CN105518521A

CN105518521A - Polymer composition and liquid crystal alignment film for in-plane-switching-type liquid crystal display element

Info

Publication number: CN105518521A
Application number: CN201480049083.1A
Authority: CN
Inventors: 金尔润; 后藤耕平; 根木隆之; 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: 2013-07-05
Filing date: 2014-07-04
Publication date: 2016-04-20
Anticipated expiration: 2034-07-04
Also published as: CN105518521B; TW201518361A; WO2015002291A1; TWI706981B; KR102324602B1; JP6681712B2; JPWO2015002291A1; KR20160030959A

Abstract

The present invention addresses the problem of providing a novel polymer composition for obtaining a liquid crystal alignment film for an in-plane-switching-type liquid crystal display element, the polymer composition having excellent image persistence characteristics and imparting alignment control performance with high efficiency, and a liquid crystal alignment film for an in-plane-switching-type liquid crystal display element that uses the polymer composition. The present invention solves the abovementioned problem by a polymer composition containing (A) a photosensitive side-chain macromolecule exhibiting liquid crystal properties in a predetermined temperature range, (B) polyurea, and (C) an organic solvent.

Description

Polymer composition and the driving liquid crystal of transverse electric field represent element liquid crystal orientation film

Technical field

The present invention relates to novel polymer compositions and use the driving liquid crystal of its transverse electric field to represent element liquid crystal orientation film and there is the manufacture method of substrate of this alignment films.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 and presents expectation state of orientation between the substrates to make liquid crystal.

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 therefore the liquid crystal that can be 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 make it that anisotropic decomposition occur.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 parallel with 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 parallel with 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, the orientation thermal stability of liquid crystal, light stability 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, therefore the liquid crystal aligning skew after liquid crystal drive easily occurs, 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 liquid crystal orientation film, the aligning agent for liquid crystal of high tropism control ability efficiently to liquid crystal orientation film.

The object of the invention is to, there is provided novel polymer composition and use the driving liquid crystal of its transverse electric field to represent that element liquid crystal orientation film and the substrate with this alignment films and the driving liquid crystal of transverse electric field with this substrate represent element, described polymer composition can provide and be endowed tropism control ability with high-level efficiency, the driving liquid crystal of transverse electric field of ghost excellent represents element liquid crystal orientation film.The present invention also aims to, even if provide the manufacture method utilizing easy fired also to have the liquid crystal orientation film that improve voltage retention and the substrate with this liquid crystal orientation film.

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> polymer composition, the especially driving liquid crystal of transverse electric field represent element liquid crystal orientation film manufacture polymer composition, and it contains:

(A) show in specific temperature range the photonasty side chain type macromolecule of liquid crystal liquid crystal property,

(B) polyureas and

(C) organic solvent.

In the above-mentioned <1> of <2>, (A) composition can have the photonasty side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.

In above-mentioned <1> or <2> of <3>, the polyureas as (B) composition can carry out polyreaction by making Diisocyanate component and diamine component and obtain.

In above-mentioned <1> or <2> of <4>, as (B) composition polyureas can by making Diisocyanate component, there is the carboxylic acid derivates of more than 2 carboxylic moiety and/or its acid anhydrides and diamine component carry out polyreaction and obtain.

In above-mentioned <3> or <4> of <5>, Diisocyanate component can be aromatic diisocyanate and/or aliphatic diisocyanate.

In any one of the above-mentioned <1> ~ <5> 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 (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> ~ <5> 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 (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> ~ <5> of <8>, (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> ~ <5> of <9>, (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> ~ <5> of <10>, (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> ~ <5> of <11>, (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> ~ <5> of <12>, (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> ~ <12> of <13>, (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 and B has 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 ester ring type hydrocarbon of the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring, carbon number 5 ~ 8, the alkyl of carbon number 1 ~ 12 or the alkoxy of carbon number 1 ~ 12;

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

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 ,-NO ₂,-CN, halogen group, 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 alkyl or alkoxy;

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

<14> 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] any combination thing of above-mentioned <1> ~ <13> is coated on there is transverse electric field driving conducting film substrate on and form the operation of film;

[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].

<15> mono-kind has the substrate that the driving liquid crystal of transverse electric field represents element liquid crystal orientation film, and it is manufactured by the method for above-mentioned <14>.

<16> driving liquid crystal of transverse electric field represents element, and it has the substrate of above-mentioned <15>.

<17> 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 <15>;

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

[IV] with the liquid crystal orientation film of the 1st substrate and the 2nd substrate across the right mode of liquid crystal phase, subtend configuration the 1st substrate and the 2nd substrate thus obtain the operation 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 the photonasty side chain type macromolecule of liquid crystal liquid crystal property, (B) polyureas and (C) organic solvent 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 '].

<18> driving liquid crystal of transverse electric field represents element, and it is manufactured by above-mentioned <17>.

In addition, following invention has been 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:

[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 the photonasty side chain type macromolecule of liquid crystal liquid crystal property, (B) polyureas and (C) organic solvent in specific temperature range;

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

In the above-mentioned <P1> of <P2>, (A) composition can have the photonasty side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.

In above-mentioned <P1> or <P2> of <P3>, the polyureas as (B) composition can carry out polyreaction by making Diisocyanate component and diamine component and obtain.

In the above-mentioned <P3> of <P4>, Diisocyanate component can be aromatic diisocyanate and/or aliphatic diisocyanate.

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 singly-bound, the group be selected from 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 independently of one another.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, m2 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;

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, its by above-mentioned <P1> ~ <P12> any one and manufacture.

<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>;

[IV] with the liquid crystal orientation film of the 1st substrate and the 2nd substrate across the right mode of liquid crystal phase, subtend configuration the 1st substrate 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 '].

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

<P17> driving liquid crystal of transverse electric field represents element liquid crystal orientation film manufacture composition, and it contains: (A) shows the photonasty side chain type macromolecule of liquid crystal liquid crystal property, (B) polyureas and (C) organic solvent in specific temperature range.

In the above-mentioned <P17> of <P18>, the polyureas as (B) composition can carry out polyreaction by making Diisocyanate component and diamine component and obtain.

In the above-mentioned <P18> of <P19>, Diisocyanate component can be aromatic diisocyanate and/or aliphatic diisocyanate.

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, in the present invention, by making polymer composition contain polyureas as (B) composition, carrying out easy fired even if can provide also there is the driving liquid crystal cell of transverse electric field of excellent voltage retention and the liquid crystal orientation film for this element.That is, according to the present invention, even if remain residual solvent (belonging to the METHYLPYRROLIDONE of high boiling solvent, N-ethyl-2-pyrrolidone etc.) in easy fired, the voltage retention higher than polyimide system alignment films can also be obtained.

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, uses foregoing polymer compositions and the film that obtains has the high molecular film of photonasty side chain type that can show liquid crystal liquid crystal property.This film does not need to carry 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 can become 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, obtains the liquid crystal orientation film being endowed high tropism control ability.

In addition, in polymer composition of the present invention, on the side chain type macromolecule as (A) composition and the basis as the organic solvent of (C) composition, also use polyureas as (B) composition.Thus, even if carry out easy fired, the voltage retention of liquid crystal orientation film also can significantly improve, and this is unexpected.Especially, as polyureas by using predetermined substance, above-mentioned effect is increased.The considerations such as the present inventor: these phenomenons are brought by adding (B) composition, in addition, (A) composition and (B) ingredient exerts interact, thus the effect that improve expectation by leaps and bounds (it should be noted that, these contain the opinion of inventor for mechanism of the present invention, do not restrict the present invention).

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:

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

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.

For the 2nd substrate, replace 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 [IV], 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] ~ [III] possessed for manufacture method of the present invention and each operation of [IV] 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 the photonasty side chain type macromolecule of liquid crystal liquid crystal property, polyureas and organic solvent.

< substrate >

Be not particularly limited for substrate, when the liquid crystal that manufacture represents that element is transmission-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 that being applicable to reflective liquid crystal represents 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 transmission-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, but be not limited to these.

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

< 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; (B) polyureas; And (C) 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 reacts 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 because of the light of the wavelength coverage of 250nm ~ 400nm.

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

(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 high molecular structure of photonasty side chain type that can show liquid crystal liquid crystal property meets this characteristic, be just not particularly limited, there is in preferential side chain structure 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 can occur; 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 the high molecular structure of photonasty side chain type 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 be 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 be 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 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 addition, side chain can be following formula (18) or the photonasty side chain shown in (19).

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

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 can be undertaken being polymerized by the photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer with above-mentioned photonasty side chain and obtain.

[photoreactivity side chain monomer]

Photoreactivity side chain monomer refers to following monomer: when forming macromolecule, can be formed in the macromolecule 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.

Have more style as photoreactivity side chain monomer, preferably there is the structure of following polymerizable group and following photonasty 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 photonasty side chain comprises at least a kind in above-mentioned formula (1) ~ (6), preferably such as comprises the photonasty side chain of at least a kind in above-mentioned formula (7) ~ (10), the photonasty side chain of at least a kind of comprising 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), the 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).

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

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

In formula (12) ~ (17), R represents hydrogen atom or methyl; S represents the alkylidene of carbon number 2 ~ 10; V represents 1 or 2; U represented for 0 or 1 (wherein, in formula (12), S represents the alkylidene of carbon number 2 ~ 9, and in formula (14), S represents the alkylidene of carbon number 1 ~ 10).

[liquid crystal liquid crystal property side chain monomer]

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

As mesogenic group that side chain has, also 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-oxetanylmethoxy) methyl esters and (methyl) acrylic acid (3-ethyl-3-oxetanylmethoxy) 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 and 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 causes 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 '-bis-(2,4-dibromo phenyl)-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 the ratio of radical initiator is preferably 0.1 % by mole ~ 10 % by mole relative to 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, for 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) composition >>

In polymer composition used in the present invention, as (B) composition, there is polyureas.(B) composition is preferably through the polymkeric substance making Diisocyanate component and diamine component carry out polyreaction and obtain.

<<< Diisocyanate component >>>

As the Diisocyanate component belonging to (B) component materials, such as aromatic diisocyanate, aliphatic diisocyanate etc. can be listed.Diisocyanate component is preferably aromatic diisocyanate, aliphatic diisocyanate.

Herein, aromatic diisocyanate refers to that the R group of diisocyanate structure (O=C=N-R-N=C=O) comprises the structure containing aromatic ring.In addition, aliphatic diisocyanate refers to that the R group of aforementioned isocyanates structure comprises ring-type or acyclic aliphatic structure.

As the concrete example of aromatic diisocyanate, adjacent phenylene diisocyanate, m-benzene diisocyanate, PPDI, toluene diisocyanate class can be listed (such as, 2,4-toluene di-isocyanate (TD.I)), 1,4-bis-isocyanic acid-2-methoxybenzene, 2,5-bis-isocyanic acid xylene, 2,2 '-bis-(4-bis-isocyanatophenyl) propane, 4,4 '-two isocyanic acid diphenyl methane, 4,4 '-two isocyanic acid diphenyl ether, 4,4 '-two isocyanic acid diphenyl sulfone, 3,3 '-two isocyanic acid diphenyl sulfone, 2,2 '-two isocyanic acid benzophenone etc.As aromatic diisocyanate, can preferably list 2,4-toluene di-isocyanate (TD.I).As the concrete example of aliphatic diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, tetramethyl ethylidene diisocyanate etc. can be listed.As aliphatic diisocyanate, preferably isophorone diisocyanate can be listed.Wherein, from the view point of polymerisation reactivity, voltage retention, be preferably isophorone diisocyanate and 2,4-toluene di-isocyanate (TD.I), and then from the view point of availability, polymerisation reactivity, voltage retention, be more preferably isophorone diisocyanate.

<<< diamine component >>>

As the diamine component belonging to (B) component materials, such as following ester ring type diamines, aromatic diamine, hetero ring type diamines, aliphatic diamine, diamines containing urea key can be listed.

As the example of ester ring type diamines, Isosorbide-5-Nitrae-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4 can be listed, 4 '-diamino-dicyclohexyl methane, 4,4 '-diamido-3,3 '-dimethyidicyclohexyl amine, isophorone diamine etc.

As the example of aromatic diamine, o-phenylenediamine can be listed, m-phenylene diamine, p-phenylenediamine (PPD), 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, Isosorbide-5-Nitrae-diamido-2-methoxybenzene, 2,5-diamido P-xylene, 1,3-diamido-4-chlorobenzene, 3,5-diaminobenzoic acid, Isosorbide-5-Nitrae-diamido-2,5-dichloro-benzenes, 4,4 '-diaminostilbene, 2-diphenylethane, 4,4 '-diamido-2,2 '-dimethyl bibenzyl, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diamido-3,3 '-dimethyl diphenylmethane, 2,2 '-diaminostilbene, 4,4 '-diaminostilbene, 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diaminobenzophenone, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzoic acid of 3,5-, 4,4 '-bis-(4-amino-benzene oxygen) bibenzyl, two [(4-amino-benzene oxygen) methyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two (4-aminophenyl) cyclohexane of 1,1-, α, α '-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene, two (4-aminophenyl) fluorenes of 9,9-, two (3-aminophenyl) HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-diamino-diphenyl amine, 2,4-diamino-diphenyl amine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diamino-anthraquinone, 1,3-diamido pyrene, 1,6-diamido pyrene, 1,8-diamido pyrene, 2,7-diamino-fluorene, two (4-aminophenyl) tetramethyl disiloxane of 1,3-, biphenylamine, 2,2 '-dimethylbenzidine, two (4-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, two (4-aminophenyl) pentane of 1,5-, two (4-aminophenyl) hexane of 1,6-, two (4-aminophenyl) heptane of 1,7-, two (4-aminophenyl) octane of 1,8-, two (4-aminophenyl) nonane of 1,9-, two (4-aminophenyl) decane of 1,10-, two (4-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, two (4-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (4-amino-benzene oxygen) decane of 1,10-, two (4-aminophenyl) propane-1,3-bis-acid esters, two (4-aminophenyl) butane-Isosorbide-5-Nitrae-two acid esters, two (4-aminophenyl) pentane-1,5-bis-acid esters, two (4-aminophenyl) hexane-1,6-bis-acid esters, two (4-aminophenyl) heptane-1,7-bis-acid esters, two (4-aminophenyl) octane-1,8-bis-acid esters, two (4-aminophenyl) nonane-1,9-bis-acid esters, two (4-aminophenyl) decane-1,10-bis-acid esters, two (4-(4-amino-benzene oxygen) phenoxy group) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-(4-amino-benzene oxygen) phenoxy group) butane, two (4-(4-amino-benzene oxygen) phenoxy group) pentane of 1,5-, two (4-(4-amino-benzene oxygen) phenoxy group) hexane of 1,6-, two (4-(4-amino-benzene oxygen) phenoxy group) heptane of 1,7-, two (4-(4-amino-benzene oxygen) phenoxy group) octane of 1,8-, two (4-(4-amino-benzene oxygen) phenoxy group) nonane of 1,9-, two (4-(4-amino-benzene oxygen) phenoxy group) decane of 1,10-etc.

As the example of aromatic-aliphatic diamines, the diamines etc. shown in following formula [DAM] can be listed.

(in formula,

Ar represents phenyl ring or naphthalene nucleus,

R ₁for the alkylidene of carbon number 1 ~ 5, and

R ₂for hydrogen atom or methyl.)

As the concrete example of aromatic-aliphatic diamines, 3-amino-benzylamine can be listed, 4-amino-benzylamine, 3-Amino-N-methyl benzylamine, 4-Amino-N-methyl benzylamine, 3-aminobenzene ethamine, 4-aminobenzene ethamine, 3-Amino-N-methyl phenyl ethylamine, 4-Amino-N-methyl phenyl ethylamine, 3-(3-aminopropyl) aniline, 4-(3-aminopropyl) aniline, 3-(3-methylaminopropyl) aniline, 4-(3-methylaminopropyl) aniline, 3-(4-aminobutyl) aniline, 4-(4-aminobutyl) aniline, 3-(4-methylaminobutyl) aniline, 4-(4-methylaminobutyl) aniline, 3-(5-Aminopentyl) aniline, 4-(5-Aminopentyl) aniline, 3-(5-methylamino amyl group) aniline, 4-(5-methylamino amyl group) aniline, 2-(the amino naphthyl of 6-) methylamine, 3-(the amino naphthyl of 6-) methylamine, 2-(the amino naphthyl of 6-) ethamine, 3-(the amino naphthyl of 6-) ethamine etc.

As the example of hetero ring type diamines, DAP, 2 can be listed, 4-diamino-pyridine, 2,4-diaminostilbenes, 3,5-triazine, 2,7-diamido dibenzofurans, 3,6-diaminocarbazole, 2,4-diamido-6-isopropyl-1,3,5-triazine, 2,5-two (4-aminophenyls)-1,3,4-oxadiazole etc.

As the example of aliphatic diamine, can 1 be listed, 2-diaminoethanes, 1, 3-diaminopropanes, 1, 4-diaminobutane, 1, 5-1,5-DAP, 1, 6-diamino hexane, 1, 7-diaminoheptane, 1, 8-diamino-octane, 1, 9-diamino nonane, 1, 10-diamino decane, 1, 3-diamido-2, 2-dimethylpropane, 1, 6-diamido-2, 5-dimethylhexane, 1, 7-diamido-2, 5-dimethyl heptane, 1, 7-diamido-4, 4-dimethyl heptane, 1, 7-diamido-3-methylheptane, 1, 9-diamido-5-methylnonane, 1, 12-diamino dodecane, 1, 18-diamido octadecane, 1, 2-two (the amino propoxyl group of 3-) ethane etc.

As the example of the diamines containing urea key, N can be listed, N '-bis-(4-aminophenethyl) urea etc.

And then, in (B) composition, as the diamine component of polyreaction will be carried out with Diisocyanate component, in the scope not damaging effect of the present invention, the diamines with vertical orientated side chain can be comprised.

In addition, the diamine component in (B) composition can containing, for example under diamines.

(in formula, m, n are respectively the integer of 1 ~ 11, and m+n is the integer of 2 ~ 12, and h is the integer of 1 ~ 3, and j is the integer of 0 ~ 3.)

By importing these diamines, the liquid crystal of the liquid crystal orientation film formed by aligning agent for liquid crystal of the present invention is used to represent that the voltage retention of element is (also referred to as VHR for improving further.) be favourable.From this liquid crystal of reduction, these diamines represent that the viewpoint of the excellent effect of the accumulated charge of element is preferred.

Further, as the diamine component in (B) composition, diamido siloxane etc. such shown in following formula can also be listed.

(in formula, m is the integer of 1 ~ 10.)

Diamine component in these (B) compositions can use a kind or combinationally use two or more respectively according to the characteristic such as liquid crystal aligning, voltage retention performance, accumulated charge when making liquid crystal orientation film.There is ratio and do not limit in mixing now.

In addition, about the molecular weight of the polyureas as (B) composition, consider gained liquid crystal aligning film strength and formed liquid crystal orientation film time workability, liquid crystal orientation film homogeneity time, the weight-average molecular weight utilizing GPC (GelPermeationChromatography, gel permeation chromatography) method to measure is preferably 5,000 ~ 1,000,000,10 are more preferably, 000 ~ 150,000.

When obtaining the polymkeric substance of above-mentioned (B) composition by the Diisocyanate component of respective raw material and the polyreaction of diamine component, known synthetic method can be used.In general, be the method that Diisocyanate component and diamine component are reacted in organic solvent.The reaction of Diisocyanate component and diamine component is from than being easier to carry out in organic solvent and the aspect that can not produce accessory substance is favourable.

As the organic solvent used in the reaction of Diisocyanate component and diamine component, as long as the organic solvent that the polyureas generated can dissolve, be just not particularly limited.

List its concrete example as follows.

As spendable organic solvent herein, DMF can be listed, DMA, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, 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.They can be used alone, also can be used in combination.And then, even the solvent of insoluble solution polyureas, in the scope that generated polyureas can not be separated out, also can be used in combination with above-mentioned solvent.

In addition, the moisture in organic solvent can become the reason hindering polyreaction, and therefore organic solvent preferably dehydrates rear use as far as possible.

When Diisocyanate component and diamine component are reacted in organic solvent, following method can be listed: stir and make diamine component be dispersed or dissolved in the solution of organic solvent, the method for directly adding Diisocyanate component or making Diisocyanate component be dispersed or dissolved in organic solvent to add; Otherwise, be dispersed or dissolved in the method for adding diamine component in the solution of organic solvent to making Diisocyanate component; Alternately add the method etc. of Diisocyanate component and diamine component, any means in these can be used.In addition, when Diisocyanate component or diamine component comprise multiple compounds, can react under the state be pre-mixed, also can react successively respectively, and then, can also be that the low-molecular weight of reacting respectively carries out hybrid reaction, thus make high molecular body.

Polymerization temperature now can select the arbitrary temp of-20 DEG C ~ 150 DEG C, is preferably the scope of-5 DEG C ~ 100 DEG C.In addition, reaction can be carried out with any concentration, the polymkeric substance obtaining high molecular is difficult to when concentration is too low, during excessive concentration, the viscosity of reactant liquor becomes too high and is difficult to uniform stirring, therefore, Diisocyanate component and the diamine component total concentration in reaction solution is preferably 1 ~ 50 quality %, is more preferably 5 ~ 30 quality %.Initial reaction stage is carried out with high concentration, can add organic solvent thereafter.

In the polyreaction of polyureas, the total mole number of Diisocyanate component is preferably 0.8 ~ 1.2 with the ratio of the total mole number of diamine component.In the same manner as common polycondensation reaction, this mol ratio is more close to 1.0, then the molecular weight of the polyureas generated becomes larger.

When reclaiming generated polyureas from the reaction solution of polyureas, reaction solution is fed into poor solvent and makes it precipitate.As the poor solvent for precipitating, methyl alcohol, acetone, hexane, butyl cellosolve, heptane, MEK, methylisobutylketone, ethanol, toluene, benzene, water etc. can be listed.Be fed into poor solvent and make it precipitate polymkeric substance after filtered and recycled, can normal pressure or decompression under carry out air drying or heat drying.In addition, when the polymkeric substance repeating 2 ~ 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 the poor solvent being selected among these more than 3 kinds, purification efficiency improves further, so preferably.

This polyureas is such as the polymkeric substance with repetitive shown in following formula [1].

(in formula [1], A ₁for divalent organic group, A ₂for divalent organic group, C ₁and C ₂for the alkyl of hydrogen atom or carbon number 1 ~ 3, can be the same or different each other.)

In above-mentioned formula [1], can be A ₁and A ₂being respectively a kind and having the polymkeric substance of identical repetitive, also can be A in addition ₁, A ₂for multiple and there is the polymkeric substance of the repetitive of different structure.

In above-mentioned formula [1], A ₁it is the group being derived from raw material Diisocyanate component.In addition, A ₂it is the group being derived from raw material diamine component.

According to optimal way of the present invention, as A ₁, be preferably derived from the group of the above-mentioned preferred Diisocyanate component enumerated.In addition, as A ₂, be preferably derived from the group of the above-mentioned preferred diamine component enumerated.

In addition, the polyureas used in the present invention is preferably obtained by diamines and diisocyanate, also can be use the compound with the reaction site of reacting with the amino of diamine component of more than 2 of a small amount of tetracarboxylic dianhydride, tetracarboxylic acid derivatives, tricarboxylic acids derivant, dicarboxylic acid derivatives etc. and so in the lump with diisocyanate and the polyureas obtained, in the scope not damaging effect of the present invention, this mode is also included within the present invention.

Herein, the compound with the reaction site of reacting with the amino of diamine component of more than 2 preferably refers to: have more than 2, the carboxylic acid derivates of the carboxylic moiety that can generate the carboxyl that can react with amido and/or its acid anhydrides, such as tetracarboxylic acid derivatives and/or its acid anhydrides, tricarboxylic acids derivant and/or its acid anhydrides, dicarboxylic acid derivatives and/or its acid anhydrides can be listed.In addition, this there are more than 2 carboxylic moiety carboxylic acid derivates and/or its acid anhydrides can list the material that carboxylic moiety defines carboxylate, carboxylic acid anhydrides, carboxylate etc., such as tetracarboxylic dianhydride, tetrabasic carboxylic acid dialkyl, tetrabasic carboxylic acid dialkyl dichloride etc. can be listed.Herein, when using the compound of the reaction site of reacting with the amino of diamine component with more than 2, the ratio of this compound and diisocyanate is preferably 99:1 ~ 0:100 with molar ratio computing.

About the consumption of this " there is the compound of the reaction site of reacting with the amino of diamine component of more than 2 ", the compound of reaction site reacted with the amino of diamine component and the total mole number of diisocyanate with more than 2 are the amount of about 0.8 ~ 1.2 relative to the ratio of the molal quantity of diamines, are preferably the amount of about 0.9 ~ 1.1.Same with common polycondensation reaction, this mol ratio is more close to 1.0, then the molecular weight of generated polymkeric substance becomes larger.

As tetracarboxylic acid derivatives and/or its acid anhydrides, such as following tetracarboxylic dianhydride can be listed.

As the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, can 1 be listed, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2-dimethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 3-dimethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic dianhydride, 2, 3, 4, 5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2, 4, 5-cyclopentanetetracarboxylic dianhydride, 3, 4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 1, 2, 3, 4-butane tetracarboxylic acid dianhydride, 1, 2, 4, 5-pentane tetracarboxylic dianhydride, dicyclo [3.3.0] octane-2, 4, 6, 8-tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-dicyclohexyl tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, cis-3, 7-dibutyl ring pungent-1, 5-diene-1, 2, 5, 6-tetracarboxylic dianhydride, three ring [4.2.1.0 ^2,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dianhydride, six ring [6.6.0.1 ^2,7.0 ^3,6.1 ^9,14.0 ^10,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydrides etc.

As aromatic tetracarboxylic acid's dianhydride, pyromellitic dianhydride, 3 can be listed, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) ether dianhydride, two (3,4-dicarboxyphenyi) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc.

Above-mentioned tetracarboxylic dianhydride can use a kind or combinationally use two or more according to characteristics such as the liquid crystal aligning of the liquid crystal orientation film that will be formed, voltage retention performance, accumulated charge.

In addition, as the tetrabasic carboxylic acid composition belonging to (B) component materials, tetrabasic carboxylic acid dialkyl, tetrabasic carboxylic acid dialkyl diester dichloride can be used.It should be noted that, when tetrabasic carboxylic acid composition contains this tetrabasic carboxylic acid dialkyl, tetrabasic carboxylic acid dialkyl dichloride, polymkeric substance becomes the poly amic acid ester belonging to polyimide precursor.Spendable tetrabasic carboxylic acid dialkyl is not particularly limited, and can list such as aliphatics tetrabasic carboxylic acid diester, aromatic tetracarboxylic acid's dialkyl etc.

Below list its concrete example.

As the concrete example of aliphatics tetrabasic carboxylic acid diester, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dialkyl can be listed, 1,2-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dialkyl, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dialkyl, 1,2,4,5-cyclopentanetetracarboxylic dialkyl, 3,4-dicarboxyl-1-cyclohexyl dialkyl succinate, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dialkyl, 1,2,3,4-butane tetracarboxylic acid dialkyl ester, 1,2,4,5-pentane tetrabasic carboxylic acid dialkyl, dicyclo [3.3.0] octane-2,4,6,8-tetrabasic carboxylic acid dialkyl, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dialkyl, 2,3,5-tricarboxylic cyclopentyl acetic acid dialkyl, pungent-1,5-diene-1,2,5, the 6-tetrabasic carboxylic acid dialkyl of cis-3,7-dibutyl ring, three ring [4.2.1.0 ^2,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dialkyl, six ring [6.6.0.1 ^2,7.0 ^3,6.1 ^9,14.0 ^10,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dialkyl, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydrides etc.

As the concrete example of aromatic tetracarboxylic acid's dialkyl, pyromellitic acid dialkyl can be listed, 3, 3 ', 4, 4 '-biphenyltetracarboxyacid acid dialkyl, 2, 2 ', 3, 3 '-biphenyltetracarboxyacid acid dialkyl, 2, 3, 3 ', 4 '-biphenyltetracarboxyacid acid dialkyl, 3, 3 ', 4, 4 '-benzophenone tetrabasic carboxylic acid dialkyl, 2, 3, 3 ', 4 '-benzophenone tetrabasic carboxylic acid dialkyl, two (3, 4-dicarboxyphenyi) ether dialkyl, two (3, 4-dicarboxyphenyi) sulfone dialkyl, 1, 2, 5, 6-naphthalene tetracarboxylic acid dialkyl, 2, 3, 6, 7-naphthalene tetracarboxylic acid dialkyl etc.

As tetrabasic carboxylic acid diester dichloride, can list and utilize known method to convert the carboxyl of above-mentioned tetrabasic carboxylic acid dialkyl to Chlorocarbonyl and the diester dichloride obtained.

As the dicarboxylic acid of ester ring type system, 1,1-cyclopropane dicarboxylic acid can be listed, 1,2-cyclopropane dicarboxylic acid, 1,1-cyclobutane dicarboxylic acid, 1,2-cyclobutane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 3,4-diphenyl-1,2-cyclobutane dicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane dicarboxylic acid, 1-cyclobutane-1,2-dicarboxylic acid, 1-cyclobutane-3,4-dicarboxylic acid, 1,1-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-(2-norborene) dicarboxylic acid, norborene-2,3-dicarboxylic acid, dicyclo [2.2.2] octane-Isosorbide-5-Nitrae-dicarboxylic acid, dicyclo [2.2.2] octane-2,3-dicarboxylic acid, 2,5-dioxa-Isosorbide-5-Nitrae-dicyclo [2.2.2] octane dicarboxylic acid, 1,3-diamantane dicarboxylic acid, 4,8-dioxa-1,3-diamantane dicarboxylic acid, 2,6-mixes spiral shell [3.3] heptane dicarboxylic acid, 1,3-diamantane two acetic acid, camphoric acid etc.

As aromatic dicarboxylic acid, phthalic acid can be listed, m-phthalic acid, terephthalic acid (TPA), oreinol dioctyl phthalate, 5-tert-butyl isophthalic acid, 5-amino isophthalic acid, 5-Hydroxy M Phthalic Acid, 2,5-dimethyl terephthalic acid, tetramethyl terephthalic acid (TPA), Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 2,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids, Isosorbide-5-Nitrae-anthracene dicarboxylic acid, Isosorbide-5-Nitrae-anthraquinone dicarboxylic acid, 2,5-diphenyl dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4 "-terphenyl dicarboxylic acid, 4,4 '-diphenyl methane dicarboxylic acid, 4,4 '-diphenylethane dicarboxylic acid, 4,4 '-diphenyl propane dicarboxylic acid, 2,2-diphenyl HFC-236fa-4,4 '-dicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acid, 4,4 '-bibenzyl dicarboxylic acid, 4,4 '-stilbene dicarboxylic acid, 4,4 '-tolane dicarboxylic acid, 4,4 '-carbonyl dibenzoic acid, 4,4 '-diphenyl sulfone dicarboxylic acid, 4,4 '-diphenyl sulfide dicarboxylic acid, to phenylenediacetic Acid, 3,3 '-to benzene dipropionic acid, 4-o-carboxy cinnamic acid, to benzene diacrylate, 3,3 '-[4,4 '-(methylene two pairs of benzene)] dipropionic acid, 4,4 '-[4,4 '-(oxygen two pairs of benzene)] dipropionic acid, 4,4 '-[4,4 '-(oxygen two pairs of benzene)] two butyric acid, (isopropylidene two pairs of benzene dioxas) two butyric acid, the dicarboxylic acid such as two (to carboxyl phenyl) dimethylsilane.

As the dicarboxylic acid comprising heterocycle, 1,5-(9-oxa-fluorenes) dicarboxylic acid, 3 can be listed, 4-furans dicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazoles-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acids, 2,5-Pyridinedicarboxylic acid, 2, dipicolimic acid 2,3,4-pyridinedicarboxylic acids, 3,5-pyridinedicarboxylic acids etc.

Above-mentioned various dicarboxylic acid can be the structures of acid ihalide or acid anhydrides.From the aspect of the orientation of maintenance liquid crystal molecule, these omega-dicarboxylic acids are particularly preferably the omega-dicarboxylic acids of the polyamide can giving linear structure.Among these, preferred use terephthalic acid (TPA), m-phthalic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl methane dicarboxylic acid, 4,4 '-diphenylethane dicarboxylic acid, 4,4 '-diphenyl propane dicarboxylic acid, 4,4 '-diphenyl HFC-236fa dicarboxylic acid, 2, two (phenyl) propane dicarboxylic acid, 4 of 2-, 4-terphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acids, 2,5-Pyridinedicarboxylic acid or their acid ihalide etc.Also there is isomeride in these compounds, also can be the potpourri comprising them.In addition, also compound of more than two kinds can be combinationally used.It should be noted that, the omega-dicarboxylic acids used in the present invention is not limited to above-mentioned exemplary compounds.

These tetracarboxylic dianhydrides, tetrabasic carboxylic acid diester, tetrabasic carboxylic acid diester dichloride, dicarboxylic acid, dicarboxylic acid halogenide etc. can use a kind or combinationally use two or more respectively according to the characteristic such as liquid crystal aligning, voltage retention performance, accumulated charge when making liquid crystal orientation film.

Tetracarboxylic dianhydride, tetrabasic carboxylic acid diester, tetrabasic carboxylic acid diester dichloride, dicarboxylic acid, dicarboxylic acid halogenide etc. are made to coexist with isocyanate compound and react with diamine component, thus when obtaining the polymkeric substance belonging to the present invention (B) composition, known synthetic method can be used.In general, be the method that tetracarboxylic dianhydride's or derivatives thereof and diamine component are reacted in organic solvent.The reaction of tetracarboxylic dianhydride and diamine component easily to be carried out and the viewpoint not producing accessory substance is favourable in organic solvent for comparing.

According to optimal way of the present invention, in polymer composition of the present invention, compounding than (quality criteria) about aforementioned (A) composition and (B) composition, when overall (total of (A) composition and (B) composition) is set to 1, (A) composition is 0.01 ~ 0.99, be more preferably 0.1 ~ 0.9, more preferably 0.2 ~ 0.5.

<< (C) 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-imidazolinone, 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 contain the composition outside above-mentioned (A), (B) and (C) 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, 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 can be listed, EF303, EF352 (TohkemproductsCorporation system), 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. make) 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-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-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, Hymecromone), 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, polarized UV rays is irradiated to substrate from particular aspects.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 liquid crystal property performance temperature) of liquid crystal liquid crystal property.Measurablely to arrive: when the film surface of film and so on, the liquid crystal liquid crystal property performance temperature of film coated surface can show the liquid crystal liquid crystal property 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 liquid crystal property 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 liquid crystal property of side chain type used.When heating-up temperature is lower than said temperature scope, there is the anisotropy amplification effect come by the torrid zone not tendency very 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 liquid crystal property 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).

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 [IV] >

[IV] operation is that the substrate (the 1st substrate) the transverse electric field driving conducting film obtained in [III] 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 '], 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 '] in, except the substrate not having transverse electric field driving conducting film in the middle use of 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].The difference of operation [I] ~ [III] and operation [I '] ~ [III '] is only with or without above-mentioned conducting film, therefore omits the explanation of operation [I '] ~ [III '].

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 side chain type polymeric membrane state before schematically showing polarizing light irradiation, (b) of Fig. 1 is the figure of the side chain type polymeric membrane state after schematically showing polarizing light irradiation, (c) of Fig. 1 is the figure of the side chain type polymeric membrane state after schematically showing heating, 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 side chain type polymeric membrane state before schematically showing polarizing light irradiation, (b) of Fig. 2 is the figure of the side chain type polymeric membrane state after schematically showing polarizing light irradiation, (c) of Fig. 2 is the figure of the side chain type polymeric membrane state after schematically showing heating, 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 side chain type polymeric membrane state before schematically showing polarizing light irradiation, (b) of Fig. 3 is the figure of the side chain type polymeric membrane state after schematically showing polarizing light irradiation, (c) of Fig. 3 is the figure of the side chain type polymeric membrane state after schematically showing heating, 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 side chain type polymeric membrane state before schematically showing polarizing light irradiation, (b) of Fig. 4 is the figure of the side chain type polymeric membrane state after schematically showing polarizing light irradiation, (c) of Fig. 4 is the figure of the side chain type polymeric membrane state after schematically showing heating, 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 making Δ A reach 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 making Δ A reach 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 making Δ A reach 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 making Δ A reach 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 making Δ A reach 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 making Δ A reach 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 making Δ A reach 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, preferentially there is the light reactions such as light fries' rearrangement in the photonasty base of among the side chain 6 that the direction parallel with ultraviolet polarization direction arranges, to have photonasty group side chain 6a.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 making Δ A reach 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 film 1 after irradiating polarized light, when making Δ A reach in the scope of 1% ~ 15% of maximum ultraviolet irradiation amount, heats and makes mesomorphic state by the ultraviolet irradiation amount of [II] operation.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 film 3 after polarizing light irradiation, when making Δ A reach in the scope of 15% ~ 70% of maximum ultraviolet irradiation amount, heats and makes mesomorphic state by the ultraviolet irradiation amount of [II] operation.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), film 5 after polarizing light irradiation, when making Δ A reach in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount, carries out heating and makes mesomorphic state by the ultraviolet irradiation amount of [II] operation.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 making Δ A reach in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount, heats the film 7 after polarizing light irradiation and makes 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.

Below, use embodiment that the present invention is described, but the present invention is not limited to this embodiment.

Embodiment

The abbreviation used in embodiment is 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).

< Diisocyanate component >

ISO1: Toluene-2,4-diisocyanate, 4-diisocyanate

ISO2: isophorone diisocyanate

< diamine component >

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

DA-1MG: two (4-amino-benzene oxygen) methane

Two (4-amino-benzene oxygen) ethane of DA-2MG:1,2-

Two (4-amino-benzene oxygen) propane of DA-3MG:1,3-

Two [2-(4-aminophenyl) ethyl] urea of BAPU:1,3-

P-PDA: p-phenylenediamine (PPD)

DDM:4,4 '-diaminodiphenyl-methane

3AMPDA:3,5-diamino-N-(pyridin-3-yl methyl) benzamide

DADPA:4,4 '-diamino-diphenylamine

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

< tetracarboxylic dianhydride >

CBDA:1,2,3,4-cyclo-butane tetrabasic carboxylic acid 1,2:3,4 dianhydride

PMDA: pyromellitic dianhydride

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

BODA: dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride

BDAM:1,2,4,5-pentane tetracarboxylic dianhydride

BDA:1,2,3,4-butane tetracarboxylic acid dianhydride

< organic solvent >

THF: tetrahydrofuran

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

BCS: butyl cellosolve

< polymerization initiator >

AIBN:2,2 '-azobis isobutyronitrile

< synthesis example 1: methacrylate polymers solution >

MA1 (2.99g, 9.0mmol) and MA2 (1.83g, 6.0mmol) is dissolved in THF (44.57g), with membrane pump carry out degassed after, add AIBN (0.12g, 0.5mmol) and also again carry out degassed.Thereafter with 50 DEG C of reactions 30 hours, the polymer solution of methacrylate is obtained.This polymer solution is dropped to diethyl ether (500ml), filter gained sediment.This sediment diethyl ether is cleaned, in the baking oven of 40 DEG C, carries out drying under reduced pressure, obtain methacrylate polymers powder.

In gained powder 4.0g, add NMP36.0g, at room temperature stir 3 hours.Obtain the methacrylate polymers solution (M1) that solid component concentration is 10.0wt%.The polymkeric substance stirring finish time dissolves completely.

< synthesis example 2: polyureas >

As diamine component, the Me-4APhA of 1.50g is dissolved in NMP12.77g, adds the 1.68gISO1 as Diisocyanate component under room temperature wherein, with 60 degree of reactions 18 hours, thus the concentration obtaining polyureas (PU-1) was the solution of 20wt%.

< synthesis example 3 ~ 10: polyureas >

According to the composition shown in table 1, use the method identical with above-mentioned synthesis example 2 (polyureas), synthesized the polyureas solution of synthesis example 3 ~ 10.

< synthesis example 11: polyamic acid >

Use CBDA1.88g as tetracarboxylic dianhydride's composition, use BAPU2.98g as diamine component, with room temperature reaction 18 hours in 19.4gNMP, thus the concentration obtaining polyamic acid (PAA-1) is the solution of 20wt%.

table 1:

[table 1]

< synthesis example 12: polyureas polyamic acid >

As diamine component, the DADPA of 1.99g is dissolved in NMP16.55g, at room temperature add the 1.55gISO2 as Diisocyanate component wherein, stir after 1 hour, the PMDA of 0.59g is added as acid dianhydride component, and then at room temperature react 6 hours, thus the concentration obtaining polyureas amic acid (PUA-1) is the solution of 20wt%.

< synthesis example 13 ~ 21: polyureas polyamic acid >

According to the composition shown in table 2, use the method identical with above-mentioned polyureas amic acid synthesis example 12, synthesized synthesis example 13 ~ polyureas amic acid solution.

table 2:

[table 2]

(embodiment 1)

In methacrylate polymers solution (M1) 3.0g utilizing above-mentioned synthesis example 1 to obtain, add polyureas solution (PU-1) 3.0g, at room temperature stir 1 hour.And then BCS4.0g and NMP5.0g is added in this solution, at room temperature stir 1 hour, obtain the polymer solution (A1) that solid component concentration is 6.0wt%.This polymer solution directly becomes the aligning agent for liquid crystal for the formation of liquid crystal orientation film.

(embodiment 2 ~ 9, comparative example 1 ~ 2)

According to the composition shown in table 3, use the method identical with embodiment 1, obtain the polymer solution of embodiment 2 ~ 9.In addition, comparative example 1 ~ 2 also utilizes identical method to be prepared.

table 3:

[table 3]

(embodiment 10)

In methacrylate polymers solution (M1) 3.0g utilizing above-mentioned methacrylic synthesis example 1 to obtain, add polyureas amic acid solution (PUA-1) 3.5g, at room temperature stir 1 hour.And then BCS6.7g and NMP3.5g is added in this solution, at room temperature stir 1 hour, thus obtain the polymer solution (A10) that solid component concentration is 6.0wt%.This polymer solution directly becomes the aligning agent for liquid crystal for the formation of liquid crystal orientation film.

(embodiment 11 ~ 19)

According to the composition shown in table 4, use the method identical with embodiment 10, obtain the polymer solution of embodiment 11 ~ 20.

table 4:

[table 4]

[making of liquid crystal cells]

Use the aligning agent for liquid crystal (A1) obtained in embodiment 1, carry out the making of liquid crystal cells according to the following step illustrated.Substrate is of a size of 30mm × 40mm and thickness is the glass substrate of 0.7mm, uses the substrate being configured with 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 its 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 embodiment 1 (A1) 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, by across polarization plates with 5mJ/cm ²after coated surface being irradiated to the ultraviolet of 313nm, heat 10 minutes with the hot plates of 140 DEG C, obtain the substrate being with liquid crystal orientation film.In addition, as subtend substrate, to not forming electrode and the glass substrate with the column spacer being highly 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.

For the aligning agent for liquid crystal obtained in embodiment 2 ~ 19 (A2 ~ A19), the method identical with A1 is also used to make liquid crystal cells.

(voltage retention (VHR) evaluation)

In the evaluation of VHR, gained liquid crystal cells is applied to the 5V voltage of 60 μ s at the temperature of 70 DEG C, measure the voltage after 1667ms, which kind of degree voltage can be remained and calculate as voltage retention.

It should be noted that, the mensuration of voltage retention employs the voltage retention determinator VHR-1 of TOYOCorporation.

Use the aligning agent for liquid crystal (B1) obtained in comparative example 1, carry out the manufacture of liquid crystal cells in the same manner as in time using above-mentioned aligning agent for liquid crystal (A1), utilize identical method evaluation VHR.

Result is as shown in following table 5 and table 6.

table 5:

[table 5]

table 6:

[table 6]

As shown in table 5 and table 6 can be clear and definite: identical with (A) composition and not containing (B) composition comparative example 1 compared with, the voltage retention (VHR) based on embodiments of the invention 1 ~ 19 uprises.

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. a polymer composition, it contains:

(B) polyureas and

(C) organic solvent.

2. composition according to claim 1, wherein, (A) composition has the photonasty side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.

3. composition according to claim 1 and 2, wherein, the polyureas as (B) composition carries out polyreaction by making Diisocyanate component and diamine component and obtains.

4. composition according to claim 1 and 2, wherein, as the polyureas of (B) composition by making Diisocyanate component, there is the carboxylic acid derivates of more than 2 carboxylic moiety and/or its acid anhydrides and diamine component carry out polyreaction and obtain.

5. the composition according to claim 3 or 4, wherein, Diisocyanate component is aromatic diisocyanate and/or aliphatic diisocyanate.

6. the composition according to any one of Claims 1 to 5, 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;

7. the composition according to any one of Claims 1 to 5, 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.

8. the composition according to any one of Claims 1 to 5, 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 m2 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.

9. the composition according to any one of Claims 1 to 5, 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.

10. the composition according to any one of Claims 1 to 5, wherein, (A) composition has following formula (16) or the photonasty side chain shown in (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.

11. compositions according to any one of Claims 1 to 5, wherein, (A) composition has following formula (18) or the photonasty side chain shown in (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; M1, m2 represent the integer of 1 ~ 3;

12. compositions according to any one of Claims 1 to 5, 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.

13. compositions according to any one of claim 1 ~ 12, 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;

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;

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

14. 1 kinds of manufacture methods that there is the driving liquid crystal of transverse electric field and represent 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:

[I] composition according to any one of claim 1 ~ 13 is coated on there is transverse electric field driving conducting film substrate on and form the operation of film;

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

15. 1 kinds of substrates having the driving liquid crystal of transverse electric field and represent element liquid crystal orientation film, it is manufactured by method according to claim 14.

16. 1 kinds of driving liquid crystal of transverse electric field represent element, and it has substrate according to claim 15.

17. 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 15 i.e. operation of the 1st substrate;

[IV] with the liquid crystal orientation film of described 1st substrate and the 2nd substrate 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 '].

18. 1 kinds of driving liquid crystal of transverse electric field represent element, and it is manufactured by method according to claim 17.