of side is pasted on another substrate, decompression injection liquid crystal and the method sealed；Alternatively, it is taken to the liquid crystal for being scattered with spacer After liquid crystal is added dropwise in film surface, adhesive substrate and the method that is sealed etc..At this point, it is preferable to use with horizontal electricity for the substrate of one side The substrate of the field driving electrode of comb teeth-shaped structure.Spacer diameter at this time is preferably 1 μm~30 μm, more preferably 2 μm~ 10μm.The spacer diameter determines to clamp the spacing of a pair of of substrate of liquid crystal layer, the i.e. thickness of liquid crystal layer.

In the manufacturing method of the substrate with film of the present invention, polymer composition is coated on substrate and forms film Afterwards, polarized UV rays are irradiated.Then, by heated to realize efficiently imported into side chain type polymeric membrane it is each to different Property, so as to manufacture the substrate with liquid crystal orientation film for possessing liquid crystal aligning control ability.

In film used in the present invention, molecule that the light reaction using side chain and the self assembly based on liquid crystal liquid crystal property are induced The principle of reorientation, realizes and efficiently imports anisotropy to film.In the manufacturing method of the present invention, side chain type macromolecule has During structure of the photocrosslinking reaction group as photoreactive group, after forming film on substrate using side chain type macromolecule, irradiation Polarized UV rays after then being heated, make liquid crystal and represent element.

Hereinafter, will use with photocrosslinking reaction group as the high molecular reality of the side chain type of the structure of photoreactive group The mode of applying is known as the 1st mode, will use with light fries' rearrangement group or has carried out the group of isomerization as photoreactivity The high molecular embodiment of side chain type of the structure of group is known as the 2nd mode, and illustrates.

Fig. 1 is schematically to illustrate to have been used in the 1st mode of the present invention with photocrosslinking reaction group as light reaction Property group structure side chain type macromolecule form, the anisotropy in the manufacturing method of liquid crystal orientation film import the one of processing The figure of example.(a) of Fig. 1 is the figure for the state for schematically illustrating the side chain type polymeric membrane before polarizing light irradiation, (b) of Fig. 1 The figure for the state for schematically illustrating the side chain type polymeric membrane after polarizing light irradiation, (c) of Fig. 1 be schematically explanation plus The figure of the state of side chain type polymeric membrane after heat, when the anisotropy especially imported is small, i.e., the 1st mode in the present invention In, the ultraviolet irradiation amount of [II] process is when making Δ A reach in the range of the 1%~15% of maximum ultraviolet irradiation amount Schematic diagram.

Fig. 2 is schematically to illustrate to have been used in the 1st mode of the present invention with photocrosslinking reaction group as light reaction Property group structure side chain type macromolecule form, the anisotropy in the manufacturing method of liquid crystal orientation film import the one of processing The figure of example.(a) of Fig. 2 is the figure for the state for schematically illustrating the side chain type polymeric membrane before polarizing light irradiation, (b) of Fig. 2 The figure for the state for schematically illustrating the side chain type polymeric membrane after polarizing light irradiation, (c) of Fig. 2 be schematically explanation plus The figure of the state of side chain type polymeric membrane after heat, when the anisotropy especially imported is big, i.e., the 1st mode in the present invention In, the ultraviolet irradiation amount of [II] process is when making Δ A reach in the range of the 15%~70% of maximum ultraviolet irradiation amount Schematic diagram.

Fig. 3 is schematically to illustrate to have been used in the 2nd mode of the present invention with photoisomerization group or above-mentioned formula (18) the light fries' rearrangement group shown in is formed as the side chain type macromolecule of the structure of photoreactive group, liquid crystal aligning Anisotropy in the manufacturing method of film imports the figure of an example of processing.(a) of Fig. 3 is before schematically illustrating polarizing light irradiation Side chain type polymeric membrane state figure, (b) of Fig. 3 is the side chain type polymeric membrane schematically illustrated after polarizing light irradiation State figure, (c) of Fig. 3 be schematically illustrate heating after side chain type polymeric membrane state figure, especially led When the anisotropy entered is small, i.e., in the 2nd mode of the present invention, the ultraviolet irradiation amount of [II] process makes Δ A reach maximum Ultraviolet irradiation amount 1%~70% in the range of when schematic diagram.

Fig. 4 be schematically illustrate to have used in the 2nd mode of the present invention it is not sharp with the light shown in above-mentioned formula (19) This is reset in manufacturing method that group is formed as the side chain type macromolecule of the structure of photoreactive group, liquid crystal orientation film Anisotropy imports the figure of an example of processing.(a) of Fig. 4 is the side chain type polymeric membrane schematically illustrated before polarizing light irradiation State figure, (b) of Fig. 4 is the figure for the state for schematically illustrating the side chain type polymeric membrane after polarizing light irradiation, Fig. 4's (c) be schematically illustrate heating after side chain type polymeric membrane state figure, when the anisotropy especially imported is big, I.e. in the 2nd mode of the present invention, the ultraviolet irradiation amount of [II] process makes Δ A reach maximum ultraviolet irradiation amount Schematic diagram when in the range of 1%~70%.

In the 1st mode of the present invention, by importing anisotropic processing, the ultraviolet irradiation amount of [II] process to film Be make Δ A reach the 1%~15% of maximum ultraviolet irradiation amount in the range of when, first, film 1 is formed on substrate.Such as Shown in (a) of Fig. 1 like that, in the film 1 formed on substrate, there is the structure of 2 random alignment of side chain.According to the side chain 2 of film 1 Random alignment, the liquid crystal ultimate constituent and photonasty group of side chain 2 be also randomly oriented, which is isotropic.

In the 1st mode of the present invention, by importing anisotropic processing, the ultraviolet irradiation amount of [II] process to film Be make Δ A reach the 15%~70% of maximum ultraviolet irradiation amount in the range of when, first, film 3 is formed on substrate.Such as Shown in (a) of Fig. 2 like that, in the film 3 formed on substrate, there is the structure of 4 random alignment of side chain.According to the side chain 4 of film 3 Random alignment, the liquid crystal ultimate constituent and photonasty group of side chain 4 be also randomly oriented, which is isotropic.

In the 2nd mode of the present invention, by importing anisotropic processing to film, using with photoisomerization During the high molecular liquid crystal orientation film of the side chain type of the structure of the light fries' rearrangement group shown in property group or above-mentioned formula (18), The ultraviolet irradiation amount of [II] process be make Δ A reach the 1%~70% of maximum ultraviolet irradiation amount in the range of when, it is first First, film 5 is formed on substrate.As shown in (a) of Fig. 3, in the film 5 formed on substrate, there is 6 random alignment of side chain Structure.According to the random alignment of the side chain 6 of film 5, the liquid crystal ultimate constituent and photonasty group of side chain 6 are also randomly oriented, The side chain type polymeric membrane 5 is isotropic.

In the 2nd mode of the present invention, by importing anisotropic processing to film, using with above-mentioned formula (19) during the high molecular liquid crystal orientation film of the side chain type of the structure of the light fries' rearrangement group shown in, the ultraviolet light of [II] process Exposure be make Δ A reach the 1%~70% of maximum ultraviolet irradiation amount in the range of when, first, formed and applied on substrate Film 7.As shown in (a) of Fig. 4, in the film 7 formed on substrate, there is the structure of 8 random alignment of side chain.According to film 7 Side chain 8 random alignment, the liquid crystal ultimate constituent and photonasty group of side chain 8 be also randomly oriented, which is isotropism 's.

In 1st mode of this implementation, the ultraviolet irradiation amount of [II] process is the ultraviolet irradiation amount that Δ A is made to reach maximum 1%~15% in the range of when, polarized UV rays are irradiated to the isotropic film 1.As a result, as Fig. 1 (b) shown in that Sample, along side chain 2a's among the side chain 2 of the direction arrangement parallel with the polarization direction of ultraviolet light, that there is photonasty group The light reactions such as dimerization reaction occur photonasty group priorities.As a result, the density that the side chain 2a of light reaction has occurred is being irradiated It is slightly become higher on the polarization direction of ultraviolet light, as a result, assigning very small anisotropy to film 1.

In 1st mode of this implementation, the ultraviolet irradiation amount of [II] process is the ultraviolet irradiation amount that Δ A is made to reach maximum 15%~70% in the range of when, polarized UV rays are irradiated to the isotropic film 3.As a result, as shown in (b) of Fig. 2 Like that, side chain 4a among the side chain 4 arranged along the direction parallel with the polarization direction of ultraviolet light, with photonasty group Photonasty group priorities the light reactions such as dimerization reaction occur.As a result, the density that the side chain 4a of light reaction has occurred is being shone It penetrates on the polarization direction of ultraviolet light and becomes higher, as a result, assigning small anisotropy to film 3.

In the 2nd mode of this implementation, using having photoisomerization group or the light shown in above-mentioned formula (18) The high molecular liquid crystal orientation film of side chain type of the structure of fries' rearrangement group, the ultraviolet irradiation amount of [II] process are to make Δ A When reaching in the range of the 1%~70% of maximum ultraviolet irradiation amount, polarized UV is irradiated to isotropic film 5 Line.As a result, as shown in (b) of Fig. 3, among the side chain 6 arranged along the direction parallel with the polarization direction of ultraviolet light, The light reactions such as light fries' rearrangement occur the photonasty group priorities of side chain 6a with photonasty group.As a result, occur The density of the side chain 6a of light reaction slightly becomes higher on the polarization direction of irradiation ultraviolet light, as a result, assigned very to film 5 Small anisotropy.

In the 2nd mode of this implementation, using the light fries' rearrangement group having shown in above-mentioned formula (19) The high molecular film of side chain type of structure, the ultraviolet irradiation amount of [II] process are the ultraviolet irradiation amounts that Δ A is made to reach maximum 1%~70% in the range of when, polarized UV rays are irradiated to the isotropic film 7.As a result, as Fig. 4 (b) shown in that Sample, along side chain 8a's among the side chain 8 of the direction arrangement parallel with the polarization direction of ultraviolet light, that there is photonasty group The light reactions such as light fries' rearrangement occur photonasty group priorities.As a result, the density that the side chain 8a of light reaction has occurred exists It irradiates on the polarization direction of ultraviolet light and becomes higher, as a result, assigning small anisotropy to film 7.

Then, in the 1st mode of this implementation, the ultraviolet irradiation amount of [II] process is the ultraviolet light that Δ A is made to reach maximum When in the range of the 1%~15% of exposure, the film 1 after irradiation polarised light is heated and mesomorphic state is made.As a result, as schemed Shown in 1 (c) like that, in film 1, in the direction of the polarization direction parallel to irradiation ultraviolet light and perpendicular to irradiation ultraviolet light Between the direction of polarization direction, the amount of the cross-linking reaction of generation is different.At this point, the side of the polarization direction parallel to irradiation ultraviolet light It is very small to the amount of the cross-linking reaction of generation, therefore the cross-linking reaction position is worked as plasticizer.Therefore, perpendicular to photograph The liquid crystal liquid crystal property for penetrating the direction of the polarization direction of ultraviolet light is higher than the liquid crystal liquid crystal property in the direction parallel to the polarization direction for irradiating ultraviolet light, Self assembly occurs parallel to the direction of the polarization direction of irradiation ultraviolet light, the side chain 2 comprising liquid crystal ultimate constituent carries out reorientation. As a result, the very small anisotropy of the film 1 induced due to photo-crosslinking is amplified due to heat, bigger is assigned to film 1 Anisotropy.

Similarly, in the 1st mode of this implementation, the ultraviolet irradiation amount of [II] process is that Δ A is made to reach the ultraviolet of maximum When in the range of the 15%~70% of line exposure, the film 3 after polarizing light irradiation is heated and mesomorphic state is made.As a result, As shown in (c) of Fig. 2, in side chain type polymeric membrane 3, parallel to irradiation ultraviolet light polarization direction direction with it is vertical Between the direction of the polarization direction of irradiation ultraviolet light, the amount of the cross-linking reaction of generation is different.Therefore, parallel to irradiation ultraviolet light The direction of polarization direction self assembly occurs, side chain 4 comprising liquid crystal ultimate constituent carries out reorientation.As a result, because of photo-crosslinking The smaller anisotropy for the film 3 for reacting and inducing is amplified due to heat, and the anisotropy of bigger is assigned to film 3.

Similarly, in the 2nd mode of this implementation, using having, photoisomerization group or above-mentioned formula (18) are shown Light fries' rearrangement group structure the high molecular film of side chain type, the ultraviolet irradiation amount of [II] process is to reach Δ A When in the range of to the 1%~70% of maximum ultraviolet irradiation amount, the film 5 after polarizing light irradiation is heated and is made Mesomorphic state.As a result, as shown in (c) of Fig. 3, in film 5, parallel to irradiation ultraviolet light polarization direction direction with Between the direction of the polarization direction of irradiation ultraviolet light, the amount of the light Fries rearrangement of generation is different.It is at this point, vertical In irradiation ultraviolet light polarization direction direction generate light fries' rearrangement body liquid crystal aligning power than the side chain before reaction Liquid crystal aligning power is strong, therefore self assembly occurs perpendicular to the direction of the polarization direction of irradiation ultraviolet light, includes liquid crystal ultimate constituent Side chain 6 carry out reorientation.As a result, the very small anisotropy of the film 5 induced due to light Fries rearrangement because Heat and amplify, to film 5 imparting bigger anisotropy.

Similarly, in the 2nd mode of this implementation, using the light fries' rearrangement base having shown in above-mentioned formula (19) The high molecular film of side chain type of the structure of group, the ultraviolet irradiation amount of [II] process are that Δ A is made to reach maximum ultraviolet light to shine When in the range of the 1%~70% of the amount of penetrating, the film 7 after polarizing light irradiation is heated and mesomorphic state is made.As a result, such as Shown in (c) of Fig. 4 like that, in side chain type polymeric membrane 7, parallel to irradiation ultraviolet light polarization direction direction with perpendicular to It irradiates between the direction of the polarization direction of ultraviolet light, the amount of the light Fries rearrangement of generation is different.Light fries' rearrangement body 8 (a) anchor force is than the side chain Final 8 before rearrangement, therefore when generating certain a certain amount of above light fries' rearrangement body, parallel to photograph Self assembly occurs for the direction for penetrating the polarization direction of ultraviolet light, and the side chain 8 comprising liquid crystal ultimate constituent carries out reorientation.As a result, The smaller anisotropy of the film 7 induced due to light Fries rearrangement is amplified due to heat, and each of bigger is assigned to film 7 Anisotropy.

Therefore, the film used in method of the invention is irradiated at polarized UV rays and heating film by carrying out successively So as to efficiently be imported anisotropy, the excellent liquid crystal orientation film of tropism control ability can be made in reason.

Also, for the film for being used in the method for the present invention, optimize the photograph of the polarized UV rays to film irradiation The amount of penetrating and the heating temperature heated.Thus, it is possible to realize efficiently to import anisotropy to film.

The irradiation of optimal polarized UV rays for the film used into the present invention efficiently imports anisotropy Amount, which corresponds to, makes the photonasty group in the film that photo-crosslinking, photoisomerization reaction or light Fries rearrangement occur Amount reaches optimal polarized UV rays exposure.It is film irradiation polarized UV rays as a result, progress light to what is used in the present invention When the photonasty group of the side chain of cross-linking reaction, photoisomerization reaction or light Fries rearrangement is few, sufficient light is not achieved Reacting dose.At this point, even if sufficient self assembly will not be carried out by carrying out heating behind.On the other hand, in the present invention For the film used, to structured illumination polarized UV rays as a result, carrying out the side of cross-linking reaction with photocrosslinking reaction group During the photonasty group excess of chain, the cross-linking reaction between side chain can be promoted excessively.At this point, gained film becomes upright and outspoken, interfere sometimes Thereafter the propulsion of the self assembly by heating.In addition, for the film used in the present invention, to light fries The structured illumination polarized UV rays of group are reset as a result, carrying out the photonasty group of the side chain of light Fries rearrangement becomes When excessive, the liquid crystal liquid crystal property of film can be reduced too.At this point, the liquid crystal liquid crystal property of gained film also reduces, interfere sometimes thereafter by adding The propulsion of the self assembly of heat.And then during to structured illumination polarized UV rays with light fries' rearrangement group, if ultraviolet light Exposure it is excessive, then side chain type macromolecule occur photodegradation, interfere the propulsion of the self assembly by heating thereafter sometimes.

Therefore, in film used in the present invention, the photonasty group of side chain occurs due to 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, more preferably it is set to 0.1 mole of %~20 mole %.By making progress The amount of the photonasty group of the side chain of light reaction is this scope, and the self assemblyization in heating thereafter can be promoted efficiently, The efficient anisotropy in film can be formed.

In film used in the method for the present invention, by the optimization of the exposure of polarized UV rays, so as to optimize side chain The photo-crosslinking of photonasty group in the side chain of type polymeric membrane, photoisomerization reaction or light Fries rearrangement Amount.Also, it is realized together with heating thereafter and efficiently imports anisotropy into film used in the present invention.This When, for suitable polarized UV rays amount, can be carried out based on the evaluation of the UV absorption of film used in the present invention.

That is, for the film used in the present invention, measure respectively it is after polarized UV rays irradiation, parallel to polarized UV The ultraviolet radiation absorption in the direction of the polarization direction of line and the ultraviolet radiation absorption perpendicular to the direction of the polarization direction of polarized UV rays. It is the side of the polarization direction parallel to polarized UV rays in the film by measurement result evaluation the Δ A, the Δ A of UV absorption To ultraviolet absorbance and ultraviolet absorbance perpendicular to the direction of the polarization direction of polarized UV rays difference.Also, it asks Go out the maximum (Δ Amax) of the Δ A realized in film used in the present invention and realize the exposure of its polarized UV rays. 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 Be set to realize the amount of the polarized UV rays of Δ Amax 1%~70% in the range of, be more preferably set to 1%~50% scope It is interior.In film used in the present invention, can realize the polarized UV rays of Δ Amax amount 1%~50% in the range of it is inclined Ultraviolet irradiation amount of shaking is equivalent to 0.1 mole of %~20 for making photonasty group entirety possessed by the side chain type polymeric membrane The amount of the polarized UV rays of photo-crosslinking occurs for mole %.

As described above, in the manufacturing method of the present invention, anisotropy is efficiently imported to film in order 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 When the high molecular liquid crystal temperature range of side chain type is 100 DEG C~200 DEG C used in bright, it is expected after irradiating polarized UV rays Heating temperature is 90 DEG C~190 DEG C.It sets in this way, the anisotropy of bigger is assigned to film used in the present invention.

It operates in this way, the liquid crystal provided by the present invention represents that element shows that height can to external stresses such as light, heat By property.

Operate as above, the driving liquid crystal of the transverse electric field manufactured by the method for the present invention represent component substrate or There is person the driving liquid crystal of the transverse electric field of the substrate to represent the of excellent in reliability of element, can be suitably employed in big picture and high definition Clear LCD TV etc..

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

Embodiment

Methacrylic monomer MA1~the MA5 used in embodiment described below.

It should be noted that MA1 and M2 following synthesis respectively.That is, MA1 is by patent document (WO2011-084546) The synthetic method and synthesize.MA2 be by the synthetic method described in patent document (Japanese Unexamined Patent Publication 9-118717) and Synthesis.

MA3 has used commercially available product.

MA4 has used the M6BC as commercially available product (Co. Ltd. system is learned in greening).

MA5 is the undocumented new compounds such as document.MA5 is synthesized using MA2 and MA5-1, and details are following "<The synthesis of compound MA5>" in illustrate.It should be noted that MA5-1 is by document (Liquid Crystals (2005), 32 (8), 1031-1044.) described in synthetic method and synthesize.

In addition, the reagent used in the present embodiment described below is referred to as.

(organic solvent)

THF：Tetrahydrofuran.

NMP：N-methyl-2-pyrrolidone.

BC：Butyl cellosolve.

(organic synthesis reagent)

EDC：1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides.

DMAP：4-dimethylaminopyridine.

(polymerization initiator)

AIBN：2,2 '-azobis isobutyronitrile.

Into 500mL four-neck flasks add compound MA2 (20.00g, 65.3mmol), compound MA5-1 (14.09g, 71.8mmol), EDC (15.02g, 78.4mmol), DMAP (0.80g, 6.53mmol), THF (200g), are reacted with 23 DEG C. Reactive tracing is carried out using HPLC, confirms after reaction, reaction solution is injected into distilled water (1.2L), adds acetic acid second Ester (2L) operates removal water layer by liquid separation.After organic layer is cleaned 3 times with distilled water (500mL), by organic layer magnesium sulfate It is dried.Thereafter, filter and using Rotary Evaporators distillation removal solvent, so as to obtain chemical combination in the form of oily compound Object MA5-2.Then, added into gained compound MA5-2 pyridine p-toluenesulfonic acid (be labeled as " PPTS ") (1.59g, 6.3mmol), ethyl alcohol (100g), with 60 DEG C of progress heating stirrings.Reactive tracing is carried out using HPLC, is confirmed after reaction, it will Reaction solution is cooled down with ice bath, and filtering solid be precipitated simultaneously is cleaned with ethyl alcohol.By subtracting to obtained solid It press dry dry, obtains compound MA519.2g (yield 69%).

¹H-NMR(400MHz,CDCl3,δppm):8.22-8.18(2H,m),8.17-8.14(2H,m),7.36-7.32 (2H,m),7.00-6.96(2H,m),6.12-6.11(1H,m),5.57-5.55(1H,m),4.20-4.16(2H,m),4.06 (2H,t),1.96-1.95(3H,m),1.90-1.46(8H,m).

MA1 (1.99g, 6.0mmol), MA2 (7.35g, 24.0mmol), MA3 (0.33g, 1.5mmol) are dissolved in THF In (85.45g), after being de-gassed with diaphragm pump, addition AIBN (0.246g, 1.5mmol) is simultaneously de-gassed again.Thereafter with 50 DEG C reaction 24 it is small when, obtain the polymer solution of methacrylate.The polymer solution is added dropwise to diethyl ether (2000ml), Filter gained sediment.The sediment with diethyl ether is cleaned, is dried under reduced pressure in 40 DEG C of baking oven, obtains metering system Acid ester polymer powder.

Into gained powder 6.0g add NMP 54.0g, be stirred at room temperature 3 it is small when.BC (40.0g) is added into the solution And stir, so as to obtain aligning agent for liquid crystal solution A 1.

MA1 (9.97g, 30.0mmol), MA3 (0.41g, 1.8mmol), MA4 (11.47g, 30.0mmol) are dissolved in In THF (126.7g), after being de-gassed with diaphragm pump, addition AIBN (0.49g, 3.0mmol) simultaneously deaerates again, carries out nitrogen and puts It changes.Thereafter with 50 DEG C reaction 24 it is small when, obtain the polymer solution of methacrylate.The polymer solution is added dropwise to diethyl Ether (4000ml) filters gained sediment.The sediment with diethyl ether is cleaned, is dried under reduced pressure in 40 DEG C of baking oven, Obtain methacrylate polymers powder.

Into gained powder 6.0g add NMP 54.0g, with 40 DEG C stirring 3 it is small when.BC (40.0g) is added into the solution And stir, so as to obtain aligning agent for liquid crystal solution A 2.

MA1 (9.97g, 30.0mmol), MA3 (0.41g, 1.8mmol), MA5 (12.79g, 30mmol) are dissolved in THF In (134.1g), after being de-gassed with diaphragm pump, addition AIBN (0.49g, 3.0mmol) simultaneously deaerates again, carries out nitrogen displacement. Thereafter with 50 DEG C reaction 24 it is small when, obtain the polymer solution of methacrylate.The polymer solution is added dropwise to diethyl ether (4000ml) filters gained sediment.The sediment with diethyl ether is cleaned, is dried under reduced pressure, obtained in 40 DEG C of baking oven To methacrylate polymers powder.

Into gained powder 6.0g add NMP 54.0g, be stirred at room temperature 3 it is small when.BC (40.0g) is added into the solution And stir, so as to obtain aligning agent for liquid crystal solution A 3.

Using the aligning agent for liquid crystal A1 obtained in synthesis example 1, the making of liquid crystal cells is carried out according to following the step of showing. Substrate is the glass substrate that size is 30mm × 40mm, thickness is 0.7mm, using be configured with by ito film pattern and formed The substrate of comb teeth-shaped pixel electrode.

Pixel electrode has the broach that " ＜ " font electrode element that middle body bends is formed through multiple arrangements Shape shape.The width of the width of each electrode element is 10 μm, between electrode element at intervals of 20 μm.Form the picture of each pixel The electrode element of " ＜ " font that plain electrode is bent by middle body is formed through multiple arrangements, therefore the shape of each pixel It is not oblong-shaped, but possesses " ＜ " word bending in the same manner as electrode element in middle body, similar to runic Shape.

Each pixel is split up and down using its central bent portion as boundary, have bent portion upside the 1st region and 2nd region of downside.When comparing the 1st region and 2 region of each pixel, the shape of the electrode element of their pixel electrode is formed It is different into direction.That is, using the orientation process direction of aftermentioned liquid crystal orientation film as during benchmark, in the 1st region of pixel, to be in The mode of angle (clockwise)+15 ° existing forms the electrode element of pixel electrode, in the 2nd region of pixel, to be presented -15 ° The mode of angle (clockwise) form the electrode element of pixel electrode.That is, the 1st region of each pixel and the 2nd following structure in region Into：Spinning movement (the plane in liquid crystal, real estate induced by applying voltage between pixel electrode and counter electrode Switching) direction opposite direction each other.

<<The preparation of liquid crystal cells>>

The aligning agent for liquid crystal A1 obtained in synthesis example 1 is spin-coated on the above-mentioned electroded substrate prepared.Then, use 70 DEG C of press drying 90 seconds forms the liquid crystal orientation film that film thickness is 100nm.Then, across polarization plates with 10mJ/cm²It is right After the ultraviolet light of coated surface irradiation 313nm, heated 10 minutes with 140 DEG C of hot plates, obtain the substrate with liquid crystal orientation film.Separately Outside, as opposite substrate, to not forming electrode and similarly being formed with the glass substrate highly for 4 μm of column spacer Film implements orientation process.Printing and sealing agent (the vertical Chemical Co., Ltd. system of association, the XN- on the liquid crystal orientation film of a substrate 1500T).Then, after pasting another substrate in a manner that liquid crystal aligning film surface is opposite and differently- oriented directivity reaches 0 °, sealant is made Heat cure and make dummy cell.Liquid crystal MLC-2041 (MERCK are injected by depressurizing in the injection normal direction dummy cell CORPORATION systems), inlet is sealed, obtains the liquid crystal for possessing IPS (In-Planes Switching, plane switching) pattern Represent the liquid crystal cells that element is formed.

In embodiment 2, heated with 200 DEG C of hot plate using aligning agent for liquid crystal A2, in embodiment 3, taken using liquid crystal It is heated to agent A3 with 180 DEG C of hot plate, in addition, liquid crystal cells is prepared using method same as Example 1.

[evaluation of liquid crystal aligning]

Element is represented for the liquid crystal for operating as above and manufacturing, and when being observed using light microscope, does not observe leakage Light is then evaluated as liquid crystal aligning " good ", observes that light leak is then evaluated as liquid crystal aligning " bad ".

<<Voltage retention (VHR) is evaluated>>

Using the liquid crystal cells of above-mentioned making, apply the 5V voltages of 60 μ s at a temperature of 70 DEG C, after measuring 16.67ms Voltage measures voltage retention.The voltage retention at the initial stage is denoted as VHR1 (%).Hereafter, under 70 DEG C of isoperibol, 16Vpp alternating voltages when small with the frequency application 168 of 30Hz.Thereafter, make the pixel electrodes of liquid crystal cells and counter electrode it Between short circuit occurs after, method same as described above is utilized to measure voltage retention.The voltage retention is denoted as VHR2 (%).

The decrement Δ VHR (%) of voltage retention is obtained by following formula, and is recorded in table 1.

Δ VHR (%)=VHR1-VHR2

It should be noted that the measure of voltage retention has used the voltage retention of TOYO Corporation to measure Device VHR-1.

By the liquid crystal aligning of embodiment 1 and VHR the results are shown in tables 1.

MA1 (1.99g, 6.0mmol), MA2 (7.35g, 24.0mmol) are dissolved in THF (85.45g), use diaphragm pump After being de-gassed, addition AIBN (0.246g, 1.5mmol) is simultaneously de-gassed again.Thereafter, with 50 DEG C reaction 24 it is small when, so as to Obtain the polymer solution of methacrylate.The polymer solution is added dropwise to diethyl ether (2000ml), filtering gained precipitation Object.The sediment with diethyl ether is cleaned, is dried under reduced pressure in 40 DEG C of baking oven, obtains methacrylate polymers powder End.

Into gained powder 6.0g add NMP 54.0g, be stirred at room temperature 3 it is small when.BC (40.0g) is added into the solution And stir, so as to obtain aligning agent for liquid crystal solution B 1.The polymer solution obtained in the above method is used as aligning agent for liquid crystal B1, In addition, liquid crystal cells are prepared similarly to Example 1, measure voltage retention and carry out the evaluation of liquid crystal aligning.It will The results are shown in tables 1.

MA1 (9.97g, 30.0mmol), MA4 (11.47g, 30mmol) are dissolved in THF (124.3g), use diaphragm pump After being de-gassed, addition AIBN (0.49g, 3.0mmol) simultaneously deaerates again, carries out nitrogen displacement.Thereafter, it is small with 50 DEG C of reactions 24 When, so as to obtain the polymer solution of methacrylate.The polymer solution is added dropwise to diethyl ether (4000ml), filters institute Obtain sediment.The sediment with diethyl ether is cleaned, is dried under reduced pressure in 40 DEG C of baking oven, is obtained methacrylate and gather Close object powder.

Into gained powder 6.0g add NMP 54.0g, with 40 DEG C stirring 3 it is small when.BC (40.0g) is added into the solution And stir, so as to obtain aligning agent for liquid crystal solution B 2.The polymer solution obtained in the above method is used as aligning agent for liquid crystal B2. The temperature heated using hot plate of embodiment 1 is set to 200 DEG C, in addition, liquid crystal list is prepared using identical method Member measures voltage retention and carries out the evaluation with liquid crystal aligning.Show the result in table 1.

MA1 (9.97g, 30.0mmol), MA5 (12.79g, 30mmol) are dissolved in THF (131.8g), use diaphragm pump After being de-gassed, addition AIBN (0.49g, 3.0mmol) simultaneously deaerates again, carries out nitrogen displacement.Thereafter, it is small with 50 DEG C of reactions 24 When, so as to obtain the polymer solution of methacrylate.The polymer solution is added dropwise to diethyl ether (4000ml), filters institute Obtain sediment.The sediment with diethyl ether is cleaned, is dried under reduced pressure in 40 DEG C of baking oven, is obtained methacrylate and gather Close object powder.

Into gained powder 6.0g add NMP 54.0g, be stirred at room temperature 3 it is small when.BC (40.0g) is added into the solution And stir, so as to obtain aligning agent for liquid crystal solution B 3.The polymer solution obtained in the above method is used as aligning agent for liquid crystal B3. The temperature heated using hot plate of embodiment 1 is set to 180 DEG C, in addition, liquid crystal list is prepared using identical method Member measures voltage retention and carries out the evaluation of liquid crystal aligning.Show the result in table 1.

MA3 (0.33g, 10.0mmol) is dissolved in THF (30.9g), after being de-gassed with diaphragm pump, adds AIBN (0.08g, 0.5mmol) is simultaneously de-gassed again.Thereafter, with 50 DEG C of reactions 24 it is small when, so as to obtain the poly- of methacrylate Polymer solution T1.0.8g T1 are added into aligning agent for liquid crystal solution B 150g, obtain aligning agent for liquid crystal B4.The above method will be utilized Obtained polymer solution is used as aligning agent for liquid crystal B4, in addition, prepares liquid crystal cells similarly to Example 1, measures electricity Press conservation rate.Show the result in table 1.

[table 1]

1. Examples 1 to 3 of table and the liquid crystal aligning of comparative example 1~4 and voltage retention VHR

It can be clear and definite by table 1：It can be formed by Examples 1 to 3 and show good liquid crystal aligning and can maintain good Electrical characteristics liquid crystal orientation film.In addition we know：In comparative example 1, comparative example 2 and comparative example 3 without MA3, voltage is kept Rate reduces.In addition we know：It is not copolymerized with MA3 but in the high molecular comparative example 4 of side chain type, does not show good liquid crystal aligning Property.

Reference sign

Fig. 1

1 side chain type polymeric membrane

2nd, 2a side chains

Fig. 2

3 side chain type polymeric membranes

4th, 4a side chains

Fig. 3

5 side chain type polymeric membranes

6th, 6a side chains

Fig. 4

7 side chain type polymeric membranes

8th, 8a side chains

Claims

1. a kind of driving liquid crystal of transverse electric field represents that element is manufactured with liquid crystal orientation film with polymer composition, contain：(A) The photonasty side chain type macromolecule of liquid crystal liquid crystal property and (B) organic solvent are shown within the scope of specific temperature,

(A) side chain type macromolecule is somebody's turn to do to possess selected from by the 1st repetitive unit with annular amine structure and the with phenol structure the 2nd At least one kind of repetitive unit in the group of repetitive unit composition,

2 adjacent with the nitrogen-atoms carbon atom of the ring-type amine structure is respectively provided with the substituent group shown in 2 following formula (S), In formula (S), R¹¹For singly-bound or optionally substituted alkyl, X is singly-bound, oxygen atom, sulphur atom ,-CO- ,-CO-O- or-O-CO-, R¹²For optionally substituted alkyl, wherein, when X is not singly-bound, R¹¹And R¹²Optionally bond together and form ring structure,

At least one carbon atom among the ortho position carbon atom of the hydroxyl of the phenol structure has the substitution shown in following formula (S) Base,

-R¹¹-x-R¹² (S)

1st repetitive unit is represented with following formula (1-1), and in formula (1-1), R is hydrogen atom or methyl, R¹¹It is optionally each identical Or it is different, there is definition same as described above, X is optionally each identical or different, has definition same as described above, R¹²It is optionally each From identical or different, there is definition same as described above, B¹For the organic of hydrogen atom, oxygen atom, halogen atom, hydroxyl or 1 valency Group, m are 0~4 integer；

2nd repetitive unit is represented with following formula (1-2), and in formula (1-2), R is hydrogen atom or methyl, R¹¹It is optionally each identical Or it is different, there is definition same as described above, X is optionally each identical or different, has definition same as described above, R¹²It is optionally each From identical or different, there is definition same as described above, n is 0~3 integer,

Wherein, A¹For singly-bound or the connection group of divalent, the connection group of the divalent is the group shown in following formula (A1),

-A¹¹-A¹²-A¹³-A¹⁴-*1 (A1)

In formula, A¹¹For singly-bound, methylene, carbon number 2~5 alkylidene or phenylene, A¹²For singly-bound ,-O- ,-CO- ,-CO-O- or- O-CO-, A¹³For singly-bound or the alkylidene of optionally substituted methylene or carbon number 2~5, A¹⁴For singly-bound ,-O- ,-CO- ,- CO-O- ,-O-CO- ,-NR '-or alkyl that-NR '-CO-O-, R ' are hydrogen atom or carbon number 1~6, wherein, not including A¹¹、A¹²、 A¹³And A¹⁴The situation of all singly-bounds, * 1 represents the company of the carbon atom bonding with the carbon atom of annular amine structure or phenol structure Connect key.

2. composition according to claim 1, wherein, (A) ingredient is not sharp with photo-crosslinking, photoisomerization or light can occur This photonasty side chain reset.

3. composition according to claim 1, wherein, the 1st repetitive unit is represented with following formula (1-1-1), formula (1- In 1-1), R be hydrogen atom or methyl, R¹³It is optionally same or different to each other, for the alkyl of carbon number 1~5, B¹It is former for hydrogen atom, oxygen Son, halogen atom, the organic group of hydroxyl or 1 valency；

2nd repetitive unit is represented with following formula (1-2-1), and in formula (1-2-1), R is hydrogen atom or methyl, R¹³For carbon number 1 ~5 alkyl, R¹⁴For hydrogen atom or the alkyl of carbon number 1~5,

4. composition according to claim 1, wherein, (A) ingredient has selected from the group being made of following formula (1)~(6) Any one of photonasty side 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-；

Y₁Represent ring in the ester ring type hydrocarbon of the phenyl ring selected from 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 or Person is the group that identical or different 2~6 ring in these substituent groups is formed by binding groups B bondings, is bonded to Their hydrogen atom is independently optionally by-COOR₀、-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, carbon The alkyl of number 1~5 or the alkoxy of carbon number 1~5 substitute, in formula, R₀Represent the alkyl of hydrogen atom or carbon number 1~5；

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

X represents singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X reach 2, X is optionally same or different to each other；

Cou represents Coumarin-6-base or coumarin-7-base, is bonded to their hydrogen atom 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 alkoxy substitution；

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 combination thereof composition；Wherein, when X is-CH=CH-CO-O- ,-O-CO-CH=CH- ,-CH= The P or Q for the one side that CH- is bonded are aromatic rings, and when the quantity of P reaches more than 2, P is optionally same or different to each other, the quantity of Q When reaching more than 2, Q is optionally same or different to each other；

L1 is 0 or 1；

L2 is 0~2 integer；

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

H and I is each independently the base in the phenyl ring selected from divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and combination thereof Group.

5. composition according to claim 1, wherein, (A) ingredient has selected from the group being made of following formula (7)~(10) Any one of photonasty side chain,

L represents 1~12 integer；

M represents 0~2 integer, and m1, m2 represent 1~3 integer；

N represents 0~12 integer, wherein, during n=0, B is singly-bound；

R⁵¹Represent hydroxyl, the alkoxy of carbon number 1~6 or expression and Y₁Identical definition.

6. composition according to claim 1, wherein, (A) ingredient has to be selected to be made of following formula (11)~(13) Any one of group photonasty side chain,

In formula, A each independently represents singly-bound ,-O- ,-CH₂- ,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO- O- or-O-CO-CH=CH-；

L represents 1~12 integer, and m represents 0~2 integer, and m1 represents 1~3 integer；

R⁵¹Represent the ring in the ester ring type hydrocarbon of the phenyl ring selected from 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, The group that identical or different 2~6 ring either in these substituent groups is formed by binding groups B bondings, bonding In their hydrogen atom independently optionally by-COOR₀、-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, The alkyl of carbon number 1~5 or the alkoxy of carbon number 1~5 substitute, in formula, R₀Represent hydrogen atom or carbon number 1~5 alkyl or R⁵¹Represent the alkoxy of hydroxyl or carbon number 1~6, the group B represents singly-bound ,-O- ,-CH₂-、-COO-、-OCO-、-CONH-、- NH-CO- ,-CH=CH-CO-O- or-O-CO-CH=CH-.

7. composition according to claim 1, wherein, photonasty of (A) ingredient shown in following formula (14) or (15) Side chain,

Y₁Represent ring in the ester ring type hydrocarbon of the phenyl ring selected from 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 or Person is the group that identical or different 2~6 ring in these substituent groups is formed by binding groups B bondings, is bonded to Their hydrogen atom is independently optionally by-COOR₀、-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, carbon The alkyl of number 1~5 or the alkoxy of carbon number 1~5 substitute, in formula, R₀Represent the alkyl of hydrogen atom or carbon number 1~5, the base Group B represents singly-bound ,-O- ,-CH₂- ,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO-O- or-O-CO-CH= CH-；

L represents 1~12 integer, and m1, m2 represent 1~3 integer.

8. composition according to claim 1, wherein, photonasty of (A) ingredient shown in following formula (16) or (17) Side chain,

In formula, A represents singly-bound ,-O- ,-CH₂- ,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO-O- or-O-CO- CH=CH-；

L represents 1~12 integer, and m represents 0~2 integer.

9. composition according to claim 1, wherein, (A) ingredient, which has, is selected from what is be made of following formula (18) or (19) Any one of group photonasty side chain,

In formula, A, B each independently represent singly-bound ,-O- ,-CH₂- ,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH- CO-O- or-O-CO-CH=CH-；

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

L represents 1~12 integer, and m1, m2 represent 1~3 integer；

R₁Represent hydrogen atom ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, the alkyl or carbon of carbon number 1~5 The alkoxy of number 1~5.

10. composition according to claim 1, wherein, (A) ingredient has the photonasty side chain shown in following formula (20),

L represents 1~12 integer, and m represents 0~2 integer.

11. according to composition according to any one of claims 1 to 10, wherein, (A) ingredient, which has, to be selected from by following formula (21) Any one of the group of~(31) composition liquid crystal liquid crystal property side chain,

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

Y₃For be selected from by the ester ring type hydrocarbon of the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring and carbon number 5~8 and it Combination composition group in group, be bonded to their hydrogen atom independently optionally by-NO₂,-CN, halogen group, The alkoxy substitution of the alkyl or carbon number 1~5 of carbon number 1~5；

R₃Represent hydrogen atom ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, phenyl ring, naphthalene nucleus, the biphenyl of 1 valency Ring, furan nucleus, nitrogen heterocyclic ring, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or the alkoxy of carbon number 1~12；

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

L represents 1~12 integer, and m represents 0~2 integer, wherein, in formula (23)~(24), the summation of all m for 2 with On, in formula (25)~(26), the summation of all m is more than 1, and m1, m2 and m3 each independently represent 1~3 integer；

R₂Represent hydrogen atom ,-NO₂,-CN, halogen group, phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring and the carbon of 1 valency The ester ring type hydrocarbon and alkyl or alkoxy of number 5~8；

Z₁、Z₂Represent singly-bound ,-CO- ,-CH₂O- ,-CH=N- ,-CF₂-。

12. a kind of manufacturing method for the substrate that element liquid crystal orientation film is represented with the driving liquid crystal of transverse electric field, passes through Possess following process and obtain having been assigned the liquid crystal orientation film of tropism control ability：

Composition any one of claim 1~11 is coated on the base with transverse electric field driving conductive film by [I] The process that film is formed on plate；

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

13. a kind of substrate that element liquid crystal orientation film is represented with the driving liquid crystal of transverse electric field, is to pass through claim Method described in 12 and manufacture.

14. a kind of driving liquid crystal of transverse electric field represents element, with the substrate described in claim 13.

15. a kind of driving liquid crystal of transverse electric field represents the manufacturing method of element, the liquid is obtained by possessing following process Crystalline substance represents element：

Prepare the substrate i.e. process of the 1st substrate described in claim 13；

[IV] in a manner that the liquid crystal orientation film of the 1st substrate and the 2nd substrate is across liquid crystalline phase pair, the oppositely disposed described 1st Substrate and the 2nd substrate, so as to obtain the process that liquid crystal represents element,

The process [I '], [II '] and [III '] is：

Composition any one of claim 1~11 is coated on the process for forming film on the 2nd substrate by [I ']；

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