CN105393167A

CN105393167A - Method for producing substrate having liquid crystal orientation film for in-plane-switching liquid-crystal display element

Info

Publication number: CN105393167A
Application number: CN201480040018.2A
Authority: CN
Inventors: 根木隆之; 芦泽亮一; 万代淳彦; 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: 2013-05-13
Filing date: 2014-05-13
Publication date: 2016-03-09
Anticipated expiration: 2034-05-13
Also published as: TWI628209B; KR102254609B1; TW201512253A; CN105393167B; WO2014185413A1; JPWO2014185413A1; KR20160007635A

Abstract

The present invention provides an in-plane-switching liquid-crystal display element having superior burn-in properties and to which an orientation control ability has been imparted at a high efficiency. The present invention achieves same by means of a method that is for producing a substrate having a liquid crystal orientation film for an in-plane-switching liquid-crystal display element to which an orientation control ability has been imparted and that obtains the liquid crystal orientation film by means of having: [I] a step for forming a coating film by applying onto a substrate having a conductive film for in-plane switching a polymer composition containing (A) a photosensitive side-chain polymer exhibiting liquid crystal properties in a predetermined temperature range and (B) an organic solvent; [II] a step for radiating polarized ultraviolet rays at the coating film obtained in [I]; [III] a step for heating the coating film obtained in [II]; and [IV] a step for cooling the coating film heated in [III] to a temperature less than the glass transition temperature of the surface of the coating film, and then re-heating to a temperature that is at least the glass transition temperature.

Description

There is the manufacture method that the driving liquid crystal of transverse electric field represents the substrate of element liquid crystal orientation film

Technical field

The present invention relates to the manufacture method that there is the driving liquid crystal of transverse electric field and represent the substrate of element liquid crystal orientation film.More specifically, the liquid crystal related to for the manufacture of ghost excellent represents the new method of element.

Background technology

Liquid crystal represents that element is light as quality, cross section is thin and the indication device that power consumption is low is known, is used to large-scale tv purposes etc. in recent years, achieves significant development.Liquid crystal represents that element such as utilizes a pair transparency carrier clamping liquid crystal layer possessing electrode to form.Further, represent in element at liquid crystal, the organic film comprising organic material is used as liquid crystal orientation film makes liquid crystal present the state of orientation of expectation between the substrates.

That is, liquid crystal orientation film is the component parts that liquid crystal represents element, and it is formed in the surface contacted with liquid crystal of the substrate of clamping liquid crystal, bears and makes liquid crystal between this substrate along this effect of specific direction orientation.Further, for liquid crystal orientation film, except making liquid crystal except these effects of specific direction orientation such as the direction being such as parallel to substrate, sometimes also require to control this effect to liquid crystal pretilt angle.The ability of the control liquid crystal aligning of this liquid crystal orientation film is (hereinafter referred to as tropism control ability.) be endowed by carrying out orientation process to the organic film forming liquid crystal orientation film.

As the method for orientation treatment of the liquid crystal orientation film for giving tropism control ability, there will be a known brushing method all the time.Brushing method refers to following method: for the organic film of the polyvinyl alcohol (PVA) on substrate, polyamide, polyimide etc., with the cloth of cotton, nylon, polyester etc. along its surface of constant direction friction (brushing), thus make liquid crystal along frictional direction (brushing direction) orientation.This brushing method can realize more stable liquid crystal aligning state easily, and the liquid crystal be therefore used in the past represents the manufacturing process of element.Further, as the organic film used in liquid crystal orientation film, the main polyimide system organic film selecting the reliabilities such as thermotolerance, electrical characteristics excellence.

But, the problem of producing dirt, producing electrostatic is existed to the brushing method that the surface of the liquid crystal orientation film comprising polyimide etc. rubs.In addition, due to liquid crystal in recent years, to represent that electrode on the high-definition of element, corresponding substrate or liquid crystal drive switch that active element causes concavo-convex, therefore, cannot with cloth rub equably liquid crystal orientation film surface, uniform liquid crystal aligning cannot be realized.

Thus, as other method for orientation treatment of liquid crystal orientation film not carrying out brushing, have studied optical alignment method energetically.

Optical alignment method has various method, forming anisotropy, making liquid crystal carry out orientation according to this anisotropy by rectilinearly polarized light or the light through collimating in the organic film forming liquid crystal orientation film.

As main optical alignment method, there will be a known the optical alignment method of breakdown type.In the method, such as, polarized UV rays is irradiated to polyimide film, utilizes the polarization direction dependence of the UVA of molecular structure and anisotropic decomposition occurs.Further, liquid crystal is made to carry out orientation (such as with reference to patent documentation 1) by undecomposed and residual polyimide.

In addition, as other optical alignment method, also there will be a known the optical alignment method of photo-crosslinking type, photoisomerization type.In the optical alignment method of photo-crosslinking type, such as, use poly-vinyl cinnamate, irradiate polarized UV rays, make double bond part generation dimerization reaction (cross-linking reaction) of 2 side chains being parallel to polarized light.Further, liquid crystal is made to carry out orientation (such as with reference to non-patent literature 1) along the direction vertical with polarization direction.In the optical alignment method of photoisomerization type, there is be used in side chain while the side chain type macromolecule of azobenzene, irradiate polarized UV rays, make the azobenzene part generation isomerization reaction of the side chain being parallel to polarized light, make liquid crystal carry out orientation (such as with reference to non-patent literature 2) along the direction vertical with polarization direction.

As above-mentioned example, utilizing optical alignment method to carry out in the method for orientation process to liquid crystal orientation film, without the need to carrying out brushing, do not worry producing dirt, producing electrostatic.Further, even if the substrate representing element for the irregular liquid crystal of surperficial tool also can implementation orientation process, thus the method for orientation treatment of the liquid crystal orientation film being suitable for industrial manufacture process is become.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent No. 3893659 publication

Non-patent literature

Non-patent literature 1:M.Shadtetal., Jpn.J.Appl.Phys.31,2155 (1992).

Non-patent literature 2:K.Ichimuraetal., Chem.Rev.100,1847 (2000).

Summary of the invention

the problem that invention will solve

As mentioned above, with represent the method for orientation treatment of element as liquid crystal and compared with the brushing method of all the time carrying out industrial utilization, optical alignment method, without the need to this operation of brushing operation, therefore possesses obvious advantage.Further, compared with the brushing method that the tropism control ability produced with brushing is fixed substantially, optical alignment method can change the exposure of polarized light to control tropism control ability.But, when optical alignment method is wanted to realize the tropism control ability identical with degree when utilizing brushing method, sometimes need a large amount of polarizing light irradiation amounts or stable liquid crystal aligning cannot be realized.

Such as, in the breakdown type optical alignment method described in above-mentioned patent documentation 1, need the ultraviolet light etc. sent by the high-pressure sodium lamp of power 500W polyimide film being irradiated to 60 minutes, need long-time and a large amount of Ultraviolet radiation.In addition, when dimeric form, photoisomerization type optical alignment method, a large amount of Ultraviolet radiation of several J (joule) ~ tens of about J are sometimes needed.And then when photo-crosslinking type, photoisomerization type optical alignment method, thermal stability, the light stability of liquid crystal aligning are poor, therefore make liquid crystal when representing element, worry to occur orientation bad, represent ghost.Especially, the driving liquid crystal of transverse electric field represents in element, is switched by liquid crystal molecule in face, the liquid crystal aligning skew after therefore easily there is liquid crystal drive, drives the expression ghost caused to be considered obvious problem by AC.

Therefore, for optical alignment method, require to realize the high efficiency of orientation process, stable liquid crystal aligning, requirement can give the liquid crystal orientation film of high tropism control ability, aligning agent for liquid crystal and alignment method efficiently to liquid crystal orientation film.

The object of the invention is to, provide with high-level efficiency be endowed tropism control ability, ghost excellent, there is the driving liquid crystal of transverse electric field represent that the element substrate of liquid crystal orientation film and the driving liquid crystal of transverse electric field with this substrate represent element.The present invention also aims to, the manufacture method with the substrate of liquid crystal orientation film of the bounds of the polarized UV rays exposure that can expand the good liquid crystal aligning that can realize in liquid crystal orientation film is provided.

for the scheme of dealing with problems

The present inventor etc. conduct in-depth research to realize above-mentioned problem, found that following invention.

<1> mono-kind has the manufacture method that the driving liquid crystal of transverse electric field represents the substrate of element liquid crystal orientation film, and it obtains being endowed the foregoing liquid crystal alignment films of tropism control ability by possessing following operation:

[I] polymer composition is coated on there is transverse electric field driving conducting film substrate on and form the operation of film, described polymer composition contains: (A) shows photonasty side chain type macromolecule and (B) organic solvent of liquid crystal liquid crystal property in specific temperature range;

[II] irradiates the operation of polarized UV rays to the film obtained in [I];

The film obtained in [II] is carried out the operation heated by [III]; And

After the film of heating in [III] is cooled to the temperature of the glass transition temperature of this film coated surface not enough by [IV], then be heated to the operation of temperature of more than this glass transition temperature.

In the above-mentioned <1> of <2>, the chilling temperature of the film in [IV] operation can be the temperature than low more than 10 DEG C of side chain type high molecular glass transition point temperature (Tg) as (A) composition.

In above-mentioned <1> or <2> of <3>, the heating-up temperature of the film after Ultraviolet radiation and cooled heating-up temperature again can be more than the glass transition temperature of film coated surface and the temperature of the homogeneous phase transition temperature of not enough film coated surface.

In any one of the above-mentioned <1> ~ <3> of <4>, (A) composition can have the photonasty side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.

In any one of the above-mentioned <1> ~ <4> of <5>, (A) composition can have any one the photonasty side chain in the group being selected from and being made up of following formula (1) ~ (6).

In formula, A, B, D represent singly-bound ,-O-,-CH independently of one another ₂-,-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 being bonded to them is optionally replaced by halogen group;

T is the alkylidene of singly-bound or carbon number 1 ~ 12, and the hydrogen atom being bonded to them is optionally replaced by halogen group;

Y ₁represent the ring in the ester ring type hydrocarbon of the phenyl ring of 1 valency that is selected from, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5 ~ 8, or be selected from the group of 2 ~ 6 the identical or different rings in these substituting groups by binding groups B bonding, be bonded to their hydrogen atom independently of one another optionally by-COOR ₀(in formula, R ₀represent the alkyl of hydrogen atom or carbon number 1 ~ 5) ,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace;

Y ₂for being selected from the group in the group that is made up of the ester ring type hydrocarbon of the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5 ~ 8 and their combination, be bonded to their hydrogen atom independently of one another optionally by-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace;

R represents the alkoxy of hydroxyl, carbon number 1 ~ 6, or represents and Y ₁identical definition;

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

Cou represents Coumarin-6-Ji or coumarin-7-Ji, is bonded to their hydrogen atom independently of one another optionally by-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace;

One in q1 and q2 is 1, and another one is 0;

Q3 is 0 or 1;

P and Q is independently of one another for being selected from the group in the group that is made up of the ester ring type hydrocarbon of the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5 ~ 8 and their combination; Wherein, when X is-CH=CH-CO-O-,-O-CO-CH=CH-, P or Q of the side of-CH=CH-institute bonding is aromatic rings, and when the quantity of P reaches more than 2, P is optionally same to each other or different to each other, and when the quantity of Q reaches more than 2, Q is optionally same to each other or different to each other;

L1 is 0 or 1;

L2 is the integer of 0 ~ 2;

When l1 and l2 is 0, when T is singly-bound, A also represents singly-bound;

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

H and I is independently of one another for being selected from the group in the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and their combination.

In any one of the above-mentioned <1> ~ <4> of <6>, (A) composition can have any one the photonasty side chain in the group being selected from and being made up of following formula (7) ~ (10).

In formula, A, B, D, Y ₁, X, Y ₂with R, there is definition same as described above;

L represents the integer of 1 ~ 12;

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

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

In any one of the above-mentioned <1> ~ <4> of <7>, (A) composition can have any one the photonasty side chain in the group being selected from and being made up of following formula (11) ~ (13).

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

In any one of the above-mentioned <1> ~ <4> of <8>, (A) composition can have following formula (14) or the photonasty side chain shown in (15).

In formula, A, Y ₁, l, m1 and m2 have definition same as described above.

In any one of the above-mentioned <1> ~ <4> of <9>, (A) composition can have following formula (16) or the photonasty side chain shown in (17).

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

In any one of the above-mentioned <1> ~ <4> of <10>, (A) composition can have following formula (18) or the photonasty side chain shown in (19).

In formula, A, B, Y ₁, q1, q2, m1 and m2 have definition same as described above.

R ₁represent hydrogen atom ,-NO ₂,-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.

In any one of the above-mentioned <1> ~ <4> of <11>, (A) composition can have the photonasty side chain shown in following formula (20).

In formula, A, Y ₁, X, l and m have definition same as described above.

In any one of the above-mentioned <1> ~ <11> of <12>, (A) composition can have any one the liquid crystal liquid crystal property side chain in the group being selected from and being made up of following formula (21) ~ (31).

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

Y ₃for being selected from the group in the group that is made up of 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 their combination, be bonded to their hydrogen atom independently of one another optionally by-NO ₂,-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace;

R ₃represent hydrogen atom ,-NO ₂,-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 carbon number 1 ~ 12 alkoxy;

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

R ₂represent hydrogen atom ,-NO2 ,-CN, halogen group, the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, the ester ring type hydrocarbon of nitrogen heterocyclic ring and carbon number 5 ~ 8 and alkyl or alkoxy;

Z ₁, Z ₂represent singly-bound ,-CO-,-CH ₂o-,-CH=N-,-CF ₂-.

<13> mono-kind has the substrate that the driving liquid crystal of transverse electric field represents element liquid crystal orientation film, and it manufactures any one of above-mentioned <1> ~ <12>.

<14> driving liquid crystal of transverse electric field represents element, and it has the substrate of above-mentioned <13>.

<15> driving liquid crystal of transverse electric field represents the manufacture method of element, and it obtains this liquid crystal by possessing following operation and represents element:

Prepare the operation of the substrate (the 1st substrate) of above-mentioned <13>;

Obtain and have the operation of the 2nd substrate of following liquid crystal orientation film, it is by possessing following operation [I '], [II '] and [III '] and obtain being endowed the liquid crystal orientation film of tropism control ability; And

[V] with the liquid crystal orientation film of aforementioned 1st substrate and the 2nd substrate across the right mode of liquid crystal phase, subtend aforementioned 1st substrate of configuration and the 2nd substrate, thus the operation obtaining that liquid crystal represents element,

Described operation [I '], [II '] and [III '] be:

[I '] coated polymeric composition and form the operation of film on the 2nd substrate, described polymer composition contains: (A) shows photonasty side chain type macromolecule and (B) organic solvent of liquid crystal liquid crystal property in specific temperature range;

[II '] irradiates the operation of polarized UV rays to the film obtained in [I ']; And

The film obtained in [II '] is carried out the operation heated by [III '].

In the above-mentioned <15> of <16>, the operation obtaining aforementioned 2nd substrate can also have [IV '] by after in [III '], the film of heating is cooled to the temperature of the glass transition temperature of this film coated surface not enough, then is heated to the operation of temperature of more than this glass transition temperature.

<17> driving liquid crystal of transverse electric field represents element, and it is manufactured by above-mentioned <15> or <16>.

In addition, following invention is found as another side.

<P1> mono-kind has the manufacture method that the driving liquid crystal of transverse electric field represents the substrate of element liquid crystal orientation film, and it obtains being endowed the foregoing liquid crystal alignment films of tropism control ability by possessing following operation

[II] irradiates the operation of polarized UV rays to the film obtained in [I];

The film obtained in [II] is carried out the operation heated by [III]; And

In the above-mentioned <P1> of <P2>, the chilling temperature of the film in [IV] operation can be the temperature than low more than 10 DEG C of side chain type high molecular glass transition point temperature (Tg) as (A) composition.

In above-mentioned <P1> or <P2> of <P3>, the heating-up temperature of the film after Ultraviolet radiation and cooled heating-up temperature again can be more than the glass transition temperature of film coated surface and the temperature of the homogeneous phase transition temperature of not enough film coated surface.

In any one of the above-mentioned <P1> ~ <P3> of <P4>, (A) composition can have the photonasty side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.

In any one of the above-mentioned <P1> ~ <P4> of <P5>, (A) composition can have any one the photonasty side chain in the group being selected from and being made up of following formula (1) ~ (6).

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

One in q1 and q2 is 1, and another one is 0;

Q3 is 0 or 1;

P and Q is independently of one another for being selected from the group in the group that is made up of the ester ring type hydrocarbon of the phenyl ring of singly-bound, divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5 ~ 8 and their combination.Wherein, when X is-CH=CH-CO-O-,-O-CO-CH=CH-, P or Q of the side of-CH=CH-institute bonding is aromatic rings;

In any one of the above-mentioned <P1> ~ <P4> of <P6>, (A) composition can have any one the photonasty side chain in the group being selected from and being made up of following formula (7) ~ (10).

L represents the integer of 1 ~ 12;

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

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

In any one of the above-mentioned <P1> ~ <P4> of <P7>, (A) composition can have any one the photonasty side chain in the group being selected from and being made up of following formula (11) ~ (13).

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

In any one of the above-mentioned <P1> ~ <P4> of <P8>, (A) composition can have following formula (14) or the photonasty side chain shown in (15).

In formula, A, Y ₁, X, l, m1 and m2 have definition same as described above.

In any one of the above-mentioned <P1> ~ <P4> of <P9>, (A) composition can have following formula (16) or the photonasty side chain shown in (17).

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

In any one of the above-mentioned <P1> ~ <P4> of <P10>, (A) composition can have following formula (18) or the photonasty side chain shown in (19).

In any one of the above-mentioned <P1> ~ <P4> of <P11>, (A) composition can have the photonasty side chain shown in following formula (20).

In formula, A, Y ₁, X, l and m have definition same as described above.

In any one of the above-mentioned <P1> ~ <P11> of <P12>, (A) composition can have any one the liquid crystal liquid crystal property side chain in the group being selected from and being made up of following formula (21) ~ (31).

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

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

R ₂represent hydrogen atom ,-NO ₂,-CN, halogen group, the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, the ester ring type hydrocarbon of nitrogen heterocyclic ring and carbon number 5 ~ 8 and alkyl or alkoxy;

Z ₁, Z ₂represent singly-bound ,-CO-,-CH ₂o-,-CH=N-,-CF ₂-.

<P13> mono-kind has the substrate that the driving liquid crystal of transverse electric field represents element liquid crystal orientation film, and it manufactures any one of above-mentioned <P1> ~ <P12>.

<P14> driving liquid crystal of transverse electric field represents element, and it has the substrate of above-mentioned <P13>.

<P15> driving liquid crystal of transverse electric field represents the manufacture method of element, and it obtains this liquid crystal by possessing following operation and represents element:

Prepare the operation of the substrate (the 1st substrate) of above-mentioned <P13>;

[V] with the liquid crystal orientation film of aforementioned 1st substrate and the 2nd substrate across the right mode of liquid crystal phase, subtend aforementioned 1st substrate of configuration and the 2nd substrate, thus the operation obtaining that liquid crystal represents element;

Described operation [I '], [II '] and [III '] be:

The film obtained in [II '] is carried out the operation heated by [III '].

In the above-mentioned <P15> of <P16>,

The operation obtaining aforementioned 2nd substrate can also have [IV '] by after in [III '], the film of heating is cooled to the temperature of the glass transition temperature of this film coated surface not enough, then is heated to the operation of temperature of more than this glass transition temperature.

<P17> driving liquid crystal of transverse electric field represents element, and it is manufactured by above-mentioned <P15> or <P16>.

the effect of invention

By the present invention, can provide with high-level efficiency be endowed tropism control ability, ghost excellent, there is the driving liquid crystal of transverse electric field represent that the element substrate of liquid crystal orientation film and the driving liquid crystal of transverse electric field with this substrate represent element.

The driving liquid crystal of transverse electric field manufactured by method of the present invention represents that element is imparted tropism control ability efficiently, even if therefore long-time continuous driving also can not damage characterization.

In addition, by the present invention, the bounds of the polarizing light irradiation amount of the good liquid crystal aligning that can realize in liquid crystal orientation film can be expanded, because the bounds of exposure expands, therefore, it is possible to play the effect of expectation in broader range of exposures.

Accompanying drawing explanation

Fig. 1 schematically illustrates that anisotropy in the manufacture method of the liquid crystal orientation film that the present invention is used imports the figure of an example of process, is that photosensitive side chain uses bridging property organic group and the figure of the anisotropy imported hour.

Fig. 2 schematically illustrates that anisotropy in the manufacture method of the liquid crystal orientation film that the present invention is used imports the figure of an example of process, be that photosensitive side chain uses bridging property organic group and the anisotropy imported is large time figure.

Fig. 3 schematically illustrates that anisotropy in the manufacture method of the liquid crystal orientation film that the present invention is used imports the figure of an example of process, is that photosensitive side chain use fries' rearrangement or isomerized organic group can occur and the figure of the anisotropy imported hour.

Fig. 4 schematically illustrates that anisotropy in the manufacture method of the liquid crystal orientation film that the present invention is used imports the figure of an example of process, be that fries' rearrangement or isomerized organic group can occur in photosensitive side chain use and the anisotropy imported is large time figure.

Embodiment

Present inventor has performed further investigation, result obtains following opinion, thus completes the present invention.

The polymer composition used in manufacture method of the present invention has the photonasty side chain type macromolecule (hereinafter also referred to as side chain type macromolecule) that can show liquid crystal liquid crystal property, and the film using foregoing polymer compositions to obtain has the high molecular film of photonasty side chain type that can show liquid crystal liquid crystal property.This film, without the need to carrying out brushing process, carries out orientation process by polarizing light irradiation.Further, after carrying out polarizing light irradiation, via the operation of this side chain type polymeric membrane of heating, thus the film (hereinafter also referred to liquid crystal orientation film) being endowed tropism control ability is become.Now, the small anisotropy shown by polarizing light irradiation becomes driving force, and the side chain type macromolecule of liquid crystal liquid crystal property self is reorientation effectively because of self assembly.Its result, can realize efficient orientation process as liquid crystal orientation film, obtain the liquid crystal orientation film being endowed high tropism control ability.

The present inventor etc. also against expectation find: by after irradiation polarized light, the product obtained by heated side chain polymeric membrane cools further and heats, obtain the film being endowed tropism control ability, thus the liquid crystal orientation film possessing good liquid crystal aligning in broader polarizing light irradiation amount bounds can be obtained.The present invention carries out based on described opinion.

Below, be described in detail for embodiments of the present invention.

< has the manufacture method > that the manufacture method > of the substrate of liquid crystal orientation film and < liquid crystal represent element

The manufacture method with the substrate of liquid crystal orientation film of the present invention possesses following operation:

[II] irradiates the operation of polarized UV rays to the film obtained in [I];

The film obtained in [II] is carried out the operation heated by [III]; And

By above-mentioned operation, the driving liquid crystal of transverse electric field that can obtain being endowed tropism control ability represents element liquid crystal orientation film, can obtain the substrate with this liquid crystal orientation film.

In addition, except substrate obtained above (the 1st substrate), by preparing the 2nd substrate, the driving liquid crystal of transverse electric field can be obtained and represent element.

2nd substrate replaces having except the substrate of transverse electric field driving conducting film except using the substrate without transverse electric field driving conducting film, by using above-mentioned operation [I] ~ [III] (owing to using the substrate without transverse electric field driving conducting film, therefore conveniently, in this application sometimes referred to as operation [I '] ~ [III ']), the 2nd substrate with the liquid crystal orientation film being endowed tropism control ability can be obtained.

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

1st substrate obtained above and the 2nd substrate are carried out subtend configuration with the liquid crystal orientation film of the 1st substrate and the 2nd substrate across the mode that liquid crystal phase is right by [V], thus obtain the operation that liquid crystal represents element.Thereby, it is possible to obtain the driving liquid crystal of transverse electric field to represent element.

Below, [I] ~ [IV] possessed for manufacture method of the present invention and each operation of [V] are described.

< operation [I] >

In operation [I], coated polymeric composition on the substrate with transverse electric field driving conducting film and form film, described polymer composition contains: in specific temperature range, show liquid crystal liquid crystal property photonasty side chain type macromolecule and organic solvent.

< substrate >

Be not particularly limited for substrate, when the liquid crystal that manufacture represents that element is through type, preferably use the substrate that the transparency is high.Now be not particularly limited, the plastic base etc. such as glass substrate or acrylic compounds substrate, polycarbonate substrate can be used.

In addition, consider the application represented at reflective liquid crystal in element, also can use the opaque substrates such as silicon wafer.

< transverse electric field drives and uses conducting film >

Substrate has transverse electric field driving conducting film.

As this conducting film, when liquid crystal represents that element is infiltration type, ITO (IndiumTinOxide: tin indium oxide), IZO (IndiumZincOxide: indium zinc oxide) etc. can be listed, be not limited to these.

In addition, when reflective liquid crystal represents element, as conducting film, the material etc. of the meeting reflected light such as aluminium can be listed, be not limited to these.

The method that substrate is formed conducting film can use existing known method.

< polymer composition >

Coated polymeric composition on the substrate with transverse electric field driving conducting film, especially coated polymeric composition on conducting film.

This polymer composition used in manufacture method of the present invention contains: (A) shows the photonasty side chain type macromolecule of liquid crystal liquid crystal property in specific temperature range; And (B) organic solvent.

<< (A) side chain type macromolecule >>

(A) composition is the photonasty side chain type macromolecule showing liquid crystal liquid crystal property in specific temperature range.

(A) side chain type macromolecule by reacting and show liquid crystal liquid crystal property in the temperature range of 100 DEG C ~ 300 DEG C under the light of the wavelength coverage of 250nm ~ 400nm.

(A) side chain type macromolecule preferably has the photonasty side chain reacted with the light of the wavelength coverage of 250nm ~ 400nm.

(A) side chain type macromolecule shows liquid crystal liquid crystal property in the temperature range of 100 DEG C ~ 300 DEG C, therefore preferably has mesogenic group.

(A) side chain type high molecular main chain bonding has photosensitive side chain, and it is responded in light, cross-linking reaction, isomerization reaction or light fries' rearrangement can occur.There is photosensitive side-chain structure be not particularly limited, be contemplated to be the structure responded to and cross-linking reaction or light fries' rearrangement occur in light, be more contemplated to be the structure that cross-linking reaction occurs.Now, even if be exposed to the hot external stress that waits also can keep the tropism control ability realized steadily in the long term.As long as the structure that can show the photonasty side chain type polymeric membrane of liquid crystal liquid crystal property meets this characteristic, be just not particularly limited, preferably at side-chain structure, there is upright and outspoken liquid crystal ultimate constituent.Now, when this side chain type macromolecule is made liquid crystal orientation film, stable liquid crystal aligning can be obtained.

This high molecular structure example is as made following structure: have main chain and be bonded to its side chain, and this side chain has the liquid crystal ultimate constituents such as xenyl, terphenyl, phenylcyclohexyl, phenylamino benzoic acid ester group, azobenzene and is bonded to the induction light of leading section and the photonasty group of cross-linking reaction, isomerization reaction occurs; Have main chain and be bonded to its side chain, this side chain has both for the phenylamino benzoic acid ester group of light Fries rearrangement also can occur liquid crystal ultimate constituent.

As can show liquid crystal liquid crystal property photonasty side chain type polymeric membrane structure have more style, preferably there is the structure of following main chain and following side chain, described main chain is by least a kind of formation be selected from group that the free-radical polymerised groups such as hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norborene and siloxane form, and described side chain comprises at least a kind in following formula (1) ~ (6).

One in q1 and q2 is 1, and another one is 0;

Q3 is 0 or 1;

L1 is 0 or 1;

L2 is the integer of 0 ~ 2;

When l1 and l2 is 0, when T is singly-bound, A also represents singly-bound;

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

Side chain can for being selected from any one the photonasty side chain in the group that is made up of following formula (7) ~ (10).

L represents the integer of 1 ~ 12;

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

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

Side chain can for being selected from any one the photonasty side chain in the group that is made up of following formula (11) ~ (13).

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

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

In formula, A, Y ₁, 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, Y ₁, X, l and m have definition same as described above.

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

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

Z ₁, Z ₂represent singly-bound ,-CO-,-CH ₂o-,-CH=N-,-CF ₂-.

The high molecular method for making >> of << photonasty side chain type

The above-mentioned photonasty side chain type macromolecule that can show liquid crystal liquid crystal property is by being undertaken being polymerized obtaining by the photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer with above-mentioned photonasty side chain.

[photoreactivity side chain monomer]

Photoreactivity side chain monomer refers to: when forming macromolecule, can be formed in the high molecular monomer that high molecular side chain position has photonasty side chain.

As the photoreactive group that side chain has, be preferably following structure and derivant thereof.

Style is had more as photoreactivity side chain monomer, preferably there is the structure of polymerizable group and photonasty side chain, described polymerizable group is by being selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, at least a kind of formation in the group of the free-radical polymerised group such as norborene and siloxane composition, described photonasty side chain is the photonasty side chain of at least a kind comprised in above-mentioned formula (1) ~ (6), preferably such as comprise the photonasty side chain of at least a kind in above-mentioned formula (7) ~ (10), comprise the photonasty side chain of at least a kind in above-mentioned formula (11) ~ (13), above-mentioned formula (14) or the photonasty side chain shown in (15), above-mentioned formula (16) or the photonasty side chain shown in (17), above-mentioned formula (18) or the photonasty side chain shown in (19), photonasty side chain shown in above-mentioned formula (20).

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

In formula, R represents hydrogen atom or methyl; S represents the alkylidene of carbon number 2 ~ 10; R10 represents Br or CN; S represents the alkylidene of carbon number 2 ~ 10; U is expressed as 0 or 1; And Py represents 2-pyridine radicals, 3-pyridine radicals or 4-pyridine radicals.In addition, v represents 1 or 2.

[liquid crystal liquid crystal property side chain monomer]

Liquid crystal liquid crystal property side chain monomer refers to: the high molecular form being derived from this monomer reveals liquid crystal liquid crystal property, and this macromolecule can form the monomer of mesogenic group at side chain position.

As the mesogenic group that side chain has, can be the group that biphenyl, phenol benzoate etc. become separately liquid crystal original structure, also can be benzoic acid etc. like that side chain carry out hydrogen bonding each other and become the group of liquid crystal original structure.As the mesogenic group that side chain has, be preferably following structure.

Style is had more as liquid crystal liquid crystal property side chain monomer, preferably there is the structure of following polymerizable group and following side chain, described polymerizable group is by least a kind of formation be selected from the group that is made up of the free-radical polymerised groups such as hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norborene and siloxane, and described side chain comprises at least a kind in above-mentioned formula (21) ~ (31).

(A) side chain type macromolecule obtains by the above-mentioned polyreaction showing the photoreactivity side chain monomer of liquid crystal liquid crystal property.In addition, can be obtained by the copolymerization of the photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer that do not show liquid crystal liquid crystal property, the copolymerization of photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer that shows liquid crystal liquid crystal property.And then, in the scope not damaging liquid crystal liquid crystal property expressive ability, copolymerization can be carried out with other monomer.

As other monomer, can list such as can the industrial monomer that can carry out Raolical polymerizable obtained.

As the concrete example of other monomer, unsaturated carboxylic acid, acrylate compounds, methacrylate compound, maleimide compound, vinyl cyanide, maleic anhydride, distyryl compound and vinyl compound etc. can be listed.

As the concrete example of unsaturated carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid etc. can be listed.

As acrylate compounds, such as methyl acrylate can be listed, ethyl acrylate, isopropyl acrylate, benzyl acrylate, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, acrylic acid 2, 2, 2-trifluoro ethyl ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2-methoxy acrylate, methoxy triethylene acrylate, acrylic acid 2-ethoxy ethyl ester, tetrahydrofurfuryl acrylate, acrylic acid 3-methoxybutyl, acrylic acid 2-methyl-2-adamantane esters, acrylic acid 2-propyl group-2-adamantane esters, acrylic acid 8-methyl-8-three ring ester in the last of the ten Heavenly stems, and acrylic acid 8-ethyl-8-three ring ester in the last of the ten Heavenly stems etc.

As methacrylate compound, such as methyl methacrylate can be listed, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthrylmethyl, phenyl methacrylate, methacrylic acid 2, 2, 2-trifluoro ethyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid 2-methoxy acrylate, methoxy triethylene methacrylate, methacrylic acid 2-ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3-methoxybutyl, methacrylic acid 2-methyl-2-adamantane esters, methacrylic acid 2-propyl group-2-adamantane esters, methacrylic acid 8-methyl-8-three ring ester in the last of the ten Heavenly stems, and methacrylic acid 8-ethyl-8-three ring ester in the last of the ten Heavenly stems etc.Also (methyl) glycidyl acrylate, (methyl) acrylic acid (3-methyl-3-oxetanyl) methyl esters and (methyl) acrylic acid (3-ethyl-3-oxetanyl) methyl esters etc. can be used to have (methyl) acrylate compounds of cyclic ether group.

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

As distyryl compound, such as styrene, methyl styrene, chlorostyrene, bromstyrol etc. can be listed.

As maleimide compound, such as maleimide, N-methylmaleimido, N-phenylmaleimide and N-N-cyclohexylmaleimide etc. can be listed.

The high molecular manufacture method of side chain type for present embodiment, is not particularly limited, and can utilize the universal method of industrial application.Specifically, by make use of liquid crystal liquid crystal property side chain monomer, the cationic polymerization of vinyl of photoreactivity side chain monomer, free radical polymerization, anionic polymerisation manufactures.Among these, from viewpoints such as reaction controlling easnesses, be particularly preferably free radical polymerization.

As the polymerization initiator of free radical polymerization, the known compounds such as radical polymerization initiator, reversibility addition-cracking type chain tra nsfer (RAFT) polymerization agent can be used.

Free radical thermal polymerization is the compound producing free radical by being heated to more than decomposition temperature.As this free radical thermal polymerization, such as peroxidating ketone (methyl ethyl ketone peroxide can be listed, Cyclohexanone peroxides etc.), diacyl peroxides 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, dilauroyl peroxide 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 ester etc.), persulfuric acid salt (potassium persulfate, sodium peroxydisulfate, ammonium persulfate etc.), Azo (azobis isobutyronitrile, with 2, 2 '-two (2-hydroxyethyl) azobis isobutyronitrile etc.).This free radical thermal polymerization can be used alone a kind, or, also can combinationally use two or more.

As long as radical photopolymerization initiating agent starts the compound of free radical polymerization because illumination is penetrated, be just not particularly limited.As this radical photopolymerization initiating agent, benzophenone can be listed, Michler's keton, 4,4 '-bis-(lignocaine) benzophenone, xanthone, sulfo-xanthone, isopropyl xanthone, 2,4-diethyl sulfide is for xanthone, 2-EAQ, acetophenone, 2-hydroxy-2-methyl propiophenone, 2-hydroxy-2-methyl-4 '-cumene acetone, 1-hydroxycyclohexylphenylketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, camphorquinone, benzanthrone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4,4 '-two (t-butylperoxycarbonyl) benzophenone, 3,4,4 '-three (t-butylperoxycarbonyl) benzophenone, TMDPO, two (trichloromethyl) s-triazine of 2-(4 '-methoxyl-styrene)-4,6-, two (trichloromethyl) s-triazine of 2-(3 ', 4 '-dimethoxy-styryl)-4,6-, two (trichloromethyl) s-triazine of 2-(2 ', 4 '-dimethoxy-styryl)-4,6-, two (trichloromethyl) s-triazine of 2-(2 '-methoxyl-styrene)-4,6-, two (trichloromethyl) s-triazine of 2-(4 '-amyl phenyl ether vinyl)-4,6-, 4-[p-N, N-bis-(ethoxy carbonyl methyl)]-2,6-bis-(trichloromethyl) s-triazine, two (trichloromethyl)-5-(2 '-chlorphenyl) s-triazine of 1,3-, two (trichloromethyl)-5-(4 '-methoxyphenyl) s-triazine of 1,3-, 2-is (to dimethylaminostyryl) benzoxazole, 2-(to dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3 '-carbonyl two (7-lignocaine cumarin), 2-(Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (4-carboethoxyphenyl)-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 ' two (2,4-dibromo phenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 3-(2-methyl-2-dimethylamino propiono) carbazole, two (2-methyl-2-morpholino the propiono)-9-dodecyl carbazole of 3,6-, 1-hydroxycyclohexylphenylketone, two (5-2,4-cyclopentadiene-1-base)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-base)-phenyl) titanium, 3,3 ', 4,4 '-four (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary hexyl peroxy carbonyl) benzophenone, 3,3 '-two (methoxycarbonyl)-4,4 '-two (t-butylperoxycarbonyl) benzophenone, 3,4 '-two (methoxycarbonyl)-4,3 '-two (t-butylperoxycarbonyl) benzophenone, 4,4 '-two (methoxycarbonyl)-3,3 '-two (t-butylperoxycarbonyl) benzophenone, 2-(3-methyl-3H-benzothiazole-2-subunit)-1-naphthalene-2-base-ethyl ketone, or 2-(3-methyl isophthalic acid, 3-benzothiazole-2 (3H)-subunit)-1-(2-benzoyl) ethyl ketone etc.These compounds can be used alone, and also can mix two or more use.

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

As the organic solvent used in the high molecular polyreaction of photonasty side chain type of liquid crystal liquid crystal property can be shown, as long as the organic solvent that the macromolecule generated can dissolve just is not particularly limited.Below list its concrete example.

Can list: DMF, DMA, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, isopropyl alcohol, methoxy amylalcohol, cinene, ethyl pentyl group ketone, methyl nonyl ketone, MEK, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, 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, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, diox, normal hexane, n-pentane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid Methylethyl, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxyl-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide etc.

These organic solvents can be used alone, also can be used in combination.And then, even do not dissolve generated high molecular solvent, as long as in the scope that generated macromolecule can not be separated out, then also can be mixed in above-mentioned organic solvent and use.

In addition, in free radical polymerization, the oxygen in organic solvent can become the reason hindering polyreaction, therefore organic solvent preferably degassed rear use as much as possible.

Polymerization temperature during free radical polymerization can select the arbitrary temp of 30 DEG C ~ 150 DEG C, is preferably the scope of 50 DEG C ~ 100 DEG C.In addition, reaction can be carried out with any concentration, is difficult to the polymkeric substance obtaining high molecular, during excessive concentration when concentration is too low, the viscosity of reactant liquor becomes too high and is difficult to stir equably, and therefore monomer concentration is preferably 1 quality % ~ 50 quality %, is more preferably 5 quality % ~ 30 quality %.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 relative to the ratio of monomer, the high molecular molecular weight of gained diminishes, during the ratio less of radical polymerization initiator relative to monomer, the high molecular molecule quantitative change of gained is large, and therefore radical initiator is preferably 0.1 % by mole ~ 10 % by mole relative to the ratio of polymerization single polymerization monomer.In addition, also various monomer component, solvent, initiating agent etc. can be added during polymerization.

[recovery of polymkeric substance]

From utilize reclaim generated macromolecule above-mentioned that be obtained by reacting, that liquid crystal liquid crystal property can the be shown high molecular reaction solution of photonasty side chain type time, reaction solution is fed into poor solvent, these polymkeric substance is precipitated.As the poor solvent for precipitating, methyl alcohol, acetone, hexane, heptane, butyl cellosolve, heptane, MEK, methylisobutylketone, ethanol, toluene, benzene, diethyl ether, ethyl methyl ether, water etc. can be listed.Be fed into the polymkeric substance that precipitation occurs in poor solvent and after filtered and recycled, air drying or heat drying can be carried out under normal or reduced pressure.In addition, when the polymkeric substance repeating 2 times ~ 10 times precipitation to be reclaimed is dissolved in organic solvent again and precipitates the operation of recovery again, the impurity in polymkeric substance can be reduced.As poor solvent now, can list such as alcohols, ketone, hydrocarbon etc., when using more than the 3 kinds poor solvents be selected among these, purification efficiency improves further, so preferably.

About the high molecular molecular weight of (A) of the present invention side chain type, consider that gained is coated with film strength, workability when forming film and the homogeneity of film time, the weight-average molecular weight utilizing GPC (GelPermeationChromatography, gel permeation chromatography) method to measure is preferably 2000 ~ 1000000, is more preferably 5000 ~ 100000.

[preparation of polymer composition]

The polymer composition used in the present invention is preferably prepared into the form of coating fluid, in order to applicable formation liquid crystal orientation film.That is, prepared by the form that polymer composition used in the present invention is preferably dissolved in the solution of organic solvent for the resinous principle forming resin coating.Herein, this resinous principle refers to the high molecular resinous principle of photonasty side chain type that can show liquid crystal liquid crystal property comprising above-mentioned explanation.Now, the content of resinous principle is preferably 1 quality % ~ 20 quality %, is more preferably 3 quality % ~ 15 quality %, is particularly preferably 3 quality % ~ 10 quality %.

In the polymer composition of present embodiment, aforementioned resin composition can be all be the above-mentioned photonasty side chain type macromolecule that can show liquid crystal liquid crystal property, in the scope not damaging liquid crystal expressive ability and photosensitive property, also can mix other polymkeric substance in addition.Now, the content of other polymkeric substance in resinous principle is 0.5 quality % ~ 80 quality %, is preferably 1 quality % ~ 50 quality %.

Other polymkeric substance this can list and such as comprise poly-(methyl) acrylate, polyamic acid, polyimide etc. and be not the high molecular polymkeric substance of photonasty side chain type etc. that can show liquid crystal liquid crystal property.

<< (B) organic solvent >>

As long as the organic solvent used in polymer composition used in the present invention can the organic solvent of dissolving resin composition just be not particularly limited.Below list its concrete example.

Can list: DMF, DMA, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3-methoxyl-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1,3-dimethyl-2-imidazolidinone, ethyl pentyl group ketone, methyl nonyl ketone, MEK, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-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, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic acid esters, tripropylene glycol methyl ether etc.They can be used alone, also can be used in combination.

The polymer composition used in the present invention can containing the composition outside above-mentioned (A) and (B) composition.As its example, solvent or the compound of raising film thickness uniformity, surface smoothness when coated polymeric composition can be listed, improve the compound etc. of the adaptation of liquid crystal orientation film and substrate, but be not limited to this.

As the concrete example of the solvent (poor solvent) of raising film thickness uniformity, surface smoothness, following solvent can be listed.

Such as isopropyl alcohol can be listed, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl 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, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, 1-hexanol, normal hexane, n-pentane, normal octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid Methylethyl, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, propylene glycol-1-single ether-2-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the solvent etc. of low surface tension.

These poor solvents can use a kind, also can be used in combination multiple.When using solvent as described above, in order to not make the dissolubility of the solvent entirety comprised in polymer composition significantly reduce, being preferably 5 quality % ~ 80 quality % of solvent entirety, being more preferably 20 quality % ~ 60 quality %.

As the compound improving film thickness uniformity, surface smoothness, fluorine system surfactant, silicone based surfactants and nonionic system surfactant etc. can be listed.

More specifically, such as Eftop (registered trademark) 301, EF303, EF352 (TohkemproductsCorporation system) can be listed; Megafac (registered trademark) F171, F173, R-30 (DICCORPORATION system); FluoradFC430, FC431 (Sumitomo3MLimited system); AsahiGuard (registered trademark) AG710 (Asahi Glass Co., Ltd's system); Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGCSEIMICHEMICALCO., LTD. system) etc.The usage ratio of these surfactants is preferably 0.01 mass parts ~ 2 mass parts relative to resinous principle 100 mass parts contained in polymer composition, is more preferably 0.01 mass parts ~ 1 mass parts.

As the concrete example of compound of adaptation improving liquid crystal orientation film and substrate, the following compound etc. containing functional silanes illustrated can be listed.

Such as 3-TSL 8330 can be listed, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-aminoethyl)-3-TSL 8330, N-(2-aminoethyl)-3-amino propyl methyl dimethoxysilane, 3-urea propyl trimethoxy silicane, 3-urea propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide three second triamine, N-trimethoxy-silylpropyl three second triamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (oxygen the ethylidene)-3-TSL 8330 of N-, two (oxygen ethylidene)-APTESs of N-etc.

And then, in order to improve the adaptation of substrate and liquid crystal orientation film and prevent from forming the electrical characteristics reduction etc. caused by backlight when liquid crystal represents element, phenoplast system as following, adjuvant containing the compound of epoxy radicals can be contained in polymer composition.Concrete phenoplast system adjuvant is below shown, but is not limited to this structure.

As the concrete compound containing epoxy radicals, ethylene glycol diglycidylether can be exemplified, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidyl ether, 1, 3, 5, 6-four glycidyl group-2, 4-hexanediol, N, N, N ', N ',-four glycidyl group m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N ',-four glycidyl group-4, 4 '-diaminodiphenyl-methane etc.

When using the compound of adaptation for improving liquid crystal orientation film and substrate, its consumption is preferably 0.1 mass parts ~ 30 mass parts relative to resinous principle 100 mass parts contained in polymer composition, is more preferably 1 mass parts ~ 20 mass parts.During by quantity not sufficient 0.1 mass parts, cannot expect the effect improving adaptation, during more than 30 mass parts, the orientation of liquid crystal is deteriorated sometimes.

As adjuvant, also photosensitizer can be used.Be preferably colourless sensitizer and triplet sensitizer.

As photosensitizer, there is aromatic nitro compound, cumarin (7-lignocaine-4-methylcoumarin, 7-hydroxyl 4-methylcoumarin), coumarin ketone, carbonyl bicoumarin, aromatic series 2-hydroxy-ketone, and by aromatic series 2-hydroxy-ketone (2-dihydroxy benaophenonel that amino replaces, single to (dimethylamino)-2-dihydroxy benaophenonel or two to (dimethylamino)-2-dihydroxy benaophenonel), acetophenone, anthraquinone, xanthone, sulfo-xanthone, benzanthrone, thiazoline (2-benzoyl methylene-3-methyl-β-aphthothiazoles quinoline, 2-(β-naphthoyl methylene)-3-methylbenzothiazole quinoline, 2-(α-naphthoyl methylene)-3-methylbenzothiazole quinoline, 2-(4-dibenzoyl methylene)-3-methylbenzothiazole quinoline, 2-(β-naphthoyl methylene)-3-methyl-β-aphthothiazoles quinoline, 2-(4-dibenzoyl methylene)-3-methyl-β-aphthothiazoles quinoline, 2-(to fluorobenzoyl methylene)-3-methyl-β-aphthothiazoles quinoline), oxazoline (2-benzoyl methylene-3-methyl-β-Nai Bing oxazoline, 2-(β-naphthoyl methylene)-3-Jia base benzoxazole quinoline, 2-(α-naphthoyl methylene)-3-Jia base benzoxazole quinoline, 2-(4-dibenzoyl methylene)-3-Jia base benzoxazole quinoline, 2-(β-naphthoyl methylene)-3-methyl-β-Nai Bing oxazoline, 2-(4-dibenzoyl methylene)-3-methyl-β-Nai Bing oxazoline, 2-(to fluorobenzoyl methylene)-3-methyl-β-naphthalene oxazoline), benzothiazole, nitroaniline (meta nitro aniline or paranitroanilinum, 2,4,6-trinitroaniline) or nitro acenaphthene (5-nitro acenaphthene), (2-[(hydroxyl is to methoxyl) styryl] benzothiazole, benzoin alkylether, N-alkylation phthalein ketone, acetophenone ketal (2,2-Dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthalene methyl alcohol, 2-naphthalene-carboxylic acid, 9-anthryl carbinol and 9-anthracene carboxylic acid), chromene, azo indolizine, plum Lip river cumarin etc.

Be preferably aromatic series 2-hydroxy-ketone (benzophenone), cumarin, coumarin ketone, carbonyl bicoumarin, acetophenone, anthraquinone, xanthone, sulfo-xanthone and acetophenone ketal.

In polymer composition except above-mentioned substance, as long as in the scope not damaging effect of the present invention, for the object of the electrical characteristics such as specific inductive capacity, electric conductivity of change liquid crystal orientation film, dielectric, conductive materials can be added, and then improve the hardness of film, the object of density for when making liquid crystal orientation film, can cross-linked compound be added.

The method be coated on by above-mentioned polymer composition on the substrate with transverse electric field driving conducting film is not particularly limited.

About coating process, the industrial method normally utilizing serigraphy, hectographic printing, flexible printing or ink-jet method etc. to carry out.As other coating process, there are infusion process, rolling method, slot coated method, spin-coating method (method of spin coating) or spraying process etc., can be used them according to object.

On the substrate with transverse electric field driving conducting film after coated polymeric composition, utilize the heater meanses such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven with 50 ~ 200 DEG C, preferably with 50 ~ 150 DEG C, solvent is evaporated, thus can film be obtained.Baking temperature is now preferably lower than side chain type high molecular liquid crystal phase performance temperature.

When the thickness of film is blocked up, be disadvantageous in the power consumption representing element at liquid crystal, when the thickness of film is crossed thin, liquid crystal represents that the reliability of element reduces sometimes, is therefore preferably 5nm ~ 300nm, is more preferably 10nm ~ 150nm.

In addition, after [I] operation, before next [II] operation, the operation substrate being formed with film being cooled to room temperature can also be set.

< operation [II] >

In operation [II], polarized UV rays is irradiated to the film obtained in operation [I].When polarized UV rays is irradiated to the face of film, across polarization plates, the ultraviolet of polarization is irradiated to substrate from specific direction.As the ultraviolet that will use, wavelength can be used for the ultraviolet of 100nm ~ 400nm scope.Preferably, according to the film kind that will use, select best wavelength by wave filter etc.Further, can choice for use wavelength be such as the ultraviolet of 290nm ~ 400nm scope, optionally photo-crosslinking can be brought out.As ultraviolet, the light such as sent by high-pressure sodium lamp can be used.

For the exposure of polarized UV rays, depend on the film that will use.About exposure, preferably be set in the scope of 1% ~ 70% of the amount of the polarized UV rays of the maximal value (hereinafter also referred to Δ Amax) realizing Δ A, be more preferably set in the scope of 1% ~ 50%, described Δ A is this film, is parallel to the ultraviolet absorbance in the direction of the polarization direction of polarized UV rays and the difference perpendicular to the ultraviolet absorbance in the direction of the polarization direction of polarized UV rays.

< operation [III] >

In operation [III], heat and irradiated the film of polarized UV rays in operation [II].Tropism control ability can be given to film by heating.

Heating can use the heater meanses such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven.Heating-up temperature can consider that the temperature making film used show liquid crystal liquid crystal property is determined.

Heating-up temperature is preferably side chain type macromolecule and can shows in the temperature range of temperature (hereinafter referred to as liquid crystal performance temperature) of liquid crystal liquid crystal property.Measurablely to arrive: when the film surface of film and so on, the liquid crystal performance temperature of film coated surface can show the liquid crystal performance temperature during photonasty side chain type macromolecule of liquid crystal liquid crystal property lower than whole observation.Therefore, heating-up temperature is more preferably in the temperature range of liquid crystal performance temperature of film coated surface.That is, the temperature range of irradiating the heating-up temperature after polarized UV rays preferably will show the temperature of low 10 DEG C of the lower limit of the temperature range of temperature as lower limit and using the temperature of the temperature of lower than the upper limit of this liquid crystal temperature range 10 DEG C as the scope of the upper limit than the high molecular liquid crystal of side chain type used.When heating-up temperature is lower than said temperature scope, there is the insufficient tendency of anisotropy amplification effect come by the torrid zone in film, in addition, when heating-up temperature is too high compared with said temperature scope, exist and be coated with the tendency of membrane stage close to isotropic liquid condition (isotropic phase), now, be sometimes difficult to because of self assembly to a direction reorientation.

It should be noted that, liquid crystal performance temperature refers to: more than side chain type macromolecule or the film coated surface glass transition temperature (Tg) from solid-phase to liquid crystal phase generation phase in version homogeneous phase transition temperature (Tiso) temperature below of phase in version occurs from liquid crystal phase to homogeneous phase (isotropic phase).

From the same reasons recorded middle with operation [I], the coating thickness formed after heating can be preferably 5nm ~ 300nm, be more preferably 50nm ~ 150nm.

< operation [IV] >

In operation [IV], after the film of heating in operation [III] being cooled to the temperature of the glass transition temperature of this film coated surface not enough, then be heated to the temperature of more than this glass transition temperature.

That is, film heating in operation [III] obtained temporarily is cooled to the temperature of the glass transition temperature of not enough film coated surface.In other words, be cooled to the temperature lower than the lower limit of the liquid crystal performance temperature of film coated surface by film heating in operation [III] obtained, thus make the liquid crystal liquid crystal property state phase in version (glass transition) of film coated surface to solid shape.Herein, due to the tendency that the liquid crystal performance temperature that there is film coated surface is lower than liquid crystal performance temperature during whole observation side chain type macromolecule, therefore the chilling temperature of film is preferably than the temperature of low more than 10 DEG C of side chain type high molecular glass transition point temperature (Tg) as (A) composition.As the preference of described chilling temperature, be room temperature (such as 25 DEG C).

The cooling of the film obtained in the middle heating of operation [III] can use cooling chamber, coolant etc. to be cooled to the chilling temperature of target energetically, also can cool lentamente by taking out from heater means and placing.

And then, in operation [IV], the film cooled is heated to again the temperature of more than the glass transition temperature of film coated surface.Specifically, the film cooled is heated to again the liquid crystal performance temperature of film coated surface.As mentioned above, the liquid crystal performance temperature of film coated surface refers to: more than the glass transition temperature of film coated surface and the temperature of the homogeneous phase transition temperature of not enough film coated surface.Irradiate the heating-up temperature (heating-up temperature of operation [III]) of the film after polarized UV rays and cooled heating-up temperature when heating again can difference also can be identical, then heating-up temperature when heating preferably reach the film after irradiation polarized UV rays heating-up temperature below temperature.

By having as above operation, in manufacture method of the present invention, can realize importing anisotropy efficiently to film.Further, can the substrate of fabricated ribbon liquid crystal orientation film efficiently.

< operation [V] >

[V] operation is that the substrate (the 1st substrate) the transverse electric field driving conducting film obtained in [IV] with liquid crystal orientation film is carried out subtend configuration across liquid crystal in the mode that both liquid crystal orientation films are relative with the substrate (the 2nd substrate) without the band liquid crystal orientation film of conducting film similarly obtained in above-mentioned [I '] ~ [III '] or [I '] ~ [IV '], utilize known method to make liquid crystal cells, thus the driving liquid crystal of making transverse electric field represent the operation of element.It should be noted that, operation [I '] ~ [III ']] or operation [I '] ~ [IV '] in, the substrate not having a transverse electric field driving conducting film except use in the operation [I] replaces having except the substrate of this transverse electric field driving conducting film, can carry out in the same manner as operation [I] ~ [III] or operation [I '] ~ [IV '].The difference of operation [I] ~ [IV] and operation [I '] ~ [IV '] is only with or without above-mentioned conducting film, therefore omits the explanation of operation [I '] ~ [IV '].

If list the production example that liquid crystal cells or liquid crystal represent element, then can exemplify following method: prepare the 1st above-mentioned substrate and the 2nd substrate, the liquid crystal orientation film of a substrate scatters sept, the mode becoming inner side with liquid crystal aligning face is pasted on another substrate, and decompression injects liquid crystal and the method for sealing; Or, after the liquid crystal aligning face dropping liquid crystalline substance being scattered with sept, the method etc. that adhesive substrate carrying out seals.Now, the substrate of side preferably uses the substrate of the electrode with transverse electric field driving comb teeth-shaped structure.Sept diameter is now preferably 1 μm ~ 30 μm, is more preferably 2 μm ~ 10 μm.This sept diameter determines the thickness of spacing, the i.e. liquid crystal layer of a pair substrate for clamping liquid crystal layer.

In the manufacture method of the substrate of band film of the present invention, polymer composition is coated on after substrate forms film, irradiates polarized UV rays.Then, realize importing efficiently anisotropy in side chain type polymeric membrane by carrying out heating, thus manufacture the substrate possessing the band liquid crystal orientation film of liquid crystal aligning control ability.

In the film that the present invention is used, the principle of Molecular reorientation utilizing the light reaction of side chain and bring out based on the self assembly of liquid crystal liquid crystal property, realizes importing anisotropy efficiently to film.In manufacture method of the present invention, when side chain type macromolecule has the structure of photocrosslinking reaction group as photoreactive group, after using side chain type macromolecule to form film on substrate, irradiate polarized UV rays, after then heating, make liquid crystal and represent element.

Below, there is photocrosslinking reaction group be called the 1st mode using employing as the high molecular embodiment of side chain type of the structure of photoreactive group, using employing, there is light fries' rearrangement group or carry out isomerized group and be called the 2nd mode as the high molecular embodiment of side chain type of the structure of photoreactive group, and be described.

Fig. 1 be schematically illustrate to employ in the 1st mode of the present invention have photocrosslinking reaction group as the structure of photoreactive group side chain type macromolecule, anisotropy in the manufacture method of liquid crystal orientation film imports the figure of an example of process.(a) of Fig. 1 is the figure of the state of side chain type polymeric membrane before polarizing light irradiation is schematically described, (b) of Fig. 1 is the figure of the state of side chain type polymeric membrane after polarizing light irradiation is schematically described, (c) of Fig. 1 is the figure of the state of side chain type polymeric membrane after heating is schematically described, especially imported anisotropy hour, namely in the 1st mode of the present invention, the schematic diagram of ultraviolet irradiation amount when making Δ A arrive in the scope of 1% ~ 15% of maximum ultraviolet irradiation amount of [II] operation.

Fig. 2 be schematically illustrate to employ in the 1st mode of the present invention have photocrosslinking reaction group as the structure of photoreactive group side chain type macromolecule, anisotropy in the manufacture method of liquid crystal orientation film imports the figure of an example of process.(a) of Fig. 2 is the figure of the state of side chain type polymeric membrane before polarizing light irradiation is schematically described, (b) of Fig. 2 is the figure of the state of side chain type polymeric membrane after polarizing light irradiation is schematically described, (c) of Fig. 2 is the figure of the state of side chain type polymeric membrane after heating is schematically described, especially when imported anisotropy is large, namely in the 1st mode of the present invention, the ultraviolet irradiation amount of [II] operation schematic diagram when making Δ A reach in the scope of 15% ~ 70% of maximum ultraviolet irradiation amount.

Fig. 3 be schematically illustrate to employ in the 2nd mode of the present invention have the light fries' rearrangement group shown in photoisomerization group or above-mentioned formula (18) as the structure of photoreactive group side chain type macromolecule, anisotropy in the manufacture method of liquid crystal orientation film imports the figure of an example of process.(a) of Fig. 3 is the figure of the state of side chain type polymeric membrane before polarizing light irradiation is schematically described, (b) of Fig. 3 is the figure of the state of side chain type polymeric membrane after polarizing light irradiation is schematically described, (c) of Fig. 3 is the figure of the state of side chain type polymeric membrane after heating is schematically described, especially imported anisotropy hour, namely in the 2nd mode of the present invention, the ultraviolet irradiation amount of [II] operation schematic diagram when making Δ A reach in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount.

Fig. 4 be schematically illustrate to employ in the 2nd mode of the present invention have the light fries' rearrangement group shown in above-mentioned formula (19) as the structure of photoreactive group side chain type macromolecule, anisotropy in the manufacture method of liquid crystal orientation film imports the figure of an example of process.(a) of Fig. 4 is the figure of the state of side chain type polymeric membrane before polarizing light irradiation is schematically described, (b) of Fig. 4 is the figure of the state of side chain type polymeric membrane after polarizing light irradiation is schematically described, (c) of Fig. 4 is the figure of the state of side chain type polymeric membrane after heating is schematically described, especially when imported anisotropy is large, namely in the 2nd mode of the present invention, the ultraviolet irradiation amount of [II] operation schematic diagram when making Δ A reach in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount.

In 1st mode of the present invention, by importing anisotropic process to film, the ultraviolet irradiation amount of [II] operation, when Δ A is reached in the scope of 1% ~ 15% of maximum ultraviolet irradiation amount, first, substrate forms film 1.As shown in (a) of Fig. 1, in the film 1 that substrate is formed, there is the structure of side chain 2 random alignment.According to the random alignment of the side chain 2 of film 1, the liquid crystal ultimate constituent of side chain 2 and photonasty group also orientation randomly, this film 1 is isotropic.

In 1st mode of the present invention, by importing anisotropic process to film, the ultraviolet irradiation amount of [II] operation, when Δ A is reached in the scope of 15% ~ 70% of maximum ultraviolet irradiation amount, first, substrate forms film 3.As shown in (a) of Fig. 2, in the film 3 that substrate is formed, there is the structure of side chain 4 random alignment.According to the random alignment of the side chain 4 of film 3, the liquid crystal ultimate constituent of side chain 4 and photonasty group also orientation randomly, this film 2 is isotropic.

In 2nd mode of the present invention, by importing anisotropic process to film, when application employs the side chain type of the structure with photoisomerization group or the light fries' rearrangement group shown in above-mentioned formula (18) high molecular liquid crystal orientation film, the ultraviolet irradiation amount of [II] operation is when Δ A is reached in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount, first, substrate forms film 5.As shown in (a) of Fig. 3, in the film 5 that substrate is formed, there is the structure of side chain 6 random alignment.According to the random alignment of the side chain 6 of film 5, the liquid crystal ultimate constituent of side chain 6 and photonasty group also orientation randomly, this side chain type polymeric membrane 5 is isotropic.

In 2nd mode of the present invention, by importing anisotropic process to film, when application employs the side chain type of the structure with the light fries' rearrangement group shown in above-mentioned formula (19) high molecular liquid crystal orientation film, the ultraviolet irradiation amount of [II] operation is when Δ A is reached in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount, first, substrate forms film 7.As shown in (a) of Fig. 4, in the film 7 that substrate is formed, there is the structure of side chain 8 random alignment.According to the random alignment of the side chain 8 of film 7, the liquid crystal ultimate constituent of side chain 8 and photonasty group also orientation randomly, this film 7 is isotropic.

In 1st mode of this enforcement, the ultraviolet irradiation amount of [II] operation, when Δ A is reached in the scope of 1% ~ 15% of maximum ultraviolet irradiation amount, irradiates polarized UV rays to this isotropic film 1.Thus, as shown in (b) of Fig. 1, there is the light reactions such as dimerization reaction the photonasty group priorities of the side chain 2a among the side chain 2 that the direction parallel with ultraviolet polarization direction arranges, there is photonasty group.Its result, the density that there occurs the side chain 2a of light reaction slightly uprises on the polarization direction of irradiation ultraviolet radiation, and its result gives very little anisotropy to film 1.

In 1st mode of this enforcement, the ultraviolet irradiation amount of [II] operation, when Δ A is reached in the scope of 15% ~ 70% of maximum ultraviolet irradiation amount, irradiates polarized UV rays to this isotropic film 3.Thus, as shown in (b) of Fig. 2, there is the light reactions such as dimerization reaction the photonasty group priorities of the side chain 4a among the side chain 4 that the direction parallel with ultraviolet polarization direction arranges, there is photonasty group.Its result, the density that there occurs the side chain 4a of light reaction uprises on the polarization direction of irradiation ultraviolet radiation, and its result gives little anisotropy to film 3.

In the 2nd mode of this enforcement, application employs the high molecular liquid crystal orientation film of side chain type of the structure with photoisomerization group or the light fries' rearrangement group shown in above-mentioned formula (18), the ultraviolet irradiation amount of [II] operation, when Δ A is reached in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount, irradiates polarized UV rays to this isotropic film 5.Thus, as shown in (b) of Fig. 3, there is the light reactions such as light fries' rearrangement the photonasty group priorities of the side chain 6a among the side chain 6 that the direction parallel with ultraviolet polarization direction arranges, there is photonasty group.Its result, the density that there occurs the side chain 6a of light reaction slightly uprises on the polarization direction of irradiation ultraviolet radiation, and its result gives very little anisotropy to film 5.

In the 2nd mode of this enforcement, application employs the high molecular film of side chain type of the structure with the light fries' rearrangement group shown in above-mentioned formula (19), the ultraviolet irradiation amount of [II] operation, when Δ A is reached in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount, irradiates polarized UV rays to this isotropic film 7.Thus, as shown in (b) of Fig. 4, there is the light reactions such as light fries' rearrangement the photonasty group priorities of the side chain 8a among the side chain 8 that the direction parallel with ultraviolet polarization direction arranges, there is photonasty group.Its result, the density that there occurs the side chain 8a of light reaction uprises on the polarization direction of irradiation ultraviolet radiation, and its result gives little anisotropy to film 7.

Then, in the 1st mode of this enforcement, the ultraviolet irradiation amount of [II] operation is when Δ A is reached in the scope of 1% ~ 15% of maximum ultraviolet irradiation amount, is heated by the film 1 after irradiating polarized light and makes mesomorphic state.Thus, as shown in (c) of Fig. 1, in film 1, be parallel between the direction of polarization direction of irradiation ultraviolet radiation and the direction perpendicular to the polarization direction of irradiation ultraviolet radiation, the amount of the cross-linking reaction of generation is different.Now, the amount of the cross-linking reaction that the direction being parallel to the polarization direction of irradiation ultraviolet radiation produces is very little, and therefore work as plastifier in this cross-linking reaction position.Therefore, perpendicular to the liquid crystal liquid crystal property in the direction of the polarization direction of irradiation ultraviolet radiation higher than the liquid crystal liquid crystal property in direction of polarization direction being parallel to irradiation ultraviolet radiation, there is self assembly in the direction being parallel to the polarization direction of irradiation ultraviolet radiation, the side chain 2 comprising liquid crystal ultimate constituent carries out reorientation.Its result, the very little anisotropy of the film 1 brought out because of photo-crosslinking is amplified because of heat, gives larger anisotropy to film 1.

Similarly, in the 1st mode of this enforcement, the ultraviolet irradiation amount of [II] operation, when Δ A is reached in the scope of 15% ~ 70% of maximum ultraviolet irradiation amount, is heated by the film 3 after polarizing light irradiation and make mesomorphic state.Thus, as shown in (c) of Fig. 2, in side chain type polymeric membrane 3, be parallel between the direction of polarization direction of irradiation ultraviolet radiation and the direction perpendicular to the polarization direction of irradiation ultraviolet radiation, the amount of the cross-linking reaction of generation is different.Therefore, there is self assembly in the direction being parallel to the polarization direction of irradiation ultraviolet radiation, the side chain 4 comprising liquid crystal ultimate constituent carries out reorientation.Its result, the less anisotropy of the film 3 brought out because of photo-crosslinking is amplified because of heat, gives larger anisotropy to film 3.

Similarly, in 2nd mode of this enforcement, application employs the high molecular film of side chain type of the structure with photoisomerization group or the light fries' rearrangement group shown in above-mentioned formula (18), the ultraviolet irradiation amount of [II] operation, when Δ A is reached in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount, is carried out heating by the film 5 after polarizing light irradiation and make mesomorphic state.Thus, as shown in (c) of Fig. 3, in film 5, be parallel between the direction of polarization direction of irradiation ultraviolet radiation and the direction perpendicular to the polarization direction of irradiation ultraviolet radiation, the amount of the light Fries rearrangement of generation is different.Now, the liquid crystal aligning power of the side chain before the liquid crystal aligning force rate reaction of the light fries' rearrangement body produced perpendicular to the direction of the polarization direction of irradiation ultraviolet radiation is strong, there is self assembly in the direction therefore perpendicular to the polarization direction of irradiation ultraviolet radiation, the side chain 6 comprising liquid crystal ultimate constituent carries out reorientation.Its result, the very little anisotropy of the film 5 brought out because of light Fries rearrangement is amplified because of heat, gives larger anisotropy to film 5.

Similarly, in 2nd mode of this enforcement, application employs the high molecular film of side chain type of the structure with the light fries' rearrangement group shown in above-mentioned formula (19), the ultraviolet irradiation amount of [II] operation, when Δ A is reached in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount, is carried out heating by the film 7 after polarizing light irradiation and make mesomorphic state.Thus, as shown in (c) of Fig. 4, in side chain type polymeric membrane 7, be parallel between the direction of polarization direction of irradiation ultraviolet radiation and the direction perpendicular to the polarization direction of irradiation ultraviolet radiation, the amount of the light Fries rearrangement of generation is different.The anchor force of light fries' rearrangement body 8 (a) is than the side chain Final 8 before rearrangement, when therefore producing certain a certain amount of above light fries' rearrangement body, there is self assembly in the direction being parallel to the polarization direction of irradiation ultraviolet radiation, the side chain 8 comprising liquid crystal ultimate constituent carries out reorientation.Its result, the less anisotropy of the film 7 brought out because of light Fries rearrangement is amplified because of heat, gives larger anisotropy to film 7.

Therefore, the film used in method of the present invention by carrying out successively irradiating polarized UV rays and heating to film, thus is imported anisotropy efficiently, can make the liquid crystal orientation film of tropism control ability excellence.

Further, for the film used in method of the present invention, the exposure of polarized UV rays to film irradiation and the heating-up temperature of heating is optimized.Can realize thus importing anisotropy efficiently to film.

The exposure importing for anisotropy best polarized UV rays efficiently for the film used in the present invention reaches best polarized UV rays exposure corresponding to the amount of the photonasty group generation photo-crosslinking made in this film, photoisomerization reaction or light Fries rearrangement.The film that uses in the present invention is irradiated to the result of polarized UV rays, carry out photo-crosslinking, photoisomerization reaction or light Fries rearrangement the photonasty group of side chain few time, do not reach sufficient light reaction amount.Now, also sufficient self assembly can not be carried out even if carry out heating thereafter.On the other hand, for the film used in the present invention, to the result of structured illumination polarized UV rays with photocrosslinking reaction group, carry out the photonasty group of the side chain of cross-linking reaction excessive time, the cross-linking reaction between side chain can excessively advance.Now, gained film becomes upright and outspoken, sometimes hinders the propelling of the self assembly by heating thereafter.In addition, for the film used in the present invention, to the result of structured illumination polarized UV rays with light fries' rearrangement group, when the photonasty group carrying out the side chain of light Fries rearrangement becomes excessive, the liquid crystal liquid crystal property of film can too reduce.Now, the liquid crystal liquid crystal property of gained film also reduces, and sometimes hinders the propelling of the self assembly by heating thereafter.And then to when having the structured illumination polarized UV rays of light fries' rearrangement group, if ultraviolet irradiation amount is too much, then side chain type macromolecule generation light decomposes, and sometimes hinders the propelling of the self assembly by heating thereafter.

Therefore, in film used in the present invention, 0.1 % by mole ~ 40 % by mole that photo-crosslinking occurs because of the irradiation of polarized UV rays for the photonasty group of side chain, the optimised quantity of photoisomerization reaction or light Fries rearrangement is preferably set to the photonasty group that this side chain type polymeric membrane has, be more preferably set to 0.1 % by mole ~ 20 % by mole.By making the amount of the photonasty group of the side chain carrying out light reaction be this scope, the self assemblyization in heating thereafter can efficiently advance, and can form the efficient anisotropy in film.

In the film that method of the present invention uses, by the optimization of the exposure of polarized UV rays, thus optimize the amount of the photo-crosslinking of the photonasty group in the side chain of side chain type polymeric membrane, photoisomerization reaction or light Fries rearrangement.Further, realize in the lump with heating thereafter importing anisotropy efficiently in film used in the present invention.Now, for the polarized UV rays amount be applicable to, can carry 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, be determined at that polarized UV rays is postradiation respectively, the UVA in direction of polarization direction that is parallel to polarized UV rays and the UVA in the direction perpendicular to the polarization direction of polarized UV rays.Evaluate Δ A by the measurement result of uv absorption, described Δ A is the ultraviolet absorbance being parallel to the direction of the polarization direction of polarized UV rays in this film and the difference perpendicular to the ultraviolet absorbance in the direction of the polarization direction of polarized UV rays.Further, the exposure of the maximal value (Δ Amax) obtaining the Δ A realized in film used in the present invention and the polarized UV rays realizing it.In manufacture method of the present invention, the polarized UV rays exposure this being realized Δ Amax, as benchmark, can determine the polarized UV rays amount of the preferred amounts of irradiating in the manufacture of liquid crystal orientation film.

In manufacture method of the present invention, preferably the exposure of the polarized UV rays of irradiating film used in the present invention is set to and is set in the scope of 1% ~ 50% in the scope of 1% ~ 70% of the amount of the polarized UV rays that can realize Δ Amax, more preferably.In film used in the present invention, the exposure that can realize the polarized UV rays in the scope of 1% ~ 50% of the amount of the polarized UV rays of Δ Amax is equivalent to the amount of the polarized UV rays of 0.1 % by mole ~ 20 % by mole generation photo-crosslinkings of the photonasty integrated group that this side chain type polymeric membrane is had.

As mentioned above, in manufacture method of the present invention, in order to realize importing anisotropy efficiently to film, using the high molecular liquid crystal temperature range of this side chain type as benchmark, determine applicable heating-up temperature as described above.Therefore, such as, when the high molecular liquid crystal temperature range of side chain type used in the present invention is 100 DEG C ~ 200 DEG C, expect to make the postradiation heating-up temperature of polarized UV rays be 90 DEG C ~ 190 DEG C.By such setting, give larger anisotropy to film used in the present invention.

By such operation, the liquid crystal provided by the present invention represents that element is to the external stress such as light, heat display high reliability.

Operate as above, the driving liquid crystal of the transverse electric field manufactured by the inventive method represents that element substrate or the driving liquid crystal of transverse electric field with this substrate represent the excellent in reliability of element, can compatibly for large picture and the LCD TV etc. of high-resolution.

Embodiment

The abbreviation used in embodiment is shown as follows.

(methacrylic monomer)

MA1 is synthesized by the synthetic method described in patent documentation (WO2011-084546).

MA2 is synthesized by the synthetic method described in patent documentation (Japanese Unexamined Patent Publication 9-118717).

(organic solvent)

THF: tetrahydrofuran

NMP:N-N-methyl-2-2-pyrrolidone N-

BC: butyl cellosolve

(polymerization initiator)

AIBN:2,2 '-azobis isobutyronitrile

[mensuration of phase transition temperature]

The liquid crystal phase transition temperature of the polymkeric substance obtained by embodiment is used means of differential scanning calorimetry to measure (DSC) DSC3100SR (マッ Network サイエ Application ス Inc.) and measures.

< synthesis example 1>

MA1 (15.29g, 46mmol), MA2 (56.37g, 184mmol) are dissolved in THF (655.1g), with membrane pump carry out degassed after, add AIBN (1.13g, 6.9mmol) and also again carry out degassed.After this, the polymer solution of methacrylate is obtained with 60 DEG C of reactions 20 hours.This polymer solution is dropped to diethyl ether (7000ml), filter gained sediment.This sediment diethyl ether is cleaned, in the baking oven of 40 DEG C, carries out drying under reduced pressure, thus obtain methacrylate polymers powder.The number-average molecular weight of this polymkeric substance is 15000, weight-average molecular weight is 40500.

The liquid crystal phase transition temperature of gained methacrylate polymers is 120 DEG C ~ 185 DEG C.

In gained methacrylate polymers powder (6.0g), add NMP (54.0g), make it dissolve with stirring at room temperature 5 hours.In this solution, add BC (40.0g) and stir, thus obtaining aligning agent for liquid crystal (A).

< embodiment 1>

(making of liquid crystal cells)

Use the aligning agent for liquid crystal (A) obtained in synthesis example 1, carry out the making of liquid crystal cells according to the following step illustrated.

Substrate be of a size of 30mm × 40mm, thickness is the glass substrate of 0.7mm, use and be configured with the substrate of the comb teeth-shaped pixel electrode formed by ito film patterning.Pixel electrode has the comb teeth-shaped shape that " < " font electrode key element that middle body bends is formed through multiple arrangement.The width of the Width of each electrode key element is 10 μm, is spaced apart 20 μm between electrode key element.The electrode key element of " < " font that the pixel electrode forming each pixel is bent by middle body is formed through multiple arrangement, therefore the shape of each pixel is not oblong-shaped, but possess in the same manner as electrode key element middle body bend, the shape of " < " word of being similar to runic.Further, each pixel for boundary is split up and down, has the 1st region of the upside of sweep and the 2nd region of downside with the sweep of these central authorities.When contrasting the 1st region and the 2nd region of each pixel, the formation direction forming the electrode key element of their pixel electrode is different.Namely, during using the orientation process direction of aftermentioned liquid crystal orientation film as benchmark, in the 1st region of pixel, the electrode key element of pixel electrode is formed in the mode of the angle (clockwise) presenting+15 °, in the 2nd region of pixel, form the electrode key element of pixel electrode in the mode of the angle (clockwise) presenting-15 °.That is, the 1st region of each pixel and the 2nd region are formed as follows: the liquid crystal brought out by applying voltage between pixel electrode and counter electrode, the direction reverse direction each other of spinning movement (plane switches) in real estate.

The aligning agent for liquid crystal obtained in synthesis example 1 (A) is spin-coated on prepared above-mentioned electroded substrate.Then, with press drying 90 second of 70 DEG C, forming thickness is the liquid crystal orientation film of 100nm.Then, across polarization plates with 10mJ/cm ²after coated surface being irradiated to the ultraviolet of 313nm, heat 10 minutes (burning till for 1 time) with the hot plates of 150 DEG C, the substrate of Slow cooling (cooling) to room temperature is heated 10 minutes (burning till for 2 times) with the hot plate of 150 DEG C again, thus obtains the substrate being with liquid crystal orientation film.Same operation, about ultraviolet irradiation amount, at 10mJ/cm ²~ 100mJ/cm ²in with 10mJ/cm ²interval, at 100mJ/cm ²above with 50mJ/cm ²interval, make different substrates respectively.

In addition, as subtend substrate, to not forming electrode and the glass substrate of column spacer with height 4 μm forms film, implementation orientation process similarly.Printing and sealing agent on the liquid crystal orientation film of a substrate (Xie Li KCC system, XN-1500T).Then, with liquid crystal aligning face relatively and after the mode that direction of orientation reaches 0 ° pastes another substrate, make sealant heat curing and make dummy cell.In this dummy cell, liquid crystal MLC-2041 (MERCKCORPORATION system) is injected by decompression injection method, sealing inlet, the liquid crystal obtaining possessing IPS (In-PlanesSwitching, plane switches) pattern represents the liquid crystal cells that element is formed.

(orientation observation)

Said method is utilized to make liquid crystal cells.Thereafter, in the baking oven of 120 DEG C, carry out the reorientation process of 60 minutes.Thereafter, the polarization microscope by polarization plates being made crossed nicols state is observed.Rotate liquid crystal cells and present when representing the state of black, the state that there is not bright spot, orientation bad regards as well.About ultraviolet irradiation amount, as mentioned above, observe the result of orientation for different substrate, the exposure border that orientation is good is as shown in table 1.

< embodiment 2>

Except the temperature of 2 times being burnt till process is set to except 130 DEG C, the method identical with embodiment 1 is utilized to make liquid crystal cells.Use gained liquid crystal cells, utilize the method identical with embodiment 1, evaluation approach.

Result is as shown in table 1.

< comparative example 1 ~ 2>

Except with or without Slow cooling operation with not containing except twice firing process, the method identical with embodiment 1 is utilized to make liquid crystal cells.Use gained liquid crystal cells, utilize the method identical with embodiment 1, evaluation approach.

Evaluation result is summed up and is shown in table 1.

Result is as shown in table 1.

[table 1]

According to result, via Slow cooling operation and under carrying out the condition of burning till for 2 times, the border showing the UV exposure of good liquid crystal aligning expands.

Infer this is because: burnt till by 1 time and determine the orientation orientation of main polymer backbone, but thereafter by being cooled to not enough glass transition temperature, for the oligomer composition more than brocken spectrum or near brocken spectrum, low molecular weight compositions present vitreousness (comparative example 1,2) when maintaining mixed and disorderly state of orientation at the temperature of to burn till for 1 time.Think: may be when again again heating with the temperature more than glass transition temperature and below liquid crystal transparent point herein, only oligomer composition, low molecular weight compositions are reset along by the form of to burn till the orientation orientation of the principal polymeric skeleton determined for 1 time, thus the orientation of alignment films entirety is improved.(it should be noted that, these are theory speculates, do not limit the present invention).

description of reference numerals

Fig. 1

1 side chain type polymeric membrane

2,2a side chain

Fig. 2

3 side chain type polymeric membranes

4,4a side chain

Fig. 3

5 side chain type polymeric membranes

6,6a side chain

Fig. 4

7 side chain type polymeric membranes

8,8a side chain

Claims

1. have the manufacture method that the driving liquid crystal of transverse electric field represents the substrate of element liquid crystal orientation film, it obtains being endowed the described liquid crystal orientation film of tropism control ability by possessing following operation:

[II] irradiates the operation of polarized UV rays to the film obtained in [I];

The film obtained in [II] is carried out the operation heated by [III]; And

2. method according to claim 1, wherein, the chilling temperature of the film in [IV] operation is the temperature than low more than 10 DEG C of side chain type high molecular glass transition point temperature (Tg) as (A) composition.

3. method according to claim 1 and 2, wherein, the heating-up temperature of the film after Ultraviolet radiation and cooled heating-up temperature are again more than the glass transition temperature of film coated surface and the temperature of the homogeneous phase transition temperature of not enough film coated surface.

4. the method according to any one of claims 1 to 3, wherein, (A) composition has the photonasty side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.

5. the method according to any one of Claims 1 to 4, wherein, (A) composition has any one the photonasty side chain in the group being selected from and being made up of following formula (1) ~ (6),

Y ₁represent the ring in the ester ring type hydrocarbon of the phenyl ring of 1 valency that is selected from, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5 ~ 8, or be selected from the group of 2 ~ 6 the identical or different rings in these substituting groups by binding groups B bonding, be bonded to their hydrogen atom independently of one another optionally by-COOR ₀,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace, in formula, R ₀represent the alkyl of hydrogen atom or carbon number 1 ~ 5;

One in q1 and q2 is 1, and another one is 0;

Q3 is 0 or 1;

L1 is 0 or 1;

L2 is the integer of 0 ~ 2;

When l1 and l2 is 0, when T is singly-bound, A also represents singly-bound;

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

6. the method according to any one of Claims 1 to 4, wherein, (A) composition has any one the photonasty side chain in the group being selected from and being made up of following formula (7) ~ (10),

L represents the integer of 1 ~ 12;

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

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

R represents the alkoxy of hydroxyl, carbon number 1 ~ 6, or represents and Y ₁identical definition.

7. the method according to any one of Claims 1 to 4, wherein, (A) composition has any one the photonasty side chain in the group being selected from and being made up of following formula (11) ~ (13),

In formula, A represents singly-bound ,-O-,-CH independently of one another ₂-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-;

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

R represents the ring in the ester ring type hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and the carbon number 5 ~ 8 being selected from 1 valency, or be selected from the group of 2 ~ 6 the identical or different rings in these substituting groups by binding groups B bonding, be bonded to their hydrogen atom independently of one another optionally by-COOR ₀,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace, in formula, R ₀represent the alkyl of hydrogen atom or carbon number 1 ~ 5, or R represents the alkoxy of hydroxyl or carbon number 1 ~ 6.

8. the method according to any one of Claims 1 to 4, wherein, (A) composition has following formula (14) or the photonasty side chain shown in (15),

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

9. the method according to any one of Claims 1 to 4, wherein, (A) composition as shown in following formula (16) or (17),

In formula, A represents singly-bound ,-O-,-CH ₂-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-;

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

10. the method according to any one of Claims 1 to 4, wherein, (A) composition has any one the photonasty side chain in the group being selected from and being made up of following formula (18) or (19),

In formula, A, B represent singly-bound ,-O-,-CH independently of one another ₂-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-;

One in q1 and q2 is 1, and another one is 0;

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

11. methods according to any one of Claims 1 to 4, wherein, (A) composition has the photonasty side chain shown in following formula (20),

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

12. methods according to any one of claim 1 ~ 11, wherein, (A) composition has any one the liquid crystal liquid crystal property side chain in the group being selected from and being made up of following formula (21) ~ (31),

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

One in q1 and q2 is 1, and another one is 0;

Z ₁, Z ₂represent singly-bound ,-CO-,-CH ₂o-,-CH=N-,-CF ₂-.

13. 1 kinds of substrates having the driving liquid crystal of transverse electric field and represent element liquid crystal orientation film, it is manufactured by the method according to any one of claim 1 ~ 12.

14. 1 kinds of driving liquid crystal of transverse electric field represent element, and it has substrate according to claim 13.

15. 1 kinds of driving liquid crystal of transverse electric field represent the manufacture method of element, and it obtains this liquid crystal by possessing following operation and represents element:

Prepare the substrate according to claim 13 i.e. operation of the 1st substrate;

[V] with described 1st liquid crystal orientation film and the 2nd liquid crystal orientation film across the right mode of liquid crystal phase, subtend described 1st substrate of configuration and the 2nd substrate, thus the operation obtaining that liquid crystal represents element,

Described operation [I '], [II '] and [III '] be:

The film obtained in [II '] is carried out the operation heated by [III '].

16. methods according to claim 15, wherein, the operation obtaining described 2nd substrate also has [IV '] by after in [III '], the film of heating is cooled to the temperature of the glass transition temperature of this film coated surface not enough, then is heated to the operation of temperature of more than this glass transition temperature.

17. 1 kinds of driving liquid crystal of transverse electric field represent element, and it is manufactured by the method described in claim 15 or 16.