CN105593308B

CN105593308B - Polymer composition and the driving liquid crystal of transverse electric field indicate element liquid crystal orientation film

Info

Publication number: CN105593308B
Application number: CN201480054146.2A
Authority: CN
Inventors: 名木达哉; 南悟志; 芦泽亮一; 万代淳彦; 根木隆之; 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: 2013-07-31
Filing date: 2014-07-31
Publication date: 2019-07-19
Anticipated expiration: 2034-07-31
Also published as: TW201520313A; KR102277348B1; KR20160037966A; JPWO2015016301A1; WO2015016301A1; JP6872315B2; CN105593308A; TWI707024B

Abstract

Element is indicated problem of the present invention is that providing and having been assigned the driving liquid crystal of the transverse electric field excellent in reliability such as tropism control ability, image retention speciality and voltage retention with high efficiency.The present invention solves the above subject by the polymer composition containing (A) side chain type macromolecule and (B) organic solvent, (A) the side chain type macromolecule is the photonasty side chain type macromolecule that liquid crystal liquid crystal property is shown within the scope of specific temperature, the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, and the upper limit value for showing the temperature range of liquid crystal liquid crystal property is 200 DEG C or more.

Description

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

Technical field

Indicate that element is taken with liquid crystal the present invention relates to novel polymer compositions, using its driving liquid crystal of transverse electric field To film and the manufacturing method of the substrate with the alignment films.In turn, the present invention relates to excellent, electric for manufacturing image retention speciality The liquid crystal for pressing conservation rate etc. excellent in reliability indicates the new method of element.

Background technique

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

That is, liquid crystal orientation film be liquid crystal indicate element component parts, be formed in clamping liquid crystal substrate and liquid crystal The surface of contact, undertaking makes liquid crystal be orientated this effect along specific direction between the substrate.Also, for liquid crystal orientation film For, other than making liquid crystal be orientated this effect along specific directions such as the directions for being for example parallel to substrate, also require sometimes Liquid crystal pretilt angle is carried out to control this effect.The ability of the control liquid crystal aligning of this liquid crystal orientation film (is hereinafter referred to as orientated Control ability.) be endowed and carrying out orientation process to the organic film for constituting liquid crystal orientation film.

As the method for orientation treatment of the liquid crystal orientation film for assigning tropism control ability, it has been known that there is brushings all the time Method.Brushing method refers to following method: for the organic film of polyvinyl alcohol, polyamide, polyimides on substrate etc., using cotton The cloth of flower, nylon, polyester etc. is along constant direction friction (brushing) its surface, to make liquid crystal along frictional direction (brushing side To) orientation.The brushing method can easily realize more stable liquid crystal aligning state, therefore can be used in previous liquid crystal expression The manufacturing process of element.It is main to select the reliabilities such as heat resistance, electricity special also, as organic film used in liquid crystal orientation film The excellent polyimides system organic film of property.

However, the brushing method to rub to the surface of the liquid crystal orientation film comprising polyimides etc. there are dust, generate The problem of electrostatic.In addition, due to electrode or liquid crystal drive on the high-definition of liquid crystal expression element in recent years, corresponding substrate With switching active element caused by bumps, therefore, it is impossible to the surface for the liquid crystal orientation film that equably rubbed with cloth, cannot achieve Even liquid crystal aligning.

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

Optical alignment method has various methods, is constituting the organic of liquid crystal orientation film by rectilinearly polarized light or collimated light Anisotropy is formed in film, is orientated liquid crystal according to the anisotropy.

As main optical alignment method, it is known to the optical alignment method of breakdown type.For example, it is purple to irradiate polarization to polyimide film Outside line brings it about anisotropic decomposition using the polarization direction dependence of the ultraviolet radiation absorption of molecular structure.Also, it is logical Crossing undecomposed and remaining polyimides is orientated liquid crystal (referring for example to patent document 1.).

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

As above-mentioned example, using optical alignment method to liquid crystal orientation film carry out orientation process method in, without into Row brushing does not have to worry dust, generates electrostatic.Also, the substrate of element is indicated even if having indent and convex liquid crystal for surface It can implement orientation process, to become the method for orientation treatment for being suitable for the liquid crystal orientation film of industrial manufacture process.

Existing technical literature

Patent document

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

Non-patent literature

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

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

Summary of the invention

Problems to be solved by the invention

As described above, with the method for orientation treatment that element is indicated as liquid crystal and carry out the brushing of industrial utilization all the time Method is compared, and optical alignment method is not necessarily to this process of brushing process, therefore has clear advantage.Also, it is taken with caused by brushing The brushing method substantially stationary to control ability is compared, and optical alignment method can change the exposure of polarised light to control tropism control energy Power.However, in the case where optical alignment method wants to realize tropism control ability identical with degree when brushing method is utilized, sometimes It needs a large amount of polarizing light irradiation amount or cannot achieve stable liquid crystal aligning.

For example, needing to irradiate polyimide film 60 minutes in the breakdown type optical alignment method described in above patent document 1 The ultraviolet light etc. that issues of the high-pressure sodium lamp by power 500W, need for a long time and a large amount of ultraviolet light irradiation.In addition, in dimerization In the case where type, photoisomerization type optical alignment method, it is sometimes desirable to a large amount of ultraviolet lights irradiation of number J (joule)~tens of J or so.Into And in the case where photo-crosslinking type, photoisomerization type optical alignment method, the thermal stability of the orientation of liquid crystal, photostability are poor, therefore When liquid crystal, which is made, indicates element, there are problems that occurring to be orientated bad, expression ghost.Especially, the driving liquid of transverse electric field Crystalline substance indicate element in, liquid crystal molecule is switched in face, thus be easy to happen the liquid crystal aligning after liquid crystal drive offset, by Indicate that ghost is considered apparent project caused by AC driving.

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

The object of the present invention is to provide being endowed with high efficiency, tropism control ability, image retention speciality be excellent, voltage is kept Rate etc. is excellent in reliability, indicates the substrate of element liquid crystal orientation film with the driving liquid crystal of transverse electric field and has the base The driving liquid crystal of the transverse electric field of plate indicates element.

The solution to the problem

The inventors of the present invention have made intensive studies to realize the above subject, as a result, it has been found that following invention.

<1>the driving liquid crystal of a kind of polymer composition, especially transverse electric field indicates that element is manufactured with liquid crystal orientation film With polymer composition, contain (A) side chain type macromolecule and (B) organic solvent, (A) the side chain type macromolecule is specific Within the temperature range of show the photonasty side chain type macromolecule of liquid crystal liquid crystal property, the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, the upper limit value for showing the temperature range of liquid crystal liquid crystal property is 200 DEG C or more.

<2>the driving liquid crystal of a kind of polymer composition, especially transverse electric field indicates that element is manufactured with liquid crystal orientation film With polymer composition, contain (A) side chain type macromolecule and (B) organic solvent, (A) the side chain type macromolecule is specific Within the temperature range of show the photonasty side chain type macromolecule of liquid crystal liquid crystal property, the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, the upper limit value for showing the temperature range of liquid crystal liquid crystal property is 220 DEG C or more.

<3>in above-mentioned<1>or<2>, (A) ingredient, which can have, can occur photo-crosslinking, photoisomerization or light fries' rearrangement Photonasty side chain.

<4>in any one of above-mentioned<1>~<3>, (A) ingredient be can have selected from the group being made of following formula (1)~(6) In any photonasty side chain.

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

S is the alkylidene of carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；

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

Y₁In the ester ring type hydrocarbon for indicating phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 Ring, or identical or different 2~6 ring in these substituent groups is by group made of binding groups B bonding, key Together in their hydrogen atom each independently optionally by-COOR₀(in formula, R₀Indicate the alkyl of hydrogen atom or carbon number 1~5) ,- NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；

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

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

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

Cou indicates Coumarin-6-base or coumarin-7-base, be bonded to their hydrogen atom each independently optionally by- NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；

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

Q3 is 0 or 1；

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

When the quantity of P is 2, P is optionally same or different to each other；

When the quantity of Q is 2, Q is optionally same or different to each other；

L1 is 0 or 1；

The integer that l2 is 0~2；

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

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

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

<5>in above-mentioned<4>, when the end of formula (1)~(6) the photonasty side chain as (A) ingredient is-COOH, the side Chain can have 2 or more the ester ring type hydrocarbons for being selected from the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 In ring structure,

When the end of the side chain is the group in addition to-COOH, the side chain can have 3 or more selected from 1 valence phenyl ring, Naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 ester ring type hydrocarbon in ring structure.

<6>in any one of above-mentioned<1>~<3>, (A) ingredient can have to be selected from and be made of following formula (7)~(10) Any photonasty side chain in group.

In formula, A, B, D, Y₁、X、Y₂There is definition same as described above with R；

L indicates 1~12 integer；

M indicates that 0~2 integer, m1, m2 indicate 1~3 integer；

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

<7>in any one of above-mentioned<1>~<3>, (A) ingredient can have to be selected from and be made of following formula (11)~(13) Any photonasty side chain in group.

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

<8>in any one of above-mentioned<1>~<3>, (A) ingredient can have photonasty shown in following formula (14) or (15) Side chain.

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

<9>in any one of above-mentioned<1>~<3>, (A) ingredient can have photonasty shown in following formula (16) or (17) Side chain.

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

<10>in any one of above-mentioned<1>~<3>, (A) ingredient can have photosensitive shown in following formula (18) or (19) Property side chain.

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

R₁Indicate hydrogen atom ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, carbon number 1~5 alkyl or The alkoxy of carbon number 1~5.

<11>in any one of above-mentioned<1>~<3>, (A) ingredient can have photonasty side chain shown in following formula (20).

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

<12>in any one of above-mentioned<1>~<11>, (A) ingredient can have to be selected from and be made of following formula (21)~(31) Group in any liquid crystal liquid crystal property side chain.

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

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

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

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

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

R₂Indicate hydrogen atom ,-NO₂,-CN, halogen group, the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and The ester ring type hydrocarbon and alkyl or alkoxy of carbon number 5~8；

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

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

Any combination object of above-mentioned<1>~<12>is coated on the substrate with transverse electric field driving conductive film by [I] And the process for forming film；

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

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

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

<15>a kind of driving liquid crystal of transverse electric field indicates element, the substrate with above-mentioned<14>.

<16>a kind of driving liquid crystal of transverse electric field indicates the manufacturing method of element, is obtained and having following process The liquid crystal indicates element:

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

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

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

The process [I '], [II '] and [III '] are as follows:

[I '] coated polymeric composition and the process that forms film, described polymer composition on the 2nd substrate contains (A) side chain type macromolecule and (B) organic solvent, (A) the side chain type macromolecule is to show liquid within the scope of specific temperature The photonasty side chain type macromolecule of crystalline substance, the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, shows liquid crystal Property temperature range upper limit value be 200 DEG C or more；

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

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

<17>a kind of driving liquid crystal of transverse electric field indicates the manufacturing method of element, is obtained and having following process The liquid crystal indicates element:

The process [I '], [II '] and [III '] are as follows:

[I '] coated polymeric composition and the process that forms film, described polymer composition on the 2nd substrate contains (A) side chain type macromolecule and (B) organic solvent, (A) the side chain type macromolecule is to show liquid within the scope of specific temperature The photonasty side chain type macromolecule of crystalline substance, the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, shows liquid crystal Property temperature range upper limit value be 220 DEG C or more；

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

<18>a kind of driving liquid crystal of transverse electric field indicates element, is manufactured by above-mentioned<16>or<17>.

The effect of invention

It is endowed that tropism control ability, image retention speciality be excellent, voltage retention with high efficiency by means of the invention it is possible to provide Etc. substrate excellent in reliability, with the driving liquid crystal expression element liquid crystal orientation film of transverse electric field and there is the substrate The driving liquid crystal of transverse electric field indicate element.

The driving liquid crystal of transverse electric field manufactured by means of the present invention indicates that element is efficiently imparted orientation Control ability, therefore characterization will not be damaged long-time Continuous Drive.

Detailed description of the invention

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

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

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

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

Specific embodiment

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

Polymer composition used in the manufacturing method of the present invention is with 150 DEG C or more within the range having a lower limit of and the upper limit is 220 DEG C or more temperature within the scope of can show photonasty side chain type macromolecule (the hereinafter also referred to as side chain type high score of liquid crystal liquid crystal property Son), it the use of film obtained from foregoing polymer compositions is with the photonasty side chain type high score that can show liquid crystal liquid crystal property The film of son.The film carries out orientation process by polarizing light irradiation without carrying out brushing processing.Also, carrying out polarised light After irradiation, via the process for heating the side chain type polymeric membrane, thus (following as the film for having been assigned tropism control ability Also referred to as liquid crystal orientation film).At this point, becoming driving force, liquid crystal liquid crystal property by the small anisotropy that polarizing light irradiation is shown Side chain type macromolecule itself due to self assembly effectively reorientation.As a result, it is possible to realize height as liquid crystal orientation film The orientation process of effect obtains the liquid crystal orientation film for having been assigned highly oriented control ability.In turn, due to adding after polarizing light irradiation Heat such as carries out at a high temperature of 150 DEG C or more, therefore can obtain voltage retention at the liquid crystal orientation film excellent in reliability.

Hereinafter, detailed description of embodiments of the present invention for needle.

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

Polymer composition containing (A) side chain type macromolecule and (B) organic solvent is coated on transverse electric field by [I] The process for forming film on the substrate of driving conductive film, (A) the side chain type macromolecule is within the scope of specific temperature The photonasty side chain type macromolecule for showing liquid crystal liquid crystal property, the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, table The upper limit value for revealing the temperature range of liquid crystal liquid crystal property is 200 DEG C or more；

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

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

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

For the 2nd substrate, replace that there is laterally electricity in addition to using the substrate without transverse electric field driving conductive film Except the substrate of field driving conductive film, transverse electric field drive (is not had due to using by using above-mentioned operation [I]~[III] The substrate of conductive film is employed, therefore for convenience, in this application sometimes referred to simply as process [I ']~[III ']), it can obtain The 2nd substrate with the liquid crystal orientation film for having been assigned tropism control ability.

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

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

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

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

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

Furthermore, it is contemplated that being suitable for reflective liquid crystal indicates element, the opaque substrate such as silicon wafer also can be used.

There is substrate transverse electric field driving to use conductive film.

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

In addition, in the case where reflective liquid crystal indicates element, as conductive film, the material of the meeting reflected light such as aluminium can be enumerated Material etc., but it is not limited to these.

Conventionally known gimmick can be used in the method that conductive film is formed on substrate.

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

The polymer composition used in the manufacturing method of the present invention contains: (A) is showed within the scope of specific temperature The photonasty side chain type macromolecule of liquid crystal liquid crystal property out, and the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, performance The aforementioned side chain type macromolecule that the upper limit value of the temperature range of liquid crystal liquid crystal property is 200 DEG C or more out；And (B) organic solvent.

<<(A) side chain type macromolecule>>

(A) ingredient is the photonasty side chain type macromolecule that liquid crystal liquid crystal property is shown within the scope of specific temperature, and is shown The lower limit value of the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, the upper limit value for the temperature range for showing liquid crystal liquid crystal property is 200 DEG C or more Aforementioned side chain type macromolecule.Alternatively, (A) ingredient is the photonasty side chain type for showing liquid crystal liquid crystal property within the scope of specific temperature Macromolecule, show the temperature range of liquid crystal liquid crystal property lower limit value be 150 DEG C or more, show liquid crystal liquid crystal property temperature range the upper limit The aforementioned side chain type macromolecule that value is 220 DEG C or more.Preferably, (A) ingredient is to show liquid within the scope of specific temperature The photonasty side chain type macromolecule of crystalline substance, the lower limit value for showing the temperature range of liquid crystal liquid crystal property are 160 DEG C or more, show liquid crystal Property the upper limit value of temperature range be 220 DEG C or more of aforementioned side chain type macromolecule.

(A) side chain type macromolecule by react under the light of the wave-length coverage of 250nm~400nm and 150 DEG C~ Liquid crystal liquid crystal property is shown within the temperature range of 300 DEG C.

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

(A) side chain type macromolecule is in order to show liquid crystal liquid crystal property within the temperature range of 150 DEG C~300 DEG C and it is preferred that have liquid crystal Former base group.

(A) lower limit value of the high molecular temperature range for showing liquid crystal liquid crystal property of ingredient, that is, photonasty side chain type is preferably 155 DEG C or more, more preferably 160 DEG C or more, in addition, the upper limit value for showing the temperature range of liquid crystal liquid crystal property be preferably 200 DEG C or more, More preferably 220 DEG C or more, further preferably 250 DEG C or more, which can also be more than 300 DEG C.

In the present invention, as described above, it is 150 DEG C or more and its upper limit that (A) ingredient, that is, photosensitive polymer, which is in lower limit value, The ingredient of liquid crystal liquid crystal property is shown within the scope of the temperature that value is 200 DEG C or more, this macromolecule more preferably has 2 in the side chain The structure of the above ring structure.Alternatively, in the present invention, as described above, it is 150 that (A) ingredient, that is, photosensitive polymer, which is in lower limit value, DEG C or more and its upper limit value be the ingredient that liquid crystal liquid crystal property is shown within the scope of 220 DEG C or more of temperature, this macromolecule is more preferably In the side chain with the structure of 2 or more ring structures.

(A) the high molecular main chain of side chain type, which has been bonded, has photosensitive side chain, and induction can be crosslinked in light Reaction, isomerization reaction or light fries' rearrangement.It is not particularly limited with photosensitive side-chain structure, is contemplated to be induction in light And crosslink the structure of reaction or light fries' rearrangement, it more desirable to be the structure for crosslinking reaction.At this point, if exposed to The external stresses such as heat can also keep the tropism control ability realized steadily in the long term.It can show the photonasty of liquid crystal liquid crystal property As long as the high molecular structure of side chain type meets this characteristic, there is no particular limitation, there is upright and outspoken liquid in preferred side-chain structure Brilliant ultimate constituent.At this point, stable liquid crystal aligning can be obtained when liquid crystal orientation film is made in the side chain type macromolecule.

The high molecular structure can for example be made such as flowering structure: with main chain and the side chain for being bonded to it, side chain tool There are the liquid crystal ultimate constituents such as xenyl, terphenyl, phenylcyclohexyl, phenylamino benzoic acid ester group, azobenzene and is bonded to front end The induction light in portion and the photonasty group that reaction, isomerization reaction can be crosslinked；It, should with main chain and the side chain for being bonded to it It is both liquid crystal ultimate constituent or the phenylamino benzoic acid ester group that light Fries rearrangement can occur that side chain, which has,.

More specific example as the high molecular structure of photonasty side chain type that can show liquid crystal liquid crystal property, it is however preferred to have such as The structure of lower main chain and following side chain, the main chain is by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, horse Come the radically polymerizable groups such as acid esters, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene group With at least one kind of composition in the group of siloxanes composition, the side chain includes at least one kind of in following formula (1)~(6).

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

Q3 is 0 or 1；

When the quantity of P is 2, P is optionally same or different to each other；

When the quantity of Q is 2, Q is optionally same or different to each other；

L1 is 0 or 1；

The integer that l2 is 0~2；

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

More preferable mode according to the present invention, when the end of previously described formula (1)~(6) photonasty side chain is-COOH, the side Chain can have 2 or more the ester ring type hydrocarbons for being selected from the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 In ring structure, when the end of the side chain is the group in addition to-COOH, the side chain can have 3 or more be selected from 1 valence benzene Ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 ester ring type hydrocarbon in ring structure.

Herein, the end of formula (1)~(6) photonasty side chain refers to: for example, the side chain in formula (1), (3), (5) and (6) In the case where be Y1 group, " end is-COOH " refers to: having as the selectable ring of Y1 group in its any position and replaces Base-COOH.In addition, being R group in the case where the side chain of formula (2), " end is-COOH " refers to: R base selects hydroxyl.

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

L indicates 1~12 integer；

M indicates that 0~2 integer, m1, m2 indicate 1~3 integer；

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The above-mentioned photonasty side chain type macromolecule that can show liquid crystal liquid crystal property can be by with above-mentioned photonasty side chain Photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer, which are polymerize, to be obtained.

[photoreactivity side chain monomer]

Photoreactivity side chain monomer refers to following monomer: when forming macromolecule, can be formed in high molecular side chain portion Position has the macromolecule of photonasty side chain.

As photoreactive group possessed by side chain, preferably following structures and its derivative.

More specific example as photoreactivity side chain monomer, it is however preferred to have following polymerizable group and following photonasty side The structure of chain: the polymerizable group by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, The radically polymerizable groups such as alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene group and silicon oxygen At least one kind of composition in the group of alkane composition；And the photonasty side chain is comprising at least one kind of in above-mentioned formula (1)~(6), it is excellent Be selected as example comprising in above-mentioned formula (7)~(10) at least one kind of photonasty side chain, comprising in above-mentioned formula (11)~(13) extremely It is photonasty side chain shown in few a kind of photonasty side chain, above-mentioned formula (14) or (15), photosensitive shown in above-mentioned formula (16) or (17) Photonasty side chain shown in property side chain, above-mentioned formula (18) or (19), photonasty side chain shown in above-mentioned formula (20).

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

In formula, R indicates hydrogen atom or methyl；The alkylidene of S expression carbon number 2~10；R¹⁰Indicate Br or CN；S indicates carbon number 2 ~10 alkylidene；U indicates 0 or 1；And Py indicates 2- pyridyl group, 3- pyridyl group or 4- pyridyl group.In addition, v indicates 1 or 2.

[liquid crystal liquid crystal property side chain monomer]

Liquid crystal liquid crystal property side chain monomer refers to following monomer: the high molecular form from the monomer reveals liquid crystal liquid crystal property, the macromolecule Mesogenic group is capable of forming at side chain position.

As the had mesogenic group of side chain, being also possible to biphenyl, phenol benzoate etc. individually becomes liquid crystal original structure Group, be also possible to the group that such ground such as benzoic acid side chain carries out hydrogen bonding each other and becomes mesogen structure.As side Mesogenic group possessed by chain, preferably following structures.

More specific example as liquid crystal liquid crystal property side chain monomer, it is however preferred to have the knot of following polymerizable group and following side chain Structure, the polymerizable group is by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, α-methylene The radically polymerizable groups such as base-gamma-butyrolacton, styrene, vinyl, maleimide, norbornene group and siloxanes composition Group at least one kind of composition, the side chain include above-mentioned formula (21)~(31) in it is at least one kind of.

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

As other monomers, can enumerate for example can the industrial monomer for being able to carry out Raolical polymerizable obtained.

As the concrete example of other monomers, unsaturated carboxylic acid, acrylate compounds, methacrylated can be enumerated Close object, maleimide compound, acrylonitrile, maleic anhydride, distyryl compound and vinyl compound etc..

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

As acrylate compounds, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, third can be enumerated Olefin(e) acid benzyl ester, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, acrylic acid 2,2,2- trifluoro second Ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2- methoxy acrylate, methoxy triethylene Acrylate, acrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxybutyl, acrylic acid 2- methyl -2- Adamantane esters, acrylic acid 2- propyl -2- adamantane esters, acrylic acid 8- methyl -8- tricyclodecyl and acrylic acid 8- second Base -8- tricyclodecyl etc..

As methacrylate compound, such as methyl methacrylate, ethyl methacrylate, methyl can be enumerated Isopropyl acrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthrylmethyl, Phenyl methacrylate, methacrylic acid 2,2,2- trifluoro ethyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, first Base isobornyl acrylate, methacrylic acid 2- methoxy acrylate, methoxy triethylene methacrylate, methacrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxybutyl, methacrylic acid 2- methyl -2- gold Rigid Arrcostab, methacrylic acid 2- propyl -2- adamantane esters, methacrylic acid 8- methyl -8- tricyclodecyl and methyl-prop Olefin(e) acid 8- ethyl -8- tricyclodecyl etc..Also (methyl) glycidyl acrylate, (methyl) acrylic acid (3- methyl-can be used 3- oxetanylmethoxy) (the first with cyclic ether group such as methyl esters and (methyl) acrylic acid (3- ethyl -3- oxetanylmethoxy) methyl esters Base) acrylate compounds.

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

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

As maleimide compound, such as maleimide, N- methylmaleimido, N- phenyl horse can be enumerated Come acid imide and N- N-cyclohexylmaleimide etc..

For the high molecular manufacturing method of side chain type of present embodiment, it is not particularly limited, can use and industrially answer Universal method.Specifically, can be by the way that the sun of the vinyl of liquid crystal liquid crystal property side chain monomer, photoreactivity side chain monomer be utilized Ionic polymerization, free radical polymerization, anionic polymerisation manufacture.Among these, from viewpoints such as reaction controlling easness, especially Preferably free radical polymerization.

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

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

As long as radical photopolymerization initiator causes the compound of free radical polymerization because of light irradiation, just do not limit especially It is fixed.As this radical photopolymerization initiator, benzophenone, Michler's keton, 4,4 '-bis- (lignocaine) hexichol first can be enumerated Ketone, xanthone, thio xanthone, isopropyl xanthone, 2,4- diethyl sulfide are for xanthone, 2- ethyl hydrazine, benzene It is ethyl ketone, 2- hydroxy-2-methyl propiophenone, 2- hydroxy-2-methyl -4 '-cumene acetone, 1- hydroxycyclohexylphenylketone, different Propyl benzoin ether, isobutyl benzoin ether, 2,2- diethoxy acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, camphor Quinone, benzanthrone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino propyl- 1- ketone, 2- benzyl-2- dimethylamino-1- (4- Morphlinophenyl) -1- butanone, 4- dimethyl ethyl aminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, 4,4 '-two (tert-butyls Peroxy carbonyl) benzophenone, 3,4,4 '-three (t-butylperoxycarbonyl) benzophenone, 2,4,6- trimethylbenzoyl Diphenyl phosphine oxide, bis- (trichloromethyl) s-triazine of 2- (4 '-methoxyl-styrene) -4,6-, 2- (3 ', 4 '-dimethoxy benzenes Vinyl) bis- (trichloromethyl) s-triazine of -4,6-, 2- (2 ', 4 '-dimethoxy-styryl) -4,6- bis- (trichloromethyls) be equal Triazine, bis- (trichloromethyl) s-triazine of 2- (2 '-methoxyl-styrene) -4,6-, 2- (4 '-amyl phenyl ether vinyl) -4,6- Bis- (trichloromethyl) s-triazine, 4- [p- N, N- bis- (ethoxy carbonyl methyl)] -2,6- two (trichloromethyl) s-triazine, 1,3- Bis- (trichloromethyl) -5- (2 '-chlorphenyl) s-triazine, bis- (trichloromethyl) -5- (4 '-methoxyphenyl) s-triazine, 2- of 1,3- (to dimethylaminostyryl) benzoxazoles, 2- (to dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3, It is 3 '-carbonyls bis- (7- lignocaine cumarins), -4,4 ', 5,5 '-tetraphenyl -1,2 ' of 2- (Chloro-O-Phenyl)-bisglyoxaline, 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-four (4- carboethoxyphenyl) -1,2 '-bisglyoxalines, 2,2 '-bis- (2,4 dichloro benzene bases) - 4,4 ', 5,5 '-tetraphenyls -1,2 '-bisglyoxaline, 2,2 ' bis- (2,4- dibromo phenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-connection miaows Azoles, 2,2 '-bis- (2,4,6- trichlorophenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines, 3- (2- methyl -2- dimethylamino Propiono) carbazole, 3,6- bis- (2- methyl -2- morpholino propiono) -9- dodecyl carbazoles, 1- hydroxycyclohexylphenyl Ketone, bis- (5-2,4- cyclopentadiene -1- bases)-bis- (the fluoro- 3- of 2,6- bis- (1H- pyrroles -1- base)-phenyl) titaniums, 3,3 ', 4,4 '-four (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary hexyl peroxy carbonyl) benzophenone, 3,3 '-two (first Epoxide carbonyl) -4,4 '-two (t-butylperoxycarbonyl) benzophenone, 3,4 '-two (methoxycarbonyl) -4,3 '-two (tertiary fourths Base peroxy carbonyl) 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-1,3- benzothiazole -2 (3H)-subunit) -1- (2- benzoyl) ethyl ketone etc..These compounds can be used alone, and can also mix two or more make With.

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

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

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

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

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

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

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

[recycling of polymer]

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

About the high molecular molecular weight of (A) side chain type of the invention, it is contemplated that when gained painting film strength, formation film When workability and the uniformity of film, utilize GPC (Gel Permeation Chromatography, gel permeation chromatography) The weight average molecular weight of method measurement is preferably 2000~1000000, more preferably 5000~200000.

[preparation of polymer composition]

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

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

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

<<(B) organic solvent>>

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

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

Polymer composition used in the present invention can contain the ingredient except above-mentioned (A) and (B) ingredient.As its example Son can enumerate the solvent or compound for improving film thickness uniformity, surface smoothness in coated polymeric composition, improve liquid Brilliant alignment films and the compound of the adaptation of substrate etc., but not limited thereto.

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

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

These poor solvents can be used a kind, can also be used in mixed way a variety of.When using solvent as described above, in order to Not making the dissolubility of the solvent for including in polymer composition entirety significantly reduces, preferably 5 mass %~80 of solvent entirety Quality %, more preferably 20 mass of mass %~60 %.

As the compound for improving film thickness uniformity, surface smoothness, fluorine system surfactant, organic silicon-type can be enumerated Surfactant and nonionic surfactants etc..

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

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

Such as 3- TSL 8330,3-aminopropyltriethoxysilane, 2- aminopropyl can be enumerated Trimethoxy silane, 2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- TSL 8330, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- urea propyl trimethoxy silicane, 3- urea propyl triethoxy Silane, N- ethoxy carbonyl -3- TSL 8330, N- ethoxy carbonyl -3-aminopropyltriethoxysilane, Three second triamine of N- triethoxysilylpropyltetrasulfide, three second triamine of N- trimethoxy-silylpropyl, 10- trimethoxy first silicon Three azepine decane of alkyl -1,4,7-, three azepine decane of 10- triethoxysilyl -1,4,7-, 9- trimethyoxysilane Base -3,6- diaza nonyl acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyl acetic acid esters, N- benzyl -3- amino Propyl trimethoxy silicane, N- benzyl -3-aminopropyltriethoxysilane, N- phenyl -3- TSL 8330, Bis- (oxygen the ethylidene) -3- TSL 8330s of N- phenyl -3-aminopropyltriethoxysilane, N-, N- are bis-, and (oxygen is sub- Ethyl) -3-aminopropyltriethoxysilane etc..

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

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

Using the adaptation for improving liquid crystal orientation film and substrate compound when, dosage is relative to combination of polymers 100 mass parts of resin component contained in object are preferably 0.1 mass parts~30 mass parts, more preferably 1 mass parts~20 mass Part.When dosage is less than 0.1 mass parts, the effect for improving adaptation can not be expected, when being more than 30 mass parts, the orientation of liquid crystal has When be deteriorated.

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

As photosensitizer, there are aromatic nitro compound, cumarin (7- lignocaine -4- methylcoumarin, 7- hydroxyl - 4- methylcoumarin), coumarin ketone, carbonyl bicoumarin, aromatic series 2- hydroxy-ketone and the aromatic series 2- hydroxyl replaced by amino (2- dihydroxy benaophenonel, single pair (dimethylamino) -2- dihydroxy benaophenonel or two are to (dimethylamino) -2- hydroxyl hexichol for base ketone Ketone), acetophenone, anthraquinone, xanthone, thio xanthone, benzanthrone, thiazoline (2- benzoyl methylene -3- first Base-β-aphthothiazoles quinoline, 2- (β-naphthoyl methylene) -3- methylbenzothiazole quinoline, 2- (α-naphthoyl methylene) -3- methyl Benzothiazoline, 2- (4- biphenyl Acylmethylene) -3- methylbenzothiazole quinoline, 2- (β-naphthoyl methylene) -3- methyl-β - Aphthothiazoles quinoline, 2- (4- biphenyl Acylmethylene) -3- methyl-β-aphthothiazoles quinoline, 2- (p- fluorobenzoyl methylene) - 3- methyl-β-aphthothiazoles quinoline), oxazoline (2- benzoyl methylene -3- methyl-β-aphthoxazoles quinoline, 2- (β-naphthoyl Methylene) -3- methylbenzoxazole quinoline, 2- (α-naphthoyl methylene) -3- methylbenzoxazole quinoline, (the 4- biphenyl acyl group Asia 2- Methyl) -3- methylbenzoxazole quinoline, 2- (β-naphthoyl methylene) -3- methyl-β-aphthoxazoles quinoline, (the 4- biphenyl acyl group Asia 2- Methyl) -3- methyl-β-aphthoxazoles quinoline, 2- (p- fluorobenzoyl methylene) -3- methyl-β-aphthoxazoles quinoline), benzo thiophene Azoles, nitroaniline (meta nitro aniline or paranitroanilinum, 2,4,6- trinitroaniline) or nitro acenaphthene (5- nitro acenaphthene), (2- [(hydroxyl is to methoxyl group) styryl] benzothiazole, benzoin alkylether, N- are alkylated phthalein ketone, acetophenone ketal (2,2- Dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2- naphthalene methanol, 2- naphthalene-carboxylic acid, 9- anthryl carbinol and 9- anthracene carboxylic acid), chromene, in azo Benzazole, plum Lip river cumarin etc..

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

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

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

About coating method, industrial is usually to be carried out using silk-screen printing, hectographic printing, flexible printing or ink-jet method etc. Method.As other coating methods, there are infusion process, rolling method, slot coated method, spin-coating method (method of spin coating) or spray coating method Deng, can according to purpose use they.

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

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

In addition, can also be arranged the substrate for being formed with film is cooling after [I] process and before next [II] process To the process of room temperature.

In process [II], polarized UV rays are irradiated to film obtained in process [I].Polarization is irradiated to the film surface of film When ultraviolet light, polarized UV rays are irradiated to substrate from particular aspects across polarization plates.As ultraviolet light to be used, can be used Wavelength is the ultraviolet light of 100nm~400nm range.Preferably, it according to film type to be used, is selected by filter etc. Optimal wavelength.Also, such as can choose using wavelength be 290nm~400nm range ultraviolet light, so as to selectivity Ground induces photo-crosslinking.As ultraviolet light, the light for example issued by high-pressure sodium lamp can be used.

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

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

The heating meanss such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven can be used in heating.Heating temperature can It is determined with considering that film used is made to show the temperature of liquid crystal liquid crystal property.

Heating temperature is preferably the temperature (hereinafter referred to as liquid crystal performance temperature) that side chain type macromolecule can show liquid crystal liquid crystal property Within the temperature range of.Can be predicted: in the case where the film surface of film etc, the liquid crystal performance temperature of film coated surface is lower than Liquid crystal when whole observation can express the photonasty side chain type macromolecule of liquid crystal liquid crystal property shows temperature.Therefore, heating temperature is more excellent It is selected as within the temperature range of the liquid crystal performance temperature of film coated surface.That is, the temperature model of the heating temperature after irradiation polarized UV rays It encloses preferably using low 10 DEG C of the temperature of lower limit of the temperature range of liquid crystal more high molecular than side chain type used performance temperature as under It limits and using low 10 DEG C of the temperature of the upper limit than the liquid crystal temperature range as the temperature of the range of the upper limit.Heating temperature is lower than upper When stating temperature range, there are not being inclined to very in film by hot bring anisotropy amplification effect, in addition, heating temperature When excessively high compared with above-mentioned temperature range, there are film state inclining close to isotropic liquid condition (isotropic phase) To at this point, being difficult to due to self assembly sometimes to a direction reorientation.

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

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

By with process as above, in the manufacturing method of the present invention, can be realized film is efficiently imported it is each to different Property.Further, it is possible to efficiently manufacture the substrate with liquid crystal orientation film.In addition, due to being taken again with 150 DEG C or more of high temperature To, therefore the substrate for the liquid crystal orientation film excellent in reliability such as can manufacture conservation rate with voltage.

[IV] process is the substrate that will have liquid crystal orientation film on the transverse electric field driving conductive film obtained in [III] (the 1st substrate) substrate with liquid crystal orientation film without conductive film obtained in above-mentioned [I ']~[III '] in the same manner as (the 2nd substrate) carried out across liquid crystal in the opposite mode of the liquid crystal orientation film of the two it is oppositely disposed, utilize well known method production Liquid crystal cells, to make the process that the driving liquid crystal of transverse electric field indicates element.It should be noted that process [I ']~ In [III '], in addition to replacing that there is the transverse direction using the substrate without transverse electric field driving conductive film in process [I] Except the substrate of electric field driven conductive film, it can be carried out similarly with process [I]~[III].Process [I]~[III] and process [I ']~[III's '] only difference is that whether there is or not above-mentioned conductive films, therefore omit the explanation of process [I ']~[III '].

If enumerating liquid crystal cells or liquid crystal indicates a production example of element, following method can be exemplified: in preparation The 1st substrate stated and the 2nd substrate spread spacer on the liquid crystal orientation film of a substrate, become interior with liquid crystal alignment film surface The method that the mode of side is pasted on another substrate, decompression injection liquid crystal and sealing；Alternatively, being taken to the liquid crystal for being scattered with spacer After liquid crystal is added dropwise to film surface, adhesive substrate and the method etc. being sealed.At this point, it is preferable to use have laterally electricity for the substrate of side The substrate of the electrode of field driving comb teeth-shaped structure.Spacer diameter at this time is preferably 1 μm~30 μm, more preferably 2 μm~ 10μm.The spacer diameter is determined for clamping the spacing of a pair of of substrate of liquid crystal layer, the i.e. thickness of liquid crystal layer.

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

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

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

Fig. 1 is schematically to illustrate to have used in the 1st mode of the invention to have photocrosslinking reaction group as light reaction Property group structure side chain type macromolecule made of, the anisotropy in the manufacturing method of liquid crystal orientation film import the one of processing The figure of example.(a) of Fig. 1 is the figure of the side chain type polymeric membrane state before schematically showing polarizing light irradiation, and (b) of Fig. 1 is The figure of side chain type polymeric membrane state after schematically showing polarizing light irradiation, (c) of Fig. 1 are after schematically showing heating Side chain type polymeric membrane state figure, the anisotropy hour especially imported, i.e., in the 1st mode of the invention, The showing when ultraviolet irradiation amount of [II] process is in the range of making Δ A reach the 1%~15% of maximum ultraviolet irradiation amount It is intended to.

Fig. 2 is schematically to illustrate to have used in the 1st mode of the invention to have photocrosslinking reaction group as light reaction Property group structure side chain type macromolecule made of, the anisotropy in the manufacturing method of liquid crystal orientation film import the one of processing The figure of example.(a) of Fig. 2 is the figure of the side chain type polymeric membrane state before schematically showing polarizing light irradiation, and (b) of Fig. 2 is The figure of side chain type polymeric membrane state after schematically showing polarizing light irradiation, (c) of Fig. 2 are after schematically showing heating Side chain type polymeric membrane state figure, when the anisotropy especially imported is big, i.e., in the 1st mode of the invention, The showing when ultraviolet irradiation amount of [II] process is in the range of making Δ A reach the 15%~70% of maximum ultraviolet irradiation amount It is intended to.

Fig. 3 is schematically to illustrate to have used in the 2nd mode of the invention to have photoisomerization group or above-mentioned formula (18) made of side chain type macromolecule of the light fries' rearrangement group as the structure of photoreactive group shown in, liquid crystal aligning Anisotropy in the manufacturing method of film imports the figure of an example of processing.(a) of Fig. 3 is before schematically showing polarizing light irradiation Side chain type polymeric membrane state figure, (b) of Fig. 3 is that the side chain type macromolecule after schematically showing polarizing light irradiation is membranaceous The figure of state, (c) of Fig. 3 are the figures for schematically showing the side chain type polymeric membrane state after heating, and what is especially imported is each Anisotropy hour, i.e., in the 2nd mode of the invention, the ultraviolet irradiation amount of [II] process makes Δ A reach maximum ultraviolet Schematic diagram when in the range of the 1%~70% of line exposure.

Fig. 4 is schematically to illustrate to have used in the 2nd mode of the invention to have light shown in above-mentioned formula (19) not sharp This is reset made of side chain type macromolecule of the group as the structure of photoreactive group, in the manufacturing method of liquid crystal orientation film Anisotropy imports the figure of an example of processing.(a) of Fig. 4 is the side chain type polymeric membrane before schematically showing polarizing light irradiation The figure of state, (b) of Fig. 4 are the figure of the side chain type polymeric membrane state after schematically showing polarizing light irradiation, (c) of Fig. 4 It is the figure of side chain type polymeric membrane state after schematically showing heating exists when the anisotropy especially imported is big In the 2nd mode of the invention, the ultraviolet irradiation amount of [II] process make Δ A reach maximum ultraviolet irradiation amount 1%~ Schematic diagram when in the range of 70%.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the manufacturing method of the present invention, preferably by the exposure for the polarized UV rays irradiated to film used in the present invention Be set as realizing the amount of the polarized UV rays of Δ Amax 1%~70% in the range of, be more preferably set as 1%~50% range It is interior.In film used in the present invention, it can realize inclined in the range of the 1%~50% of the amount of the polarized UV rays of Δ Amax Vibration ultraviolet irradiation amount is equivalent to 0.1 mole of %~20 for making the entirety of photonasty group possessed by the side chain type polymeric membrane The amount of the polarized UV rays of photo-crosslinking occurs for mole %.

As described above, in the manufacturing method of the present invention, anisotropy is efficiently imported to film to realize, with the side The high molecular liquid crystal temperature range of chain determines suitable heating temperature as described above as benchmark.Thus, for example this hair When the high molecular liquid crystal temperature range of side chain type used in bright is 150 DEG C~250 DEG C, it is expected that after irradiating polarized UV rays The temperature of heating is 140 DEG C~240 DEG C.It sets in this way, bigger anisotropy is assigned to film used in the present invention.

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

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

Embodiment

It is referred to as follows used in embodiment.

(methacrylic monomer)

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

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

MA3 is the not yet noval chemical compound disclosed in document etc., its synthetic method is described in detail in synthesis example 1 below.

MA3-1 is by synthetic method described in document (Liquid Crystals (2005), 32 (8), 1031-1044.) And synthesize.

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

(organic solvent)

THF: tetrahydrofuran

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

BC: butyl cellosolve

EDC:1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride

DMAP:4- dimethylamino naphthyridine

(polymerization initiator)

AIBN:2,2 '-azobis isobutyronitrile

The synthesis of compound [MA3] (being MA9 in following formula)

Compound [MA2] (20.00g, 65.3mmol), compound [MA9-1] are added into 500mL four-neck flask (that is, changing Close object MA3-1) (14.09g, 71.8mmol), EDC (15.02g, 78.4mmol), DMAP (0.80g, 6.53mmol), THF (200g) is reacted with 23 DEG C.Reactive tracing is carried out using HPLC, reaction solution after reaction, is injected into steaming by confirmation Distilled water (1.2L) is added ethyl acetate (2L), removes water layer by liquid separation operation.Organic layer is clear with distilled water (500mL) It is after washing 3 times, organic layer is dry with magnesium sulfate.Thereafter, it filters and distills removal solvent with evaporator, thus with oily compound Form obtain compound [MA9-2] (that is, compound MA3-2).

Then, to addition p-methyl benzenesulfonic acid pyridine (being labeled as PPTS) in gained compound [MA9-2] (1.59g, 6.3mmol), ethyl alcohol (100g), with 60 DEG C of progress heating stirrings.Reactive tracing is carried out using HPLC, confirmation after reaction, will Reaction solution is cooled with an ice bath, and filters solid be precipitated and is cleaned with ethyl alcohol.By being dried under reduced pressure to obtained solid, from And obtain compound [MA9] (that is, compound MA3) 19.2g (yield 69%).

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

[measurement of phase transition temperature]

The liquid crystal phase transition temperature of the polymer obtained by embodiment comparative example is measured using differential scanning calorimetry (DSC) DSC3100SR (マッ Network サイエ Application ス corporation) is measured.

MA1 (3.99g, 12.0mmol), MA2 (2.45g, 8.0mmol), MA4 (7.65g, 20.0mmol) are dissolved in NMP In (128.6g), after being de-gassed with diaphragm pump, adds AIBN (0.197g, 1.2mmol) and be de-gassed again.Thereafter with 55 DEG C reaction 24 hours, obtain the polymer solution of methacrylate.The polymer solution is added dropwise to methanol (1.5L), is filtered Gained sediment.After the sediment is cleaned with methanol, it is dried under reduced pressure with 50 DEG C of baking oven, obtains methacrylic acid Ester polymer powder (A).The number-average molecular weight of the polymer is 20,000, weight average molecular weight 118,000.

The liquid crystal performance temperature of gained methacrylate polymers is 160 DEG C~250 DEG C.

NMP (64.8g) is added in gained methacrylate polymer powder (A) (7.2g), to be stirred at room temperature 5 hours And it makes it dissolve.By adding BC (48g) into the solution and stirring, to obtain aligning agent for liquid crystal (A1).

[production of liquid crystal cells]

Using aligning agent for liquid crystal obtained in embodiment 1 (A), the system of liquid crystal cells is carried out according to following the step of showing Make.Substrate is having a size of 30mm × 40mm and with a thickness of the glass substrate of 0.7mm, using configured with the shape by ito film patterning At comb teeth-shaped pixel electrode substrate." < " font electrode element that there is pixel electrode center portion to bend is through multiple The comb teeth-shaped shape for arranging and constituting.The width of the width direction of each electrode element is 10 μm, between electrode element between be divided into 20 μ m.The electrode element for forming " < " font that the pixel electrode of each pixel is bent by center portion is constituted through multiple arrangements, Therefore the shape not instead of oblong-shaped of each pixel, has bend in the same manner as electrode element in center portion, class It is similar to the shape of " < " word of runic.Also, each pixel is divided using the bending part in its center as boundary up and down, has bending section 1st region of the upside divided and the 2nd region of downside.When comparing the 1st region and 2 region of each pixel, their picture is constituted The formation direction of the electrode element of plain electrode is different.That is, using the orientation process direction of aftermentioned liquid crystal orientation film as when benchmark, In 1st region of pixel, the electrode element of pixel electrode is formed in a manner of+15 ° of angle (clockwise) is presented, in pixel In 2nd region, the electrode element of pixel electrode is formed in a manner of -15 ° of angle (clockwise) is presented.That is, the 1st of each pixel the Region and the 2nd region are constituted as follows: the liquid crystal induced and applying voltage between pixel electrode and counter electrode, substrate The direction of spinning movement (plane switching) in face opposite direction each other.By aligning agent for liquid crystal obtained in synthesis example 1 (A) spin coating On the above-mentioned electroded substrate prepared.Then, with press drying 90 seconds of 70 DEG C, the liquid that film thickness is 100nm is formed Brilliant alignment films.Then, across polarization plates with 20mJ/cm²After the ultraviolet light of coated surface irradiation 313nm, the hot plate with 220 DEG C adds Heat 10 minutes, obtains the substrate with liquid crystal orientation film.In addition, being 4 μm to not formed electrode and with height as opposite substrate The glass substrate of column spacer similarly form film, implement orientation process.On the liquid crystal orientation film of a substrate Printing and sealing agent (assists vertical Chemical Co., Ltd. system, XN-1500T).Then, opposite with liquid crystal alignment film surface and differently- oriented directivity reaches After 0 ° of mode pastes another substrate, makes sealant heat cure and make dummy cell.The normal direction dummy cell is injected by decompression Middle injection liquid crystal MLC-2041 (MERCK CORPORATION system) seals inlet, obtains having IPS (In-Planes Switching, plane switching) mode liquid crystal indicate element constitute liquid crystal cells.

[measurement of voltage retention]

The measurement of voltage retention about liquid crystal cells, 60 DEG C at a temperature of apply the 4V voltage of 60 μ s, will Voltage, which is able to maintain, after 16.67ms is calculated for which kind of degree as voltage retention.It should be noted that voltage retention Measurement used the VHR-1 of TOYO Corporation.

As reliability evaluation, with the 10V of the frequency application 360 hours of 30Hz in 70 DEG C of baking oven_PPAlternating voltage.It surveys The respective voltage retention of liquid crystal cells after liquid crystal cells and reliability test before determining reliability test.

As a result as described in Table 1 like that.

MA1 (1.99g, 6mmol), MA3 (5.97g, 14mmol) are dissolved in NMP (73.2g), taken off with diaphragm pump After gas, adds AIBN (0.164g, 1.0mmol) and be de-gassed again.Thereafter it is reacted 24 hours with 55 DEG C, obtains metering system The polymer solution of acid esters.The polymer solution is added dropwise to methanol (1.5L), gained sediment is filtered.By the sediment first It after alcohol is cleaned, is dried under reduced pressure with 50 DEG C of baking oven, obtains methacrylate polymer powder (A2).The polymer Number-average molecular weight be 30000, weight average molecular weight 126800.

NMP (65.2g) is added in gained methacrylate polymer powder (A2) (7.2g), it is small to be stirred at room temperature 5 When and make it dissolve.By adding BC (48.3g) into the solution and stirring, to obtain aligning agent for liquid crystal (A2).

For the aligning agent for liquid crystal (A2), the heating on hot plate is set as 200 DEG C, in addition to this, using with embodiment 1 After identical step production liquid crystal cells, reliability test is carried out, liquid crystal cells and reliability examination before measuring reliability test The respective voltage retention of liquid crystal cells after testing.

As a result as described in Table 1 like that.

MA1 (5.32g, 16.0mmol), MA2 (4.90g, 16.0mmol), MA4 (3.05g, 8.0mmol) are dissolved in NMP In (121.3g), after being de-gassed with diaphragm pump, adds AIBN (0.197g, 1.2mmol) and be de-gassed again.Thereafter with 55 DEG C reaction 24 hours, obtain the polymer solution of methacrylate.The polymer solution is added dropwise to methanol (1.5L), is filtered Gained sediment.After the sediment is cleaned with methanol, it is dried under reduced pressure with 50 DEG C of baking oven, obtains methacrylic acid Ester polymer powder (A3).The number-average molecular weight of the polymer is 18,000, weight average molecular weight 100,000.

The liquid crystal performance temperature of gained methacrylate polymers is 155 DEG C~215 DEG C.

NMP (64.8g) is added in gained methacrylate polymer powder (A3) (7.2g), it is small to be stirred at room temperature 5 When and make it dissolve.By adding BC (48g) into the solution and stirring, to obtain aligning agent for liquid crystal (A3).

For the aligning agent for liquid crystal (A2), the heating on hot plate is set as 180 DEG C, in addition to this, using with embodiment 1 After identical step production liquid crystal cells, reliability test is carried out, liquid crystal cells and reliability examination before measuring reliability test The respective voltage retention of liquid crystal cells after testing.

As a result as described in Table 1 like that.

MA1 (5.32g, 16.0mmol), MA2 (3.68g, 12.0mmol), MA3 (5.12g, 12.0mmol) are dissolved in In NMP (81.1g), after being de-gassed with diaphragm pump, adds AIBN (0.197g, 1.2mmol) and be de-gassed again.Thereafter with 55 DEG C are reacted 24 hours, and the polymer solution of methacrylate is obtained.The polymer solution is added dropwise to methanol (1.5L), mistake Filter gained sediment.After the sediment is cleaned with methanol, it is dried under reduced pressure with 50 DEG C of baking oven, obtains metering system Acid ester polymer powder (A4).The number-average molecular weight of the polymer is 26000, weight average molecular weight 115000.

The liquid crystal performance temperature of gained methacrylate polymers is 150 DEG C~200 DEG C.

NMP (65.2g) is added in gained methacrylate polymer powder (A4) (7.2g), it is small to be stirred at room temperature 5 When and make it dissolve.By adding BC (48.3g) into the solution and stirring, to obtain aligning agent for liquid crystal (A4).

For the aligning agent for liquid crystal (A4), the heating on hot plate is set as 180 DEG C, in addition to this, using with embodiment 1 After identical step production liquid crystal cells, reliability test is carried out, liquid crystal cells and reliability examination before measuring reliability test The respective voltage retention of liquid crystal cells after testing.

As a result as described in Table 1 like that.

MA1 (4.99g, 15.0mmol), MA2 (4.60g, 15.0mmol) are dissolved in THF (88.5g), diaphragm pump is used After being de-gassed, adds AIBN (0.246g, 1.5mmol) and be de-gassed again.Thereafter it is reacted 30 hours with 50 DEG C, obtains first The polymer solution of base acrylate.The polymer solution is added dropwise to diethyl ether (1000ml), gained sediment is filtered.It should Sediment is cleaned with diethyl ether, is dried under reduced pressure in 40 DEG C of baking oven, obtains methacrylate polymer powder (B).The number-average molecular weight of the polymer is 14000, weight average molecular weight 29000.

The liquid crystal phase transition temperature of gained methacrylate polymers is 135 DEG C~180 DEG C.

NMP (29.29g) is added in gained methacrylate polymer powder (B1) (6.0g), it is small to be stirred at room temperature 5 When and make it dissolve.By adding NMP (24.7g), BC (450.0g) into the solution and stirring, to obtain aligning agent for liquid crystal (B1)。

For the aligning agent for liquid crystal (B1), ultraviolet irradiation amount is set as 5mJ, is set as the temperature heated on hot plate 140 DEG C, in addition to this, after making liquid crystal cells using step same as Example 1, reliability test is carried out, measurement is reliable Property test before liquid crystal cells and the respective voltage retention of liquid crystal cells after reliability test.

As a result as described in Table 1 like that.

[table 1]

It is as shown in Table 1: after irradiating ultraviolet light to the side chain type polymeric membrane for showing liquid crystal liquid crystal property, in high-temperature temperature area Also the side chain type polymeric membrane that liquid crystal liquid crystal property is shown in domain can be improved orientation process temperature.And then it is found that in high-temperature temperature area Also the side chain type polymeric membrane that liquid crystal liquid crystal property is shown in domain can reduce the reduction of the voltage retention after reliability test, and compare It is reduced compared with the voltage retention after reliability long-term in example 1.Material of the invention is able to carry out orientation process in high-temperature region, Therefore residual solvent, the residual monomer etc. for including in alignment films distil, and liquid crystal indicates that the impurity for including in element reduces, because The excellent characteristic of this display long-term reliability.In addition, with energy in the firing temperature region of available liquid crystal alignment films same degree Orientation process is enough carried out, therefore adjusts firing furnace also without taking time and energy, therefore is also from the viewpoint of production efficiency stabilisation Preferably.It so confirmed to indicate that element shows very excellent expression quality using liquid crystal produced by the present invention.

Description of symbols

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 kind of polymer composition, described (A) side chain type macromolecule can be dissolved by containing (A) side chain type macromolecule and (B) Organic solvent, (A) the side chain type macromolecule is the photonasty side chain type that liquid crystal liquid crystal property is shown within the scope of specific temperature Macromolecule, the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, shows the upper limit of the temperature range of liquid crystal liquid crystal property Value is 200 DEG C or more and 300 DEG C or less.

2. a kind of polymer composition, described (A) side chain type macromolecule can be dissolved by containing (A) side chain type macromolecule and (B) Organic solvent, (A) the side chain type macromolecule is the photonasty side chain type that liquid crystal liquid crystal property is shown within the scope of specific temperature Macromolecule, the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, shows the upper limit of the temperature range of liquid crystal liquid crystal property Value is 220 DEG C or more and 300 DEG C or less.

3. composition according to claim 1 or 2, wherein (A) ingredient have photo-crosslinking, photoisomerization or light can occur The photonasty side chain of fries' rearrangement.

4. composition according to claim 1 or 2, wherein (A) ingredient has to be selected to be made of following formula (1)~(6) Any photonasty side chain in group,

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

Y₁Indicate the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of identical or different 2~6 ring in these substituent groups is bonded by binding groups B, is bonded to The phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 ester ring type hydrocarbon in ring hydrogen it is former It son and is bonded to identical or different 2~6 ring in these substituent groups and is bonded by binding groups B Group hydrogen atom each independently optionally by-COOR₀、-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, The alkyl of carbon number 1~5 or the alkoxy of carbon number 1~5 replace, in formula, R₀Indicate the alkyl of hydrogen atom or carbon number 1~5；

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

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

Cou indicates Coumarin-6-base or coumarin-7-base, is bonded to their hydrogen atom each independently optionally by-NO₂、- CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；

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

Q3 is 0 or 1；

P and Q be each independently selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 alicyclic ring Group in the group of formula hydrocarbon and their combination composition；Wherein, when X is-CH=CH-CO-O- ,-O-CO-CH=CH- ,-CH= The P or Q for the side that CH- is bonded are aromatic rings；

When the quantity of P is 2, P is optionally same or different to each other；

When the quantity of Q is 2, Q is optionally same or different to each other；

L1 is 0 or 1；

The integer that l2 is 0~2；

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

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

5. composition according to claim 4, wherein the end of formula (1)~(6) the photonasty side chain as (A) ingredient End be-COOH when, the side chain have 2 or more be selected from 1 valence phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon numbers 5~ Ring structure in 8 ester ring type hydrocarbon,

When the end of the side chain is the group in addition to-COOH, which has 3 or more phenyl ring, naphthalene nucleus, the connection for being selected from 1 valence Phenyl ring, furan nucleus, pyrrole ring and carbon number 5~8 ester ring type hydrocarbon in ring structure.

6. composition according to claim 1 or 2, wherein (A) ingredient has to be selected to be made of following formula (7)~(10) Group in any photonasty side chain,

L indicates 1~12 integer；

M indicates that 0~2 integer, m1, m2 indicate 1~3 integer；

N indicates 0~12 integer, wherein when n=0, B is singly-bound；

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

7. composition according to claim 1 or 2, wherein (A) ingredient has to be selected to be made of following formula (11)~(13) Group in any photonasty side chain,

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

L indicates that 1~12 integer, m indicate that 0~2 integer, m1 indicate 1~3 integer；

R indicates the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of identical or different 2~6 ring in these substituent groups is bonded by binding groups B, is bonded to The phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 ester ring type hydrocarbon in ring hydrogen it is former It son and is bonded to identical or different 2~6 ring in these substituent groups and is bonded by binding groups B Group hydrogen atom each independently optionally by-COOR₀、-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, The alkyl of carbon number 1~5 or the alkoxy of carbon number 1~5 replace, in formula, R₀Indicate the alkyl or R of hydrogen atom or carbon number 1~5 Indicate the alkoxy of hydroxyl or carbon number 1~6.

8. composition according to claim 1 or 2, wherein (A) ingredient has photosensitive shown in following formula (14) or (15) Property side chain,

L indicates that 1~12 integer, m1, m2 indicate 1~3 integer.

9. composition according to claim 1 or 2, wherein (A) ingredient has photosensitive shown in following formula (16) or (17) Property side chain,

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

X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-C=C- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH=CH-, X Quantity be 2 when, X is optionally same or different to each other；

L indicates that 1~12 integer, m indicate 0~2 integer.

10. composition according to claim 1 or 2, wherein (A) ingredient has selected from by following formula (18) or (19) group At group in any photonasty side chain,

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

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

L indicates that 1~12 integer, m1, m2 indicate 1~3 integer；

R₁Indicate hydrogen atom ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen group, carbon number 1~5 alkyl or carbon number 1~5 alkoxy.

11. composition according to claim 1 or 2, wherein (A) ingredient has photonasty side shown in following formula (20) Chain,

L indicates that 1~12 integer, m indicate 0~2 integer.

12. composition according to claim 1 or 2, wherein (A) ingredient has selected from by following formula (21)~(31) group At group in any liquid crystal liquid crystal property side chain,

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

Y₃For selected from by the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and carbon number 5~8 ester ring type hydrocarbon and it The group that is combined into of group in group, be bonded to their hydrogen atom each independently optionally by-NO₂,-CN, halogen group, The alkyl of carbon number 1~5 or the alkoxy of carbon number 1~5 replace；

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

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

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

R₂Indicate hydrogen atom ,-NO₂,-CN, halogen group, phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and the carbon number of 1 valence 5~8 ester ring type hydrocarbon and alkyl or alkoxy；

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

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

Composition described in any one of claim 1~12 is coated on the base with transverse electric field driving conductive film by [I] The process of film is formed on plate；

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

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

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

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

Prepare the substrate i.e. process of the 1st substrate described in claim 14；

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

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

The process [I '], [II '] and [III '] are as follows:

[I '] on the 2nd substrate coated polymeric composition and the process that forms film, the polymer composition contain the side (A) Chain macromolecule and (B) organic solvent, (A) the side chain type macromolecule is to show liquid crystal liquid crystal property within the scope of specific temperature Photonasty side chain type macromolecule, the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, shows the temperature of liquid crystal liquid crystal property The upper limit value for spending range is 200 DEG C or more and 300 DEG C or less；

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

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

The process [I '], [II '] and [III '] are as follows:

[I '] on the 2nd substrate coated polymeric composition and the process that forms film, the polymer composition contain the side (A) Chain macromolecule and (B) organic solvent, (A) the side chain type macromolecule is to show liquid crystal liquid crystal property within the scope of specific temperature Photonasty side chain type macromolecule, the lower limit value for showing the temperature range of liquid crystal liquid crystal property is 150 DEG C or more, shows the temperature of liquid crystal liquid crystal property The upper limit value for spending range is 220 DEG C or more and 300 DEG C or less；

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

It 18. a kind of driving liquid crystal of transverse electric field indicates element, is manufactured by method described in claim 16 or 17 's.