CN105593751A

CN105593751A - Polymer, polymer composition, and liquid crystal alignment film for horizontal-electric-field drive-type liquid crystal display element

Info

Publication number: CN105593751A
Application number: CN201480052684.8A
Authority: CN
Inventors: 根木隆之; 川野勇太; 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: 2013-07-24
Filing date: 2014-07-24
Publication date: 2016-05-18
Anticipated expiration: 2034-07-24
Also published as: KR20160035010A; KR102290811B1; TW201522583A; JPWO2015012341A1; JP6523169B2; TWI637044B; WO2015012341A1; CN105593751B

Abstract

In order to provide a horizontal-electric-field drive-type liquid crystal display element that imparts alignment control functionality with high efficiency and exhibits superior burn-in properties, a photosensitive side-chain polymer, which expresses liquid crystallinity in a prescribed temperature range, according to the present invention includes a side chain expressed by formula (0). In the formula, G is a group selected from formula (G-1), (G-2), (G-3), and (G-4) (in the formula: a dashed line represents a bonding means; R50 represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1-3 carbon atoms, and a phenyl group, and may be the same or different when there is a plurality thereof; J represents O, S, NH, or NR51; and R51 represents a group selected from an alkyl group having 1-3 carbon atoms and a phenyl group).

Description

The driving liquid crystal of polymer, polymer composition and transverse electric field represents element liquid crystal orientation film

Technical field

The composition that the present invention relates to new polymers, comprise this polymer and used its driving liquid of transverse electric fieldCrystalline substance represents element liquid crystal orientation film and has the manufacture method of the substrate of this alignment films. And then, the present invention relates to for systemThe liquid crystal of making ghost excellent represents the new method of element.

Background technology

Liquid crystal represents that the indication device that element is light as quality, cross section is thin and power consumption is low is known, is used in recent yearsLarge-scale tv purposes etc., have realized significant development. Liquid crystal represents that element is for example to utilize a pair of transparency carrier that possesses electrodeClamping liquid crystal layer forms. And, representing in element at liquid crystal, the organic film that comprises organic material is used as liquid crystal orientation filmMake liquid crystal between substrate, present expectation state of orientation.

That is, liquid crystal orientation film is the component parts that liquid crystal represents element, its be formed on holding liquid crystal substrate and liquid crystalThe surface of contact, bears and makes liquid crystal be orientated this effect along specific direction between this substrate. And, for liquid crystal orientation film, except liquid crystal is orientated this effect along being for example parallel to the specific directions such as the direction of substrate, also requirement sometimesLiquid crystal pretilt angle is controlled to this effect. The ability of the control liquid crystal aligning of this liquid crystal orientation film is (hereinafter referred to as orientationControl ability. ) be endowed by the organic film that forms liquid crystal orientation film is carried out to orientation process.

As the method for orientation treatment of liquid crystal orientation film for giving orientation control ability, all the time known have a brushingMethod. Brushing method refers to following method: for the organic film of the polyvinyl alcohol on substrate, polyamide, polyimides etc., with cottonThe cloth of flower, nylon, polyester etc. is along its surface of constant direction friction (brushing), thereby makes liquid crystal along frictional direction (brushing sideTo) orientation. This brushing method can realize more stable liquid crystal aligning state easily, and the liquid crystal that therefore can be used in the past representsThe manufacturing process of element. And, as the organic film using in liquid crystal orientation film, mainly select the reliabilities such as heat resistance, electricity spyThe polyimides of property excellence is organic film.

But the brushing method that the surface of the liquid crystal orientation film that comprises polyimides etc. is rubbed exists produces dirt, generationThe problem of static. In addition, because liquid crystal in recent years represents electrode or the liquid crystal drive on high-definition, the corresponding substrate of elementWith switching concavo-convex that active element causes, therefore, cannot with cloth rub equably liquid crystal orientation film surface, cannot realize allEven liquid crystal aligning.

Thereby, as other method for orientation treatment of liquid crystal orientation film that does not carry out brushing, study energetically light orientationMethod.

Optical alignment method has the whole bag of tricks, is forming liquid crystal orientation film organic by rectilinearly polarized light or through the light of collimationIn film, form anisotropy, according to this anisotropy, liquid crystal is orientated.

As main optical alignment method, the known optical alignment method that has breakdown type. For example, polyimide film is irradiated to polarization purpleOutside line, utilize molecular structure ultraviolet radiation absorption polarization direction dependence and make it that anisotropic decomposition occur. And, logicalCrossing undecomposed and residual polyimides is orientated (for example, with reference to patent documentation 1 liquid crystal. ).

In addition, the known optical alignment method that has photo-crosslinking type, photoisomerization type also. For example use poly-vinyl cinnamate, shinePenetrate polarized UV rays, make two key part generation dimerization reactions (cross-linking reaction) of 2 side chains that are parallel to polarised light. And, makeLiquid crystal is orientated (for example, with reference to non-patent literature 1 along the direction vertical with polarization direction. ). In addition, use at side chain toolWhile having the side chain type macromolecule of azobenzene, irradiate polarized UV rays, the azobenzene part of the side chain that is parallel to polarised light is occurredIsomerization reaction, makes liquid crystal be orientated (for example, with reference to non-patent literature 2 along the direction vertical with polarization direction. ).

As above-mentioned example, utilizing optical alignment method liquid crystal orientation film to be carried out in the method for orientation process, without enteringRow brushing, does not worry producing dirt, produces static. And, even if the substrate that represents element for the irregular liquid crystal of surperficial tool is alsoCan implementation orientation processing, thus the method for orientation treatment of the liquid crystal orientation film that is suitable for industrial manufacture process become.

Prior art document

Patent documentation

Patent documentation 1: No. 3893659 communique of Japanese Patent

Non-patent literature

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

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

Summary of the invention

The problem that invention will solve

As mentioned above, carry out the brushing of industrial utilization with representing the method for orientation treatment of element as liquid crystal all the timeMethod is compared, and optical alignment method, without this operation of brushing operation, therefore possesses obvious advantage. And, with getting that brushing producesThe brushing method of substantially fixing to control ability is compared, and optical alignment method can change the exposure of polarised light and control orientation control energyPower. But, want to realize the orientation control ability identical with degree while utilizing brushing method, sometimes at optical alignment methodNeed a large amount of polarizing light irradiation amounts or cannot realize stable liquid crystal aligning.

For example, in the breakdown type optical alignment method described in above-mentioned patent documentation 1, need to irradiate 60 minutes polyimide filmThe ultraviolet light that sends of the high-pressure sodium lamp by power 500W etc., need long-time and a large amount of ultraviolet rays to irradiate. In addition, in dimerizationIn the situation of type, photoisomerization type optical alignment method, sometimes need a large amount of ultraviolet rays of several J (joule)～tens of J left and right to irradiate. EnterAnd the in the situation that of photo-crosslinking type, photoisomerization type optical alignment method, heat endurance, the photostability of the orientation of liquid crystal are poor, thereforeWhen making liquid crystal and representing element, there is the problem that orientation is bad, represent ghost that occurs. Especially, the driving liquid of transverse electric fieldBrilliant expression, in element, switches liquid crystal molecule in face, and therefore the liquid crystal aligning skew after liquid crystal drive easily occurs, byAC drives the expression ghost causing to be considered obvious problem.

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

The object of the invention is to, provide with high efficiency be endowed orientation control ability, ghost excellent, there is horizontal strokeRepresent the substrate of element liquid crystal orientation film and there is the driving liquid crystal of transverse electric field of this substrate to electric field drive liquid crystalRepresent element.

In addition, the object of the invention is to, on the basis of above-mentioned purpose, provide and possess the horizontal stroke that voltage retention has improvedTo electric field drive liquid crystal cell and for the liquid crystal orientation film of this element.

For the scheme of dealing with problems

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

<1>a side chain type macromolecule, it for showing the photonasty side chain type of liquid crystal liquid crystal property in specific temperature rangeMacromolecule, also has the side chain shown in following formula (0).

[in formula, A, B represent singly-bound ,-O-,-CH independently of one another₂-、-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 that is 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 that is bonded to them is optionally replaced by halogen group;

X represent singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-,-C ≡ C-,-CH=CH-CO-O-or-O-CO-CH=CH-, the quantity of X is 2 o'clock, X is optionally same to each other or different to each other;

P and Q are independently of one another for selecting phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the carbon number 5～8 of free divalentGroup in the group of ester ring type hydrocarbon and their combination composition; Wherein, X is-when CH=CH-CO-O-,-O-CO-CH=CH-,-P or the Q of one side of CH=CH-institute bonding are aromatic rings, and the quantity of P is 2 when above, and P is optionally same to each other or different to each other, the number of QAmount is 2 when above, and Q is optionally same to each other or different to each other;

L1 is 0 or 1;

L2 is 0～2 integer;

L1 and l2 are at 0 o'clock, and when T is singly-bound, A also represents singly-bound;

L1 is 1 o'clock, and when T is singly-bound, B also represents singly-bound;

G for be selected from following formula (G-1), (G-2), (G-3) and (G-4) in group,

(in formula, dotted line represents connecting key; R⁵⁰Represent to be selected from the alkyl, phenyl of hydrogen atom, halogen atom, carbon number 1～3Group, there are multiple R⁵⁰Time, be optionally same to each other or different to each other; T is 1～7 integer; J represents O, S, NH or NR⁵¹，R⁵¹RepresentBe selected from the group in alkyl and the phenyl of carbon number 1～3)]

<2>above-mentioned<1>in, side chain type macromolecule can have can there is photo-crosslinking, photoisomerization or light fries' rearrangementPhotonasty side chain.

<3>above-mentioned<1>or<2>in, side chain type macromolecule can have in the choosing group that freely following formula (1)～(6) formAny photonasty side chain.

In formula, A, B, D represent singly-bound ,-O-,-CH independently of one another₂-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-or-O-CO-CH=CH-;

Y₁Represent in the ester ring type hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8 of 1 valency that is selected fromRing, or be selected from the group that 2～6 the identical or different rings in these substituting groups form by binding groups B bonding, keyClose in their hydrogen atom independently of one another optionally by-COOR₀(in formula, R₀Represent the alkyl of hydrogen atom or carbon number 1～5) ,-NO₂、-CN、-CH＝C(CN)₂The alkyl of ,-CH=CH-CN, halogen group, carbon number 1～5 or the alkoxyl of carbon number 1～5 replace;

Y₂For selecting the ester ring type hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5～8 of free divalent and itThe group of combination composition in group, the hydrogen atom that is bonded to them is independently of one another optionally by-NO₂、-CN、-CH＝C(CN)₂The alkyl of ,-CH=CH-CN, halogen group, carbon number 1～5 or the alkoxyl of carbon number 1～5 replace;

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

Cou represents Coumarin-6-Ji or coumarin-7-Ji, the hydrogen atom that is bonded to them independently of one another optionally by-NO₂、-CN、-CH＝C(CN)₂The alkyl of ,-CH=CH-CN, halogen group, carbon number 1～5 or the alkoxyl of carbon number 1～5 replace;

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

Q3 is 0 or 1;

L1 is 0 or 1;

L2 is 0～2 integer;

L1 is 1 o'clock, and when T is singly-bound, B also represents singly-bound;

H and I are independently of one another for to be selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and their combination of divalentGroup.

<4>above-mentioned<1>or<2>in, side chain type macromolecule can have in the choosing group that freely following formula (7)～(10) formAny photonasty side chain.

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

L represents 1～12 integer;

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

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

<5>above-mentioned<1>or<2>in, side chain type macromolecule can have the freely group of following formula (11)～(13) composition of choosingIn any photonasty side chain.

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

<6>above-mentioned<1>or<2>in, side chain type macromolecule can have the photonasty side shown in following formula (14) or (15)Chain.

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

<7>above-mentioned<1>or<2>in, side chain type macromolecule can have the photonasty side shown in following formula (16) or (17)Chain.

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

<8>above-mentioned<1>or<2>in, side chain type macromolecule can have the photonasty side shown in following formula (18) or (19)Chain.

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

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

<9>above-mentioned<1>or<2>in, side chain type macromolecule can have the photonasty side chain shown in following formula (20).

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

<10>above-mentioned<1>～<9>any one in, side chain type macromolecule can have freely following formula (21)～(31) of choosingAny liquid crystal liquid crystal property side chain in the group of composition.

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

Y₃For select freely phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring and the carbon number 5～8 of 1 valency ester ring type hydrocarbon,And group in the group of their combination composition, the hydrogen atom that is bonded to them is independently of one another optionally by-NO₂,-CN, halogenElement group, the alkyl of carbon number 1～5 or the alkoxyl of carbon number 1～5 replace;

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

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

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

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

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

<11>polymer composition, is characterized in that, it contains (A) above-mentioned<1>～<10>in described in any oneSide chain type macromolecule and (B) organic solvent.

<12>above-mentioned<11>in, polymer composition can also contain (C) amines, and described amines is in moleculeThere is 1 primary amino radical and nitrogenous heteroaromatic, and aforementioned primary amino radical is bonded to aliphatic alkyl or non-aromatic ring type hydrocarbonBase.

<13>above-mentioned<12>in, (C) composition can be following formula A-[1] (in formula, Y₁₁For thering is aliphatic alkyl or non-aromaticThe divalent organic group of fragrant family ring type alkyl, Y₁₂For nitrogenous heteroaromatic) shown in amines.

<14>there is the manufacture method that the driving liquid crystal of transverse electric field represents the substrate of element liquid crystal orientation film, itsObtained being endowed the foregoing liquid crystal alignment films of orientation control ability by possessing following operation:

[I] is by above-mentioned<11>～<13>in arbitrary composition be coated on and there is transverse electric field and drive with on the substrate of conducting filmAnd the operation of formation film;

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

The operation that [III] heats the film obtaining in [II].

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

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

<17>the driving liquid crystal of transverse electric field represents a manufacture method for element, and it obtains by possessing following operationThis liquid crystal represents element:

Prepare above-mentioned<15>the operation of substrate (the 1st substrate);

Acquisition has the operation of the 2nd substrate of following liquid crystal orientation film, its by possess following operation [I '], [II '] and[III '] and obtained being endowed the liquid crystal orientation film that is orientated control ability; And

[IV] with the liquid crystal orientation film of the 1st substrate and the 2nd substrate across the right mode of liquid crystalline phase, subtend configuration the 1st substrateWith the 2nd substrate, thereby obtain the operation that liquid crystal represents element,

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

[I '] is coated with above-mentioned<11 on the 2nd substrate>～<13>in arbitrary polymer composition and form the work of filmOrder;

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

The operation that [III '] heats the film obtaining in [II '].

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

The effect of invention

By the present invention, can provide with high efficiency be endowed orientation control ability, ghost excellent, have laterallyElectric field drive liquid crystal represents the substrate of element liquid crystal orientation film and has the driving liquid crystal watch of transverse electric field of this substrateShow element.

The driving liquid crystal of transverse electric field of manufacturing by method of the present invention represents that element given orientation efficientlyControl ability, even if therefore long-time continuous driving can not damage characterization yet.

In addition, by the present invention, on the basis of above-mentioned effect, can provide the Interfacial Adsorption liquid crystal at liquid crystal orientation filmIn ionic impurity, possess the driving liquid crystal cell of transverse electric field of the voltage retention being improved and for this elementLiquid crystal orientation film.

Brief description of the drawings

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

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

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

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

Detailed description of the invention

The inventor conducts in-depth research, and result obtains following opinion, thereby has completed the present invention.

The polymer composition using in manufacture method of the present invention has the photonasty side chain that can show liquid crystal liquid crystal propertyType macromolecule (below also referred to as side chain type macromolecule), uses aforementioned polymer composition and the film that obtains is that have canShow the high molecular film of photonasty side chain type of liquid crystal liquid crystal property. This film is without carrying out brushing processing, by polarizing light irradiationCarry out orientation process. And, carrying out after polarizing light irradiation, via the operation of this side chain type polymeric membrane of heating, thereby becomeBe endowed the film (below also referred to as liquid crystal orientation film) of orientation control ability. Now, show by polarizing light irradiationSmall anisotropy become driving force, the side chain type macromolecule of liquid crystal liquid crystal property self is because of self assembly reorientation effectively. ItsAs a result, can realize efficient orientation process as liquid crystal orientation film, obtain being endowed the liquid crystal of high orientation control abilityAlignment films.

Below, be elaborated for embodiments of the present invention.

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

[I] by contain (A) side chain type macromolecule and (B) polymer composition of organic solvent be coated on and there is transverse electric fieldDrive with on the substrate of conducting film and form the operation of film, described (A) side chain type macromolecule is in specific temperature rangeThe photonasty side chain type macromolecule that shows liquid crystal liquid crystal property, also has the side chain shown in above-mentioned formula (0);

The operation that [III] heats the film obtaining in [II].

By above-mentioned operation, can obtain the transverse electric field driving liquid crystal that has been endowed orientation control ability and represent elementWith liquid crystal orientation film, can obtain the substrate with this liquid crystal orientation film.

In addition, except substrate obtained above (the 1st substrate), by preparing the 2nd substrate, can obtain transverse electric fieldDriving liquid crystal represents element.

For the 2nd substrate, except replacing and there is transverse electric with the substrate of conducting film with not thering is transverse electric field drivingField drives with outside the substrate of conducting film, by using above-mentioned operation [I]～[III] (to drive because use does not have transverse electric fieldEmploy the substrate of conducting film, therefore for convenient, in this application sometimes referred to as operation [I ']～[III ']), can obtainThere is the 2nd substrate of the liquid crystal orientation film that has been endowed orientation control ability.

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

[IV] 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 liquidThe mode that crystalline phase is right is carried out subtend configuration, thereby obtains the operation that liquid crystal represents element. Thus, can obtain transverse electric field drivesType liquid crystal represents element.

Below, [I]～[III] possessing for manufacture method of the present invention and each operation of [IV] describe.

In operation [I], have transverse electric field drive form painting with coated polymeric composition on the substrate of conducting filmFilm, described polymer composition contains side chain type macromolecule, organic solvent and amines as required, described side chain typeMacromolecule is the photonasty side chain type macromolecule that shows liquid crystal liquid crystal property in specific temperature range, also has above-mentioned formula (0) instituteThe side chain showing, described amines has 1 primary amino radical and nitrogenous heteroaromatic in molecule, and aforementioned primary amino radical keyClose in aliphatic alkyl or non-aromatic ring type alkyl.

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

In addition, consider that being applicable to reflective liquid crystal represents element, also can use the opaque substrates such as silicon wafer.

Substrate has transverse electric field driving conducting film.

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

In addition, in the situation that reflective liquid crystal represents element, as conducting film, can list the catoptrical materials of meeting such as aluminiumMaterial etc., but be not limited to these.

The method that forms conducting film on substrate can be used existing known gimmick.

Thering is transverse electric field driving coated polymeric composition on the substrate of conducting film, especially on conducting film, be coated withCloth polymer composition.

This polymer composition using in manufacture method of the present invention contains: (A) in specific temperature range, showGo out the photonasty side chain type macromolecule of liquid crystal liquid crystal property; (B) organic solvent; And according to thering is 1 uncle's ammonia in (C) molecule of expectingBase and nitrogenous heteroaromatic and aforementioned primary amino radical are bonded to the amine compounds of aliphatic alkyl or non-aromatic ring type alkylThing.

The side chain type of<<(A) macromolecule>>

(A) composition is the photonasty side chain type macromolecule that shows liquid crystal liquid crystal property in specific temperature range, on also havingState the side chain shown in formula (0).

(A) side chain type macromolecule reacts and 100 DEG C～300 under the light of the wave-length coverage of 250nm～400nmDEG C temperature range in show liquid crystal liquid crystal property.

(A) side chain type macromolecule preferably has the photonasty reacting because of the light of the wave-length coverage of 250nm～400nmSide chain.

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

(A) the high molecular main chain bonding of side chain type there is photosensitive side chain, it is responded in light and can be cross-linkedReaction, isomerization reaction or light fries' rearrangement. There is photosensitive side-chain structure and be not particularly limited, be contemplated to be and respond in lightAnd the structure of generation cross-linking reaction or light fries' rearrangement is more contemplated to be the structure that cross-linking reaction occurs. Now, even if be exposed toThe external stresses such as heat also can keep the orientation control ability having realized steadily in the long term. Can show the photonasty of liquid crystal liquid crystal propertyAs long as the structure of side chain type polymeric membrane meets this specific character, be just not particularly limited, in preferential side chain structure, have upright and outspokenLiquid crystal ultimate constituent. Now, when this side chain type macromolecule is made to liquid crystal orientation film, can obtain stable liquid crystal aligning.

(A) to give voltage retention (VHR) etc. reliable by having the group shown in above-mentioned formula (0) for side chain type macromoleculeThe liquid crystal orientation film that property is high. Consider this be because: while making liquid crystal orientation film, the group shown in above-mentioned formula (0) as crosslinking agent thatPlay a role, thereby film density improves, ionic impurity is minimized to the stripping in liquid crystal sample.

This high molecular structure example is as made following structure: have main chain and be bonded to its side chain, this side chain toolThere are the liquid crystal ultimate constituents such as xenyl, terphenyl, benzyl ring hexyl, phenylamino benzoic acid ester group, azobenzene and are bonded to front endThe induction light of portion and the photonasty group of cross-linking reaction, isomerization reaction can occur; There is main chain and be bonded to its side chain, shouldSide chain has the phenylamino benzoic acid ester group that light Fries rearrangement both also can occur for liquid crystal ultimate constituent.

As can show liquid crystal liquid crystal property photonasty side chain type polymeric membrane structure have more style, be preferably and haveThe structure of following main chain and following side chain, described main chain by select free hydrocarbon, (methyl) acrylate, itaconate, fumarate,The free-radical polymerised bases such as maleate, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, ENBAt least a kind of formation in the group of group and siloxanes composition, described side chain comprises the group shown in above-mentioned formula (0) and following formula(1) in～(6) at least a kind.

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

Q3 is 0 or 1;

L1 is 0 or 1;

L2 is 0～2 integer;

L1 is 1 o'clock, and when T is singly-bound, B also represents singly-bound;

Side chain can be any photonasty side chain in the choosing group that freely following formula (7)～(10) form.

L represents 1～12 integer;

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

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

Side chain can be any photonasty side chain in the choosing group that freely following formula (11)～(13) form.

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

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

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

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

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

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

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

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

In addition, (A) side chain type macromolecule can have freely any in the group of following formula (21)～(31) composition of choosingLiquid crystal liquid crystal property side chain.

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

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

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

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

The above-mentioned photonasty side chain type macromolecule that can show liquid crystal liquid crystal property can be by having above-mentioned photonasty side chainPhotoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer carry out polymerization and obtain.

[thering is the monomer of side chain shown in formula (0)]

As have side chain shown in aforementioned formula (0) monomer have more style, be preferably have following polymerizable group andThe structure of following side chain, described polymerizable group is by selecting free hydrocarbon, (methyl) acrylate, itaconate, fumarate, MalaysiaThe free-radical polymerised groups such as acid esters, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, ENB andAt least a kind of formation in the group of siloxanes composition, above-mentioned formula for described side chain (0) represents.

Among that monomer, as the monomer with epoxy radicals, particularly, for example can list the contracting of (methyl) acrylic acidThe compounds such as water glyceride, (methyl) acrylic acid (3,4-epoxycyclohexyl) methyl esters, allyl glycidyl ether, wherein, can be listed asEnumerate (methyl) glycidyl acrylate, (methyl) acrylic acid (3,4-epoxycyclohexyl) methyl esters, 3-vinyl-7-oxa-pairRing [4.1.0] heptane, 1,2-epoxy radicals-5-hexene, 1,7-octadiene monoepoxide etc.

As the monomer with thiirane, particularly, can list in the above-mentioned monomer with epoxy radicals for exampleEpoxy radicals structure is replaced as monomer that thiirane forms etc.

As the monomer with aziridine, particularly, can list the ring in the above-mentioned monomer with epoxy radicals for exampleOxygen based structures is replaced as monomer that aziridine or 1-methylaziridine form etc.

As the monomer with oxetanyl, can list (methyl) acrylic acid for example with oxetanylEster etc. Among this monomer, be preferably 3-(methacryloxy methyl) oxetanes, 3-(acryloyl-oxy ylmethyl) oxygenHeterocycle butane, 3-(methacryloxy methyl)-3-Ethyloxetane, 3-(acryloyl-oxy ylmethyl)-3-ethyl oxygenHeterocycle butane, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-tri-Methyl fluoride oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 2-(methacryloxy methyl) oxetanes, 2-(acryloyl-oxy ylmethyl) oxa-ring fourthAlkane, 2-(methacryloxy methyl)-4-trifluoromethyl oxetanes, 2-(acryloyl-oxy ylmethyl)-4-trifluoromethylOxetanes, can list 3-(methacryloxy methyl)-3-Ethyloxetane, 3-(acryloxy firstBase)-3-Ethyloxetane etc.

As the monomer with Thietane base, be for example preferably the oxa-having in the monomer of oxetanylCyclobutane base is replaced into the monomer that Thietane base forms.

As the monomer with Azetane base (アゼタ Application base, azetidinyl), be preferably and for example will there is oxa-Oxetanyl in the monomer of cyclobutane base is replaced into the monomer that Azetane base forms.

Among above-mentioned, from the viewpoint of the property obtained etc., be preferably and there is the monomer of epoxy radicals and there is oxetanesThe monomer of base, more preferably has the monomer of epoxy radicals. Wherein, from the viewpoint of the property obtained, be preferably (methyl) acrylic acidEthylene oxidic ester.

[photoreactivity side chain monomer]

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

The photoreactive group having as side chain, is preferably following structure and derivative thereof.

As the style that has more of photoreactivity side chain monomer, be preferably and there is following polymerizable group and following photonasty sideThe structure of chain: described polymerizable group by select free hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate,Free-radical polymerised group and the silica such as alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, ENBAt least a kind of formation in the group of alkane composition; And described photonasty side chain comprises at least a kind in above-mentioned formula (1)～(6), excellentElect the photonasty side chain of at least a kind that for example comprises in above-mentioned formula (7)～(10) as, comprise in above-mentioned formula (11)～(13) extremelySensitization shown in photonasty side chain shown in the photonasty side chain of few a kind, above-mentioned formula (14) or (15), above-mentioned formula (16) or (17)Photonasty side chain shown in property side chain, above-mentioned formula (18) or (19), the photonasty side chain shown in above-mentioned formula (20).

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

In formula, R represents hydrogen atom or methyl; S represents the alkylidene of carbon number 2～10; R¹⁰Represent Br or CN; S represents carbon number 2～10 alkylidene; U represents 0 or 1; And Py represents 2-pyridine radicals, 3-pyridine radicals or 4-pyridine radicals. In addition, v represents 1 or 2.

[liquid crystal liquid crystal property side chain monomer]

Liquid crystal liquid crystal property side chain monomer refers to following monomer: the high molecular form that is derived from this monomer reveals liquid crystal liquid crystal property, this macromoleculeCan form mesogenic group at side chain position.

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

As the style that has more of liquid crystal liquid crystal property side chain monomer, be preferably the knot with following polymerizable group and following side chainStructure, described polymerizable group is by selecting free hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, α-methyleneThe free-radical polymerised groups such as base-gamma-butyrolacton, styrene, vinyl, maleimide, ENB and siloxanes compositionGroup at least a kind of formation, described side chain comprises at least a kind in above-mentioned formula (21)～(31).

(A) side chain type macromolecule can obtain by the polymerisation of the above-mentioned photoreactivity side chain monomer that shows liquid crystal liquid crystal property. In addition, can be by not showing the photoreactivity side chain monomer of liquid crystal liquid crystal property and the copolymerization of liquid crystal liquid crystal property side chain monomer, performance fluidThe copolymerization of the photoreactivity side chain monomer of crystallinity and liquid crystal liquid crystal property side chain monomer obtains. And then, do not damaging liquid crystal liquid crystal property performance energyIn the scope of power, can carry out copolymerization with other monomer.

As other monomer, can list the monomer that can carry out Raolical polymerizable that for example can industrial obtain.

As the concrete example of other monomer, can list unsaturated carboxylic acid, acrylate compounds, methacrylatedCompound, maleimide compound, acrylonitrile, maleic anhydride, distyryl compound and vinyl compound etc.

As the concrete example of unsaturated carboxylic acid, can list acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acidDeng.

As acrylate compounds, can list for example methyl acrylate, ethyl acrylate, isopropyl acrylate, thirdAlkene acid benzyl ester, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthryl methyl esters, phenyl acrylate, acrylic acid 2,2,2-trifluoro secondEster, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2-methoxyl group ethyl ester, methoxyl group triethylene glycolAcrylate, acrylic acid 2-ethoxy ethyl ester, tetrahydrofurfuryl acrylate, acrylic acid 3-methoxyl group butyl ester, acrylic acid 2-methyl-2-Adamantane esters, acrylic acid 2-propyl group-2-adamantane esters, acrylic acid 8-methyl-8-tri-encircle ester and acrylic acid 8-second in the last of the ten Heavenly stemsBase-8-tri-encircles ester in the last of the ten Heavenly stems etc.

As methacrylate compound, can list for example methyl methacrylate, EMA, methylIsopropyl acrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthryl methyl esters,Phenyl methacrylate, methacrylic acid 2,2,2-trifluoro ethyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, firstBase isobornyl acrylate, methacrylic acid 2-methoxyl group ethyl ester, methoxyl group triethylene glycol methacrylate, methacrylic acid2-ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3-methoxyl group butyl ester, methacrylic acid 2-methyl-2-goldJust Arrcostab, methacrylic acid 2-propyl group-2-adamantane esters, methacrylic acid 8-methyl-8-tri-encircle ester and methyl-prop in the last of the ten Heavenly stemsOlefin(e) acid 8-ethyl-8-tri-encircles ester in the last of the ten Heavenly stems etc.

As vinyl compound, can list for example vinethene, ethylene methacrylic ether, benzyl ethylene ether, 2-hydroxyethylVinethene, phenylvinyl ether and propyl vinyl ether etc.

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

As maleimide compound, can list for example maleimide, N-methyl maleimide, N-phenyl horseCome acid imide and N-N-cyclohexylmaleimide etc.

From improving reliability, this point that affects on liquid crystal aligning, the formula in side chain type macromolecule of the present invention(0) content of side chain shown in is preferably 0.1 % by mole～20 % by mole, more preferably 0.5 % by mole～10 % by mole, furtherBe preferably 1 % by mole～5 % by mole.

From liquid crystal aligning this point, the content of the photoreactivity side chain in side chain type macromolecule of the present invention is preferredBe 20 % by mole～99.9 % by mole, more preferably 30 % by mole～95 % by mole, more preferably 40 % by mole～90 rubYou are %.

From liquid crystal aligning this point, the content of the liquid crystal liquid crystal property side chain in side chain type macromolecule of the present invention is preferably80 % by mole following, more preferably 10 % by mole～70 % by mole, more preferably 20 % by mole～60 % by mole.

Side chain type macromolecule of the present invention can contain except side chain, photoreactivity side chain and the liquid crystal shown in above-mentioned formula (0)Other side chain outside property side chain. Its content is total side chain, photoreactivity side chain and the liquid crystal liquid crystal property side chain shown in above-mentioned formula (0)Content is its remainder while not meeting 100%.

For the high molecular manufacture method of side chain type of present embodiment, be not particularly limited, can utilize industrial answeringWith universal method. Particularly, can be by having utilized the sun of vinyl of liquid crystal liquid crystal property side chain monomer, photoreactivity side chain monomerIonic polymerization, radical polymerization, anionic polymerisation are manufactured. Among these, control the viewpoints such as easness from reaction, specialBe preferably radical polymerization.

As the polymerization initiator of radical polymerization, can use radical polymerization initiator, invertibity addition-cracking typeChain shifts the known compounds such as (RAFT) polymerization agent.

Free radical thermal polymerization is by being heated to the above compound that produces free radical of decomposition temperature. As thisKind of free radical thermal polymerization, can list such as peroxidating ketone (methyl ethyl ketone peroxide, Cyclohexanone peroxides etc.),Peroxidating diacyl class (acetyl peroxide, benzoyl peroxide etc.), hydroperoxide kind (hydrogen peroxide, TBHP,Cumene hydroperoxide etc.), dialkyl peroxide class (di-tert-butyl peroxide, dicumyl peroxide, two lauroyl peroxidesCompound etc.), ketal peroxide class (dibutyl peroxidating cyclohexane etc.), alkyl peroxyesters (new peroxide tert-butyl caprate,The peroxidating pivalic acid tert-butyl ester, peroxidating 2-ethyl cyclohexane acid tert-pentyl ester etc.), persulfuric acid salt (potassium peroxydisulfate, persulfuric acidSodium, ammonium persulfate etc.), azo based compound (azobis isobutyronitrile and 2,2 '-bis-(2-hydroxyethyl) azobis isobutyronitrile etc.).This free radical thermal polymerization can use separately a kind, or, also can be used in combination two or more.

Radical photopolymerization initator, as long as cause the compound of radical polymerization because of irradiation, is not just limit especiallyFixed. As this radical photopolymerization initator, can list benzophenone, Michler's keton, 4,4 '-bis-(lignocaine) hexichol firstKetone, xanthone, sulfo-xanthone, isopropyl xanthone, 2,4-diethyl sulfide is for xanthone, 2-EAQ, benzeneEthyl ketone, 2-hydroxy-2-methyl propiophenone, 2-hydroxy-2-methyl-4 '-cumene acetone, 1-hydroxycyclohexylphenylketone, differentPropyl group benzoin ether, isobutyl group benzoin ether, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, camphorQuinone, benzanthrone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-Morpholino phenyl)-1-butanone, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4,4 '-bis-(tert-butyl groupsPeroxy carbonyl) benzophenone, 3,4,4 '-tri-(t-butylperoxy carbonyl) benzophenone, 2,4,6-trimethylbenzoylDiphenyl phosphine oxide, 2-(4 '-methoxyl-styrene)-4, two (trichloromethyl) s-triazine of 6-, 2-(3 ', 4 '-dimethoxy benzeneVinyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(2 ', 4 '-dimethoxy-styryl)-4,6-two (trichloromethyl) is equalTriazine, 2-(2 '-methoxyl-styrene)-4, two (trichloromethyl) s-triazine of 6-, 2-(4 '-amyl phenyl ether vinyl)-4,6-Two (trichloromethyl) s-triazine, the p-N of 4-[, N-bis-(ethoxy carbonyl methyl)]-2,6-bis-(trichloromethyl) s-triazine, 1,3-Two (trichloromethyl)-5-(2 '-chlorphenyl) s-triazine, 1, two (trichloromethyl)-5-(4 '-methoxyphenyl) s-triazine of 3-, 2-(to dimethylamino styryl) benzoxazole, 2-(to dimethylamino styryl) benzothiazole, 2-mercaptobenzothiazole, 3,3 '-carbonyl two (7-lignocaine cumarin), 2-(Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetra-(4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-Lian miaowAzoles, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 3-(2-methyl-2-dimethylaminoPropiono) carbazole, 3, two (2-methyl-2-morpholino propiono)-9-dodecyl carbazoles of 6-, 1-hydroxy-cyclohexyl phenylKetone, two (5-2,4-cyclopentadiene-1-yls)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-yl)-phenyl) titanium, 3,3 ', 4,4 '-tetra-(t-butylperoxy carbonyl) benzophenone, 3,3 ', 4,4 '-tetra-(tertiary hexyl peroxy carbonyl) benzophenone, 3,3 '-bis-(firstOxygen base carbonyl)-4,4 '-bis-(t-butylperoxy carbonyl) benzophenone, 3,4 '-bis-(methoxycarbonyl)-4,3 '-bis-(tertiary fourthsBase peroxy carbonyl) benzophenone, 4,4 '-bis-(methoxycarbonyl)-3,3 '-bis-(t-butylperoxy carbonyl) benzophenone,2-(3-methyl-3H-benzothiazole-2-subunit)-1-naphthalene-2-base-ethyl ketone or 2-(3-methyl isophthalic acid, 3-benzothiazole-2(3H)-subunit)-1-(2-benzoyl) ethyl ketone etc. These compounds can use separately, also can mix two or more makingWith.

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

As showing the organic solvent using in the high molecular polymerisation of photonasty side chain type of liquid crystal liquid crystal property, onlyIf the organic solvent that the macromolecule generating can dissolve is just not particularly limited. Below list its concrete example.

Can list: DMF, DMA, METHYLPYRROLIDONE, N-ethyl-2-Pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-DingLactone, isopropyl alcohol, methoxy amylalcohol, cinene, ethyl pentyl group ketone, methyl nonyl ketone, MEK, methyl isoamyl ketone,Methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl card mustAlcohol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol list isopropyl ether, ethylene glycol monobutyl ether, propane diols, propane diolsMonoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate,Diethylene glycol dimethyl ether, DPG monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, DPGMonoacetate list ether, DPG list propyl ether, DPG monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acidEster, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, fourthAcid butyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ether, dioxs, n-hexane, pentane, normal octane, diethylEther, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, the positive fourth of acetic acidEster, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-c acid methyl secondEster, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxypropionic acid fourthEster, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxyl group-N, N-dimethyl propylene acid amides, 3-ethyoxyl-N, N-Dimethyl propylene acid amides, 3-butoxy-N, N-dimethyl propylene acid amides etc.

These organic solvents can be used alone, but also also mix together. And then, even do not dissolve generated high scoreThe solvent of son, as long as in the scope that can not separate out at generated macromolecule, also can be mixed in above-mentioned organic solvent and makeWith.

In addition, in radical polymerization, the oxygen in organic solvent can become the reason that hinders polymerisation, therefore organic moltenAgent is degassed rear use as much as possible preferably.

Polymerization temperature when radical polymerization can be selected the arbitrary temp of 30 DEG C～150 DEG C, is preferably 50 DEG C～100 DEG CScope. In addition, reaction can be carried out with any concentration, is difficult to obtain the polymer of HMW when concentration is too low, concentration mistakeGao Shi, the viscosity of reactant liquor becomes too high and is difficult to stir equably, and therefore monomer concentration is preferably 1 quality %～50 matterAmount %, 5 quality %～30 quality % more preferably. Initial reaction stage is carried out with high concentration, can append thereafter organic solvent.

In above-mentioned Raolical polymerizable, when radical polymerization initiator is more with respect to the ratio of monomer, gained is highThe molecular weight of molecule diminishes, and radical polymerization initiator is during with respect to the ratio less of monomer, the high molecular molecule quantitative change of gainedGreatly, therefore, the ratio of radical initiator is preferably 0.1 % by mole～10 % by mole with respect to polymerization single polymerization monomer. In addition, when polymerizationAlso can append various monomer components, solvent, initator etc.

[recovery of polymer]

That above-mentioned reaction obtains from utilizing, can the to show liquid crystal liquid crystal property high molecular reaction solution of photonasty side chain typeWhile reclaiming the macromolecule generating, reaction solution is fed into poor solvent, makes these polymer precipitations. As for heavyThe poor solvent forming sediment, can list methyl alcohol, acetone, hexane, heptane, butyl cellosolve, heptane, MEK, methylisobutylketone, secondAlcohol, toluene, benzene, diethyl ether, ethyl methyl ether, water etc. The polymer being fed in poor solvent and precipitation occurs can filter backAfter receipts, under normal pressure or decompression, carry out air drying or heat drying. In addition, repeat to make for 2 times～10 times precipitation to reclaimWhen polymer is dissolved in the operation of organic solvent precipitation recovery more again, can reduce the impurity in polymer. As nowPoor solvent, can list such as alcohols, ketone, hydrocarbon etc., when use is selected from the more than 3 kinds poor solvent among these, refiningEfficiency further improves, so preferably.

About the high molecular molecular weight of (A) of the present invention side chain type, consider when gained is coated with film strength, formation filmWhen the uniformity of workability and film, utilize GPC (GelPermeationChromatography, gel permeation chromatography)The weight average molecular weight that method is measured is preferably 2000～1000000, more preferably 5000～200000.

[preparation of polymer composition]

The polymer composition using in the present invention is preferably prepared into the form of coating fluid, for being applicable to forming liquid crystal aligningFilm. , polymer composition used in the present invention is preferably dissolved in organic molten for the resinous principle that forms resin coatingPrepared by the form of the solution that agent forms. Herein, this resinous principle refers to the liquid crystal liquid crystal property that can show that comprises above-mentioned explanationThe high molecular resinous principle of photonasty side chain type. Now, the content of resinous principle is preferably 1 quality %～20 quality %, more excellentElect 3 quality %～15 quality % as, be particularly preferably 3 quality %～10 quality %.

In the polymer composition of present embodiment, aforementioned resin composition can be to be all above-mentionedly can show fluidThe photonasty side chain type macromolecule of crystallinity, not damaging in the scope of liquid crystal expressive ability and photosensitive property, also can mix and removeOther polymer outside this. Now, the content of other polymer in resinous principle is 0.5 quality %～80 quality %, excellentElect 1 quality %～50 quality % as.

This other polymer can list for example comprise poly-(methyl) acrylate, polyamic acid, polyimides etc. andIt not high molecular polymer of photonasty side chain type that can show liquid crystal liquid crystal property etc.

The polymer composition using in the present invention preferably has specific amines, particularly, is in moleculeThere is 1 primary amino radical and nitrogenous heteroaromatic, and aforementioned primary amino radical is bonded to aliphatic alkyl or non-aromatic ring type hydrocarbonThe amines of base. By containing described amines, in the time making liquid crystal orientation film, be perhaps because reduce ionic impurityStripping and promote the cross-linking reaction of group shown in aforementioned formula (0), thereby can obtain the liquid crystal orientation film that durability is higher.

Specific amines as long as can bring into play in the time that polymer composition used in the present invention forms liquid crystal orientation filmFollowing effect i) and/or ii), be just not particularly limited. I) ionic in the Interfacial Adsorption liquid crystal of liquid crystal orientation film of performanceImpurity and/or, ii) voltage retention improved.

The amount of specific amines is as long as the above-mentioned effect of performance is just not particularly limited, in polymerization used in the present inventionIn compositions 100 mass parts, be 0.01～10 mass parts, be preferably 0.1～5 mass parts.

As the concrete example of aliphatic alkyl, can list straight chain shape alkylidene, have apparatus derivatorius alkylidene, haveThe divalent alkyl of unsaturated bond etc. The carbon number of aliphatic alkyl is preferably 1～20, and more preferably 1～15, more preferably 1～10。

As the concrete example of the non-aromatic ring type alkyl of divalent, can list cyclopropane ring, cyclobutane ring, pentamethylene ring,Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecaneRing, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring 20 carbonAlkane ring, three ring icosane rings, three ring docosane rings, norbornane ring, decahydro naphthalene nucleus, ENB ring, adamantane ring etc.Be preferably the ring that comprises 3～20 carbon, more preferably comprise 3～15 carbon ring, more preferably comprise 3～10 carbonThe non-aromatic ring type alkyl of ring.

The nitrogenous heteroaromatic comprising in amines can be to contain at least 1, preferably contain 1～4 and be selected fromBy following formula [20a], formula [20b] and formula [20c] (in formula, Z₂For straight chain or the branch alkyl of carbon number 1～5) composition group inThe aromatic series ring type hydrocarbon of structure.

Particularly, can list pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinolineQuinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidineRing, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzo thiopheneAzoles ring, phenthazine Huan, oxadiazole rings, acridine ring etc. And then, the carbon atom of these nitrogenous heteroaromatics optionally have comprise assortedThe substituting group of atom.

Preferred amines can be following formula A-[1] (in formula, Y₁₁For thering is aliphatic alkyl or non-aromatic ringThe divalent organic group of formula alkyl, Y₁₂For nitrogenous heteroaromatic) shown in amines. Formula A-[1] in, Y₁₂As long as havingThe divalent organic group of aliphatic alkyl or non-aromatic ring type alkyl, is just not particularly limited.

Formula A-[1] in preferred Y₁₁Can be to have to be selected from the non-aromatic of the aliphatic alkyl of carbon number 1～20 and carbon number 3～20The divalent organic group of a kind in fragrant family ring type alkyl. As non-aromatic ring type alkyl, can list said structure. Y₁₁Can be morePreferably list aliphatic alkyl, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, the cycloheptane of carbon number 1～15Ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, fallBornylene ring, adamantane ring etc. Y₁₁The particularly preferably straight chain of carbon number 1～10 or branch alkylidene.

In addition, Y₁₁In not adjacent with the amino any aliphatic alkyl comprising or non-aromatic ring type alkyl-CH₂-optionally by-O-,-NH-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-CO-,-S-,-S (O)₂-、-CF₂-、-C(CF₃)₂-、-C(CH₃)₂-、-Si(CH₃)₂-、-O-Si(CH₃)₂-、-Si(CH₃)₂-O-、-O-Si(CH₃)₂The cyclic hydrocarbon of-O-, divalentBase or heterocycle displacement. In addition, the hydrogen atom that is bonded to any carbon atom optionally by the straight chain of carbon number 1～20 or branch alkylidene,Replacing containing fluoroalkyl, heterocycle, fluorine atom, hydroxyl of cyclic hydrocarbon group, carbon number 1～10.

As the concrete example of divalent cyclic hydrocarbon group, can list phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, azulenes, indenes ring, fluorenes ring,Anthracene nucleus, phenanthrene ring, non-that alkene ring, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, ring ninth of the ten Heavenly StemsAlkane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecaneRing, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring icosane ring, three ring icosane rings, three ring docosaneRing, norbornane ring, decahydro naphthalene nucleus, ENB ring, adamantane ring etc.

In addition, as the concrete example of divalent heterocycle, can list pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring,Pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, pyrazolineRing, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, indolesRing, quinoxaline ring, benzothiazole ring, phenthazine Huan, oxadiazole rings, acridine ring etc.

Formula A-[1] in Y₁₂Nitrogenous heteroaromatic, with above-mentioned can be similarly to contain free style [20a], the formula selectedThe aromatic series ring type hydrocarbon of at least 1 structure in the group of [20b] and formula [20c] composition. As its concrete example, can list above-mentionedStructure. Among these, be preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring,Pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepines ring, two azepines rings, naphthyridines ring, azophenlyene ring, phthalazinesRing.

In addition, the carboxyl from nitrogenous heteroaromatic and specific polyimides forms salt, is called as the static phase of hydrogen bondThe viewpoint of mutual effect easness is set out, Y₁₁Preferably be bonded to Y₁₂In comprise not with formula [20a], formula [20b] and formula [20c] phaseAdjacent substituting group.

And then, formula A-[1] as Y₁₂The carbon atom of nitrogenous heteroaromatic optionally there is halogen atom and/or organicThe substituting group of base, this organic group optionally contains the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.

Formula A-[1] in Y₁₁With Y₁₂Preferred compositions be: Y₁₁For have select free carbon number 1～20 aliphatic alkyl and1 kind of divalent organic group in the group of the non-aromatic ring type alkyl composition of carbon number 3～20, Y₁₂For pyrrole ring, imidazole ring, pyrazolesRing, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring,Azepines ring, two azepines rings, naphthyridines ring, azophenlyene ring or phthalazines ring. It should be noted that Y₁₂The carbon of nitrogenous heteroaromaticAtom optionally has the substituting group of halogen atom and/or organic group, and this organic group can contain oxygen atom, sulphur atom, nitrogenThe hetero atoms such as atom.

As further preferred amines, be following formula A-[2] (in formula, Y₁₃For the fat of the divalent of carbon number 1～10Family's alkyl or non-aromatic ring type alkyl, Y₁₄For singly-bound or-O-,-NH-,-S-,-SO₂-or the divalent organic group of carbon number 1～19Group. In addition, Y₁₃And Y₁₄The total carbon atom having is 1～20. Y₁₅For nitrogenous heteroaromatic. ) shown in amines.

Formula A-[2] in Y₁₃For aliphatic alkyl or the non-aromatic ring type alkyl of the divalent of carbon number 1～10. If listIts concrete example is the straight chain of carbon number 1～10 or branch alkylidene, the unsaturated alkylene of carbon number 1～10, cyclopropane ring, ringButane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, ring tenDioxane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring tenNine alkane rings, ring icosane ring, three ring icosane rings, three ring docosane rings, norbornane ring, decahydro naphthalene nucleus, norborneolAlkene ring, adamantane ring etc. Can more preferably list the straight chain of carbon number 1～10 or branch alkylidene, cyclopropane ring, cyclobutaneRing, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecaneRing, ring tridecane ring, ring tetradecane ring, ENB ring, adamantane ring. Be particularly preferably straight chain or the branch of carbon number 1～10Alkylidene.

Y₁₃In in any aliphatic alkyl that comprise, not adjacent with amino or non-aromatic ring type alkyl-CH₂-RenChoosing quilt-O-,-NH-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-CO-,-S-,-S (O)₂-、-CF₂-、-C(CF₃)₂-、-C(CH₃)₂-、-Si(CH₃)₂-、-O-Si(CH₃)₂-、-Si(CH₃)₂-O-、-O-Si(CH₃)₂The cyclic hydrocarbon group of-O-, divalent or heterocycleDisplacement. In addition, the hydrogen atom that is bonded to any carbon atom is optionally by the straight chain of carbon number 1～20 or branch alkyl, cyclic hydrocarbon group, carbonSeveral 1～10 replace containing fluoroalkyl, heterocycle, fluorine atom, hydroxyl. The cyclic hydrocarbon group of herein mentioning and heterocycle and formula A-[1] inY₁₁The meaning of described definition is identical.

Formula A-[2] in Y₁₄For singly-bound or-O-,-NH-,-S-,-SO₂-or the divalent organic group of carbon number 1～19. This carbonSeveral 1～19 divalent organic group is the divalent organic group with 1～19 carbon atom, optionally comprises oxygen atom, nitrogen-atoms, sulphurAtom, silicon atom etc. Below list this Y₁₄Concrete example.

For example can list singly-bound ,-O-,-NH-,-S-,-SO₂-, the alkyl of carbon number 1～19 ,-CO-O-,-O-CO-,-CO-NH-、-NH-CO-、-CO-、-CF₂-、-C(CF₃)₂-、-CH(OH)-、-C(CH₃)₂-、-Si(CH₃)₂-、-O-Si(CH₃)₂-、-Si(CH₃)₂-O-、-O-Si(CH₃)₂-O-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctaneRing, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring,Ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring icosane ring, three ring icosane rings, three ringsDocosane ring, norbornane ring, decahydro naphthalene nucleus, ENB ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, azulenes,Indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring, non-that alkene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidineRing, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, threeAzoles ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring,Phenthazine Huan, oxadiazole rings, acridine Huan, oxazole ring, piperazine ring, piperidine ring, diox ring, morpholine ring etc. As Y₁₄, optionally bagContain two or more in these.

Comprise concrete example of more than two kinds as described, can list-NH-CH₂-、-NH-C₂H₄-、-NH-C₃H₆-、-NH-C₄H₈-、-S-CH₂-、-S-C₂H₄-、-S-C₃H₆-、-S-C₄H₈-、-O-CH₂-、-O-C₂H₄-、-O-C₃H₆-、-O-C₄H₈-、-NH-CO-CH₂-、-NH-CO-C₂H₄-、-NH-CO-C₃H₆-、-NH-CO-C₄H₈-、-CO-CH₂-、-CO-C₂H₄-、-CO-C₃H₆-、-CO-C₄H₈-、-CO-NH-CH₂-、-CO-NH-C₂H₄-、-CO-NH-C₃H₆-、-CO-NH-C₄H₈-、-NH-CH₂-CH(CH₃)-、-NH-C₂H₄-CH(CH₃)-、-NH-C₃H₆-CH(CH₃)-、-NH-C₄H₈-CH(CH₃)-、-S-CH₂-CH(CH₃)-、-S-C₂H₄-CH(CH₃)-、-S-C₃H₆-CH(CH₃)-、-S-C₄H₈-CH(CH₃)-、-O-CH₃-CH(CH₃)-、-O-C₂H₄-CH(CH₃)-、-O-C₃H₆-CH(CH₃)-、-O-C₄H₈-CH(CH₃)-、-NH-CO-CH₂-CH(CH₃)-、-NH-CO-C₂H₄-CH(CH₃)-、-NH-CO-C₃H₆-CH(CH₃)-、-NH-CO-C₄H₈-CH(CH₃)-、-CH(OH)-CH₂-、-CH(OH)-C₂H₄-、-CH(OH)-C₃H₆-、-CH(OH)-C₄H₈-、-CH(CH₂OH)-CH₂-、-CH(CH₂OH)-C₂H₄-、-CH(CH₂OH)-C₃H₆-、-CH(CH₂OH)-C₄H₈-、-NH-CH(CH₂OH)-CH₂-、-CO-NH-CH(CH₂OH)-CH₂-、-NH-CO-CH(CH₂OH)-CH₂-、-CO-CH(CH₂OH)-CH₂-、-S-CH(CH₂OH)-CH₂-、-O-CH(CH₂OH)-CH₂-、-CH(N(CH₃)₂)-、-C₆H₄-O-、-C₆H₄-NH-、-C₆H₄-CO-NH-、-C₆H₄-NH-CO-、-C₆H₄-CO-、-C₆H₄-CH₂-、-C₆H₄-S-etc.

Formula A-[2] in Y₁₅For nitrogenous heteroaromatic, with formula A-[1] in Y₁₂Definition identical. Concrete as itExample, can list and above-mentioned Y₁₂Identical structure. Among these, be preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidineRing, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepines ring, two a word used for translation heptanBecause of ring, naphthyridines ring, azophenlyene ring or phthalazines ring.

In addition, the carboxyl from nitrogenous heteroaromatic and specific polyimides forms salt, is called as the static phase of hydrogen bondThe viewpoint of mutual effect easness is set out, Y₁₄Preferably be bonded to Y₁₅In comprise not with formula [20a], formula [20b] or formula [20c] phaseAdjacent carbon atom.

And then, formula A-[2] as Y₁₅The carbon atom of nitrogenous heteroaromatic optionally there is halogen atom and/or organicThe substituting group of group, this organic group optionally contains the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.

Formula A-[2] in Y₁₃、Y₁₄With Y₁₅Preferred compositions be: Y₁₃For the straight chain of carbon number 1～10 or branch alkylidene, ringPropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring 11Alkane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, ENB ring or adamantane ring, Y₁₄For singly-bound, carbon number 1～10Straight chain or branch alkylidene ,-O-,-NH-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-CO-,-S-,-SO₂-、-CF₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-O-Si(CH₃)₂-、-Si(CH₃)₂-O-、-O-Si(CH₃)₂-O-、-CH(OH)-、-NH-CH₂-、-NH-C₂H₄-、-NH-C₃H₆-、-NH-C₄H₈-、-S-CH₂-、-S-C₂H₄-、-S-C₃H₆-、-S-C₄H₈-、-O-CH₂-、-O-C₂H₄-、-O-C₃H₆-、-O-C₄H₈-、-NH-CO-CH₂-、-NH-CO-C₂H₄-、-NH-CO-C₃H₆-、-NH-CO-C₄H₈-、-CO-CH₂-、-CO-C₂H₄-、-CO-C₃H₆-、-CO-C₄H₈-、-CO-NH-CH₂-、-CO-NH-C₂H₄-、-CO-NH-C₃H₆-、-CO-NH-C₄H₈-、-NH-CH₂-CH(CH₃)-、-NH-C₂H₄-CH(CH₃)-、-NH-C₃H₆-CH(CH₃)-、-NH-C₄H₈-CH(CH₃)-、-S-CH₂-CH(CH₃)-、-S-C₂H₄-CH(CH₃)-、-S-C₃H₆-CH(CH₃)-、-S-C₄H₈-CH(CH₃)-、-O-CH₃-CH(CH₃)-、-O-C₂H₄-CH(CH₃)-、-O-C₃H₆-CH(CH₃)-、-O-C₄H₈-CH(CH₃)-、-NH-CO-CH₂-CH(CH₃)-、-NH-CO-C₂H₄-CH(CH₃)-、-NH-CO-C₃H₆-CH(CH₃)-、-NH-CO-C₄H₈-CH(CH₃)-、-CH(OH)-CH₂-、-CH(OH)-C₂H₄-、-CH(OH)-C₃H₆-、-CH(OH)-C₄H₈-、-CH(CH₂OH)-CH₂-、-CH(CH₂OH)-C₂H₄-、-CH(CH₂OH)-C₃H₆-、-CH(CH₂OH)-C₄H₈-、-NH-CH(CH₂OH)-CH₂-、-CO-NH-CH(CH₂OH)-CH₂-、-NH-CO-CH(CH₂OH)-CH₂-、-CO-CH(CH₂OH)-CH₂-、-S-CH(CH₂OH)-CH₂-、-O-CH(CH₂OH)-CH₂-、-CH(N(CH₃)₂)-、-C₆H₄-O-、-C₆H₄-NH-、-C₆H₄-CO-NH-、-C₆H₄-NH-CO-、-C₆H₄-CO-、-C₆H₄-CH₂-、-C₆H₄-S-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ringHendecane ring, cyclododecane ring, ENB ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, azulenes, indenes ring, fluorenes ring,Anthracene nucleus, phenanthrene ring, non-that alkene ring, Y₁₅For pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazoleRing, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepines ring, two azepines rings, naphthyridines ring, azophenlyene ring orPhthalazines ring. It should be noted that Y₁₅The carbon atom of nitrogenous heteroaromatic optionally there is halogen atom and/or organic groupSubstituting group, this organic group optionally contains the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.

Formula A-[2] in Y₁₃、Y₁₄With Y₁₅More preferably combination be: Y₁₃For the straight chain of carbon number 1～5 or branch alkylidene, ringPropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, ENB ring or adamantane ring, Y₁₄For singly-bound, carbon number1～5 straight chain or branch alkylidene ,-O-,-NH-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-CO-,-S-,-S(O)₂-、-CH(OH)-、-NH-CH₂-、-S-CH₂-、-O-CH₂-、-O-C₂H₄-、-NH-CO-CH₂-、-CO-CH₂-、-CO-NH-CH₂-、-NH-CH₂-CH(CH₃)-、-S-CH₂-CH(CH₃)-、-O-CH₃-CH(CH₃)-、-NH-CO-CH₂-CH(CH₃)-、-CH(OH)-CH₂-、-CH(OH)-C₂H₄-、-CH(CH₂OH)-CH₂-、-NH-CH(CH₂OH)-CH₂-、-CO-NH-CH(CH₂OH)-CH₂-、-NH-CO-CH(CH₂OH)-CH₂-、-CO-CH(CH₂OH)-CH₂-、-S-CH(CH₂OH)-CH₂-、-O-CH(CH₂OH)-CH₂-、-CH(N(CH₃)₂)-、-C₆H₄-O-、-C₆H₄-NH-、-C₆H₄-CO-NH-、-C₆H₄-NH-CO-、-C₆H₄-CO-、-C₆H₄-CH₂-、-C₆H₄-S-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, ENB ring, adamantaneRing, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, azulenes, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring or non-that alkene ring, Y₁₅For pyrrole ring, imidazolesRing, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinolineQuinoline ring, azepines ring, two azepines rings, naphthyridines ring, azophenlyene ring or phthalazines ring. It should be noted that Y₁₅Nitrogenous aromatic seriesThe carbon atom of heterocycle optionally has the substituting group of halogen atom and/or organic group, and this organic group optionally contains oxygen atom, sulphurThe hetero atom such as atom, nitrogen-atoms.

Formula A-[2] in Y₁₃、Y₁₄With Y₁₅Further preferred combination be: Y₁₃For straight chain or the branch Asia of carbon number 1～5Alkyl, cyclopropane ring, cyclobutane ring, pentamethylene ring or cyclohexane ring, Y₁₄For straight chain or the branch alkylene of singly-bound, carbon number 1～5Base ,-O-,-NH-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-CO-,-CH (OH)-,-NH-CH₂-、-S-CH₂-、-O-CH₂-、-NH-CO-CH₂-、-CO-CH₂-、-CO-NH-CH₂-、-NH-CH₂-CH(CH₃)-、-S-CH₂-CH(CH₃)-、-O-CH₃-CH(CH₃)-、-NH-CO-CH₂-CH(CH₃)-、-CH(OH)-CH₂-、-CH(OH)-C₂H₄-、-CH(CH₂OH)-CH₂-、-NH-CH(CH₂OH)-CH₂-、-CO-NH-CH(CH₂OH)-CH₂-、-NH-CO-CH(CH₂OH)-CH₂-、-CO-CH(CH₂OH)-CH₂-、-S-CH(CH₂OH)-CH₂-、-O-CH(CH₂OH)-CH₂-、-CH(N(CH₃)₂)-、-C₆H₄-O-、-C₆H₄-NH-、-C₆H₄-CO-NH-、-C₆H₄-NH-CO-、-C₆H₄-CO-、-C₆H₄-CH₂-、-C₆H₄-S-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, ringHeptane ring, ENB ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring or anthracene nucleus, Y₁₅For pyrrole ring, imidazole ring, pyrroleAzoles ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring or benzimidazole ring. NeedBright, Y₁₅The carbon atom of nitrogenous heteroaromatic optionally there is the substituting group of halogen atom and/or organic group, this is organicGroup optionally contains the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.

Formula A-[2] in Y₁₃、Y₁₄With Y₁₅Particularly preferred combination be: Y₁₃For straight chain or the branch alkylene of carbon number 1～5Base, cyclobutane ring or cyclohexane ring, Y₁₄For singly-bound ,-O-,-CO-O-,-O-CO-,-CO-NH-,-NH-CO-,-CH (OH)-, benzeneRing, naphthalene nucleus, fluorenes ring or anthracene nucleus, Y₁₅For pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring. It should be noted that Y₁₅'sThe carbon atom of nitrogenous heteroaromatic optionally has the substituting group of halogen atom and/or organic group, and this organic group optionally containsThere are the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.

As the concrete example of the certain amines compound of (B) of the present invention composition, can list the compound of M1～M156.

As preferred compound, can list M6～M8, M10, M16～M21, M31～M36, M40～M45, M47～M57、M59～M63、M68、M69、M72～M82、M95～M98、M100～M103、M108～M125、M128～M137、M139～M143, M149～M156. More preferably M6～M8, M16～M20, M32～M36, M40, M41, M44, M49～M54、M59～M62、M68、M69、M75～M82、M100～M103、M108～M112、M114～M116、M118～M121、M125、M134～M136、M139、M140、M143、M150、M152～M156。

The organic solvent using in polymer composition used in the present invention as long as can dissolving resin composition haveMachine solvent is just not particularly limited. Below list its concrete example.

Can list: DMF, DMA, METHYLPYRROLIDONE, N-methyl oneselfLactams, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, twoMethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3-methoxyl group-N, N-dimethyl propylene acid amides, 3-ethyoxyl-N, N-dimethyl propionylAmine, 3-butoxy-N, N-dimethyl propylene acid amides, 1,3-dimethyl-imidazolinone, ethyl pentyl group ketone, methyl nonyl ketone, MEK,Methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxyl-4-Methyl-2 pentanone, propane diols monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol,Diethylene glycol monoacetate, diethylene glycol dimethyl ether, DPG monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropyl twoAlcohol list ether, DPG monoacetate list ether, DPG list propyl ether, DPG monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, tripropylene glycol methyl ether etc. They can be used alone, but also also mix together.

The polymer composition using in the present invention can contain above-mentioned (A), (B) and (C) composition outside composition. AsIts example, can list the solvent or the compound that in the time of coated polymeric composition, improve film thickness uniformity, surface smoothness, carriesThe compound of the adaptation of high liquid crystal orientation film and substrate etc., but be not limited to this.

As the concrete example of solvent (poor solvent) that improves film thickness uniformity, surface smoothness, can list following moltenAgent.

Can list for example isopropyl alcohol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, firstBase cellosolve acetic acid esters, ethyl cellosolve acetate, BC, ethyl carbitol, ethyl carbitol acetic acid esters, second twoAlcohol, ethylene glycol acetate, ethylene glycol list isopropyl ether, ethylene glycol monobutyl ether, propane diols, propane diols monoacetate, propane diols listMethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, twoPropane diols monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, DPG monoacetate list ether, twoPropylene glycol monopropyl ether, DPG monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, tripropylene glycol methyl ether, 3-Methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, two isobutylsKetone, methylcyclohexene, propyl ether, two hexyl ethers, 1-hexanol, n-hexane, pentane, normal octane, diethyl ether, methyl lactate, lactic acid secondEster, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3-methoxyBase methyl propionate, 3-ethoxy-c acid methyl ethyl ester, 3-methoxy propyl acetoacetic ester, 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-thirdAlcohol, 1-phenoxy group-2-propyl alcohol, propane diols monoacetate, propylene-glycol diacetate, propane diols-1-monomethyl ether-2-acetic acid esters, thirdMono-ether-the 2-of glycol-1-acetic acid esters, DPG, 2-(2-ethyoxyl propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acidN-propyl, n-butyl lactate, isoamyl lactate etc. have the solvent of low surface tension etc.

These poor solvents can use a kind, also can mix use multiple. While using solvent as described above, forDo not make the dissolubility of the solvent entirety comprising in polymer composition significantly reduce, be preferably 5 quality %～80 of solvent entiretyQuality %, 20 quality %～60 quality % more preferably.

As the compound that improves film thickness uniformity, surface smoothness, can list fluorine is surfactant, silicon-typeSurfactant and nonionic are surfactant etc.

More specifically, can list for example Eftop (registration mark) 301, EF303, EF352 (TohkemproductsCorporation system), Megafac (registration mark) F171, F173, R-30 (DICCORPORATION system), FluoradFC430, FC431 (Sumitomo3MLimited system), AsahiGuard (registration mark) AG710 (Asahi Glass Co., LtdSystem), Surflon (registration mark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGCSEIMICHEMICALCO., LTD. system) etc. The usage ratio of these surfactants is with respect to the resin containing in polymer compositionComposition 100 mass parts are preferably 0.01 mass parts～2 mass parts, 0.01 mass parts～1 mass parts more preferably.

As the concrete example of compound of adaptation that improves liquid crystal orientation film and substrate, can list following containing of illustratingThe compound of functional silanes etc.

Can list for example 3-TSL 8330, APTES, 2-aminopropylTrimethoxy silane, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea propyl trimethoxy silicane, 3-urea propyl triethoxySilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES,N-triethoxysilylpropyltetrasulfide three second triamines, N-trimethoxy-silylpropyl three second triamines, 10-trimethoxy first siliconAlkyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxy monosilaneBase-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-aminoPropyl trimethoxy silicane, N-benzyl-APTES, N-phenyl-3-TSL 8330,N-phenyl-APTES, two (oxygen the ethylidene)-3-TSL 8330s of N-, two (the oxygen Asias of N-Ethyl)-APTES etc.

And then, while representing element in order to improve the adaptation of substrate and liquid crystal orientation film and to prevent from forming liquid crystal by backlightThe electrical characteristics reductions that cause etc. can contain the system of phenoplasts as following, change containing epoxy radicals in polymer compositionThe additive of compound. Below illustrate that concrete phenoplasts are additive, but be not limited to this structure.

As the concrete compound containing epoxy radicals, can exemplify ethylene glycol diglycidylether, polyethylene glycol two shrinksGlycerin ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycolDiglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol two shrinks sweetOil ether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N ' ,-four glycidyl group m-xylene diamine, 1,3-is two(N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N ' ,-four glycidyl group-4,4 '-diamino-diphenyl firstAlkane etc.

Use while being used for improving the compound of adaptation of liquid crystal orientation film and substrate, its consumption is with respect to combination of polymersResinous principle 100 mass parts that contain in thing are preferably 0.1 mass parts～30 mass parts, 1 mass parts～20 quality more preferablyPart. During by quantity not sufficient 0.1 mass parts, cannot expect to improve the effect of adaptation, during more than 30 mass parts, the orientation of liquid crystal hasTime variation.

As additive, also can use sensitising agent. Be preferably colourless sensitizer and triplet sensitizer.

As sensitising agent, have aromatic nitro compound, cumarin (7-lignocaine-4-methylcoumarin, 7-hydroxyl-4-methylcoumarin), coumarin ketone, carbonyl bicoumarin, aromatic series 2-hydroxy-ketone and by the amino aromatic series 2-hydroxyl replacingBase ketone (2-dihydroxy benaophenonel, single to (dimethylamino)-2-dihydroxy benaophenonel or two to (dimethylamino)-2-hydroxyl hexicholKetone), acetophenone, anthraquinone, xanthone, sulfo-xanthone, benzanthrone, thiazoline (2-benzoyl methylene-3-firstBase-β-aphthothiazoles quinoline, 2-(β-naphthoyl methylene)-3-methylbenzothiazole quinoline, 2-(α-naphthoyl methylene)-3-methylBenzothiazoline, 2-(4-dibenzoyl methylene)-3-methylbenzothiazole quinoline, 2-(β-naphthoyl methylene)-3-methyl-β-Aphthothiazoles quinoline, 2-(4-dibenzoyl methylene)-3-methyl-β-aphthothiazoles quinoline, 2-(to fluorobenzoyl methylene)-3-Methyl-β-aphthothiazoles quinoline), oxazoline (2-benzoyl methylene-3-methyl-β-Nai Bing oxazolines, 2-(β-naphthoyl AsiaMethyl)-3-first base benzoxazole quinoline, 2-(α-naphthoyl methylene)-3-first base benzoxazole quinoline, 2-(4-biphenyl acyl group methyleneBase)-3-first base benzoxazole quinoline, 2-(β-naphthoyl methylene)-3-methyl-β-naphthalene oxazoline, 2-(4-biphenyl acyl group methyleneBase)-3-methyl-β-naphthalene oxazoline, 2-(to fluorobenzoyl methylene)-3-methyl-β-naphthalene oxazoline), benzothiazole,Nitroaniline (meta nitro aniline or paranitroanilinum, 2,4,6-trinitroaniline) or nitro acenaphthene (5-nitro acenaphthene), (hydroxyl between 2-[(Base is to methoxyl group) styryl] benzothiazole, benzoin alkylether, N-alkylation phthalein ketone, acetophenone ketal (2,2-dimethoxyBase Phenyl ethyl ketone), naphthalene, anthracene (2-naphthalene methyl alcohol, 2-naphthalene-carboxylic acid, 9-anthryl carbinol and 9-anthracene carboxylic acid), chromene, azo indolizine,Plum Lip river cumarin etc.

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

In polymer composition, except above-mentioned substance, need only not damaging in the scope of effect of the present invention, for changingBecome the object of the electrical characteristics such as dielectric constant, electric conductivity of liquid crystal orientation film, can add dielectric substance, conductive materials, and then forIn the time making liquid crystal orientation film, improve the hardness of film, the object of density, can add cross-linked compound.

Above-mentioned polymer composition is coated on and has transverse electric field and drive and there is no spy by the method on the substrate of conducting filmXian Ding not.

About coating process, industrial serigraphy, hectographic printing, flexible printing or the ink-jet method etc. normally utilized are carried outMethod. As other coating process, there are infusion process, rolling method, slot coated method, spin-coating method (method of spin coating) or spraying processDeng, can use them according to object.

Thering is transverse electric field driving with after coated polymeric composition on the substrate of conducting film, utilize hot plate, thermal cycleThe heater meanses such as type baking oven or IR (infrared ray) type baking oven with 50～200 DEG C, preferably make solvent evaporation with 50～150 DEG C, therebyCan obtain film. Baking temperature is now preferably lower than the high molecular liquid crystalline phase performance of side chain type temperature.

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

In addition, after [I] operation and before next [II] operation, can also arrange cooling the substrate that is formed with filmTo the operation of room temperature.

In operation [II], the film obtaining in operation [I] is irradiated to polarized UV rays. The face of film is irradiated to polarizationWhen ultraviolet ray, across polarization plates, substrate is irradiated to polarized UV rays from particular aspects. As the ultraviolet ray that will use, can useWavelength is the ultraviolet ray of 100nm～400nm scope. Preferably, according to the film kind that will use, by selections such as wave filtersBest wavelength. And, for example, can choice for use wavelength be the ultraviolet ray of 290nm～400nm scope, so that can be selectiveGround brings out photo-crosslinking. As ultraviolet ray, can use the light for example being sent by high-pressure sodium lamp.

For the exposure of polarized UV rays, depend on the film that will use. About exposure, be preferably made as and realize Δ A1%～70% the scope of amount of polarized UV rays of maximum (below also referred to as Δ Amax) in, be more preferably made as 1%～In 50% scope, described Δ A is this film, be parallel to the ultraviolet absorbance of the direction of the polarization direction of polarized UV raysPoor with the ultraviolet absorbance of the direction of the polarization direction perpendicular to polarized UV rays.

In operation [III], the film of polarized UV rays has been irradiated in heating in operation [II]. Can be to being coated with by heatingFilm is given orientation control ability.

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

Heating-up temperature is preferably the temperature (hereinafter referred to as liquid crystal performance temperature) that side chain type macromolecule can show liquid crystal liquid crystal propertyTemperature range in. Measurable arriving: in the case of the film surface of film and so on, the liquid crystal of film coated surface performance temperature lower thanLiquid crystal performance temperature when whole observation can show the photonasty side chain type macromolecule of liquid crystal liquid crystal property. Therefore, heating-up temperature is more excellentElect as in the temperature range of liquid crystal performance temperature of film coated surface. , irradiate the temperature model of the heating-up temperature after polarized UV raysEnclose preferably using than the temperature of low 10 DEG C of the lower limit of the temperature range of the high molecular liquid crystal performance of side chain type used temperature as underLimit and using the temperature as the scope of the upper limit than the temperature of low 10 DEG C of the upper limit of this liquid crystal temperature range. Heating-up temperature is lower than upperWhile stating temperature range, there is the not tendency very of the anisotropy amplification effect of being come by the torrid zone in film, in addition, heating-up temperatureWhen too high compared with said temperature scope, exist and be coated with membrane stage inclining close to isotropic liquid condition (isotropic phase)To, now, be sometimes difficult to because self assembly is 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 solid-phase to liquid crystalline phaseMore than the glass transition temperature (Tg) that occurs to change mutually and from liquid crystalline phase to homogeneous phase (isotropic phase), occur to change mutuallyThe temperature that homogeneous phase transition temperature (Tiso) is following.

For the reason identical with the reason of recording in operation [I], the thickness of the film forming after heating can be preferably5nm～300nm, 50nm～150nm more preferably.

By thering is as above operation, in manufacture method of the present invention, can realize film is imported efficiently each to differentProperty. And, can manufacture efficiently the substrate with liquid crystal orientation film.

[IV] operation is that the transverse electric field obtaining in [III] is driven with the substrate on conducting film with liquid crystal orientation film(the 1st substrate) and the substrate with liquid crystal orientation film without conducting film similarly obtaining in above-mentioned [I ']～[III '](the 2nd substrate) carries out subtend configuration across liquid crystal in the relative mode of both liquid crystal orientation films, utilizes known method to makeLiquid crystal cells, thus the operation that the driving liquid crystal of transverse electric field represents element made. It should be noted that, operation [I ']～In [III '], except driving with the substrate of conducting film and replace and have that this is horizontal with not thering is transverse electric field in operation [I]Electric field driven, with outside the substrate of conducting film, can similarly be carried out with operation [I]～[III]. Operation [I]～[III] and operationThe difference of [I ']～[III '] is only to have or not above-mentioned conducting film, therefore omits the explanation of operation [I ']～[III '].

If list the production example that liquid crystal cells or liquid crystal represent element, can exemplify following method: in preparationThe 1st substrate of stating and the 2nd substrate scatter sept on the liquid crystal orientation film of a substrate, in becoming with liquid crystal aligning faceThe mode of side is pasted on another substrate, and the method for liquid crystal sealing is injected in decompression; Or, get to the liquid crystal that is scattered with septDrip after liquid crystal adhesive substrate the method that seals etc. to face. Now, the substrate of a side preferably uses and has transverse electricField drives the substrate with the electrode of comb teeth-shaped structure. Sept diameter be now preferably 1 μ m～30 μ m, more preferably 2 μ m～10 μ m. This sept diameter determines for the spacing of a pair of substrate of clamping liquid crystal layer, the i.e. thickness of liquid crystal layer.

In the manufacture method of the substrate with film of the present invention, polymer composition is coated on substrate and forms filmAfter, irradiate polarized UV rays. Then, by heat realize to importing efficiently in side chain type polymeric membrane each to differentProperty, thereby manufacture the substrate with liquid crystal orientation film that possesses liquid crystal aligning control ability.

In the present invention's film used, the molecule that utilizes the light reaction of side chain and the self assembly based on liquid crystal liquid crystal property to bring outThe principle of reorientation, realizes film is imported to anisotropy efficiently. In manufacture method of the present invention, side chain type macromolecule hasPhotocrosslinking reaction group during as the structure of photoreactive group, uses side chain type macromolecule on substrate, to form after film, irradiatesPolarized UV rays, after then heating, makes liquid crystal and represents element.

Below, there is the side chain type high molecular reality of photocrosslinking reaction group as the structure of photoreactive group using having usedThe mode of executing is called the 1st mode, has light fries' rearrangement group or carries out isomerized group as photoreactivity having usedThe high molecular embodiment of side chain type of the structure of group is called the 2nd mode, and describes.

Fig. 1 schematically illustrates in the 1st mode of the present invention to have used and had photocrosslinking reaction group as light reactionProperty group the side chain type macromolecule manufacture method that form, liquid crystal orientation film of structure in anisotropy import process oneThe figure of example. (a) of Fig. 1 is the figure that schematically shows the side chain type polymeric membrane state before polarizing light irradiation, and Fig. 1 (b) isThe figure of the side chain type polymeric membrane state after schematically illustrated polarizing light irradiation, after (c) of Fig. 1 is schematically illustrated heatingThe figure of side chain type polymeric membrane state, the anisotropy hour that especially imported, in the 1st mode of the present invention,The ultraviolet irradiation amount of [II] operation showing in the time making Δ A arrive in 1%～15% scope of maximum ultraviolet irradiation amountIntention.

Fig. 2 schematically illustrates in the 1st mode of the present invention to have used and had photocrosslinking reaction group as light reactionProperty group the side chain type macromolecule manufacture method that form, liquid crystal orientation film of structure in anisotropy import process oneThe figure of example. (a) of Fig. 2 is the figure that schematically shows the side chain type polymeric membrane state before polarizing light irradiation, and Fig. 2 (b) isThe figure of the side chain type polymeric membrane state after schematically illustrated polarizing light irradiation, after (c) of Fig. 2 is schematically illustrated heatingThe figure of side chain type polymeric membrane state, when the anisotropy that especially imported is large, in the 1st mode of the present invention,The ultraviolet irradiation amount of [II] operation showing in the time making Δ A reach in 15%～70% scope of maximum ultraviolet irradiation amountIntention.

Fig. 3 schematically illustrates in the 2nd mode of the present invention to have used and had photoisomerization group or above-mentioned formula(18) that the light fries' rearrangement group shown in forms as the side chain type macromolecule of the structure of photoreactive group, liquid crystal aligningAnisotropy in the manufacture method of film imports the figure of an example of processing. Fig. 3 (a) schematically shows before polarizing light irradiationThe figure of side chain type polymeric membrane state, (b) of Fig. 3 is that the side chain type macromolecule after schematically illustrated polarizing light irradiation is membranaceousThe figure of state, (c) of Fig. 3 is the figure of the side chain type polymeric membrane state after schematically illustrated heating, what especially imported is eachAnisotropy hour,, in the 2nd mode of the present invention, the ultraviolet irradiation amount of [II] operation makes Δ A reach maximum ultravioletSchematic diagram in 1%～70% scope of line exposure time.

Fig. 4 schematically illustrates to have used in the 2nd mode of the present invention to have not profit of the light shown in above-mentioned formula (19)This resets group as in the side chain type macromolecule manufacture method that form, liquid crystal orientation film of the structure of photoreactive groupAnisotropy imports the figure of an example of processing. (a) of Fig. 4 is the side chain type polymeric membrane schematically showing before polarizing light irradiationThe figure of state, (b) of Fig. 4 is the figure of the side chain type polymeric membrane state after schematically illustrated polarizing light irradiation, (c) of Fig. 4Be the figure of the side chain type polymeric membrane state after schematically illustrated heating, when the anisotropy that especially imported is large, existIn the 2nd mode of the present invention, the ultraviolet irradiation amount of [II] operation make Δ A reach 1% of maximum ultraviolet irradiation amount～Schematic diagram in 70% scope time.

In the 1st mode of the present invention, by film being imported to anisotropic processing, the ultraviolet irradiation amount of [II] operationIn the time making Δ A reach in 1%～15% scope of maximum ultraviolet irradiation amount, first, on substrate, form film 1. AsShown in Fig. 1 (a), in the film 1 forming on substrate, there is the structure of side chain 2 random alignment. According to the side chain 2 of film 1Random alignment, the liquid crystal ultimate constituent of side chain 2 and photonasty group also randomly orientation, this film 1 is isotropic.

In the 1st mode of the present invention, by film being imported to anisotropic processing, the ultraviolet irradiation amount of [II] operationIn the time making Δ A reach in 15%～70% scope of maximum ultraviolet irradiation amount, first, on substrate, form film 3. AsShown in Fig. 2 (a), in the film 3 forming on substrate, there is the structure of side chain 4 random alignment. According to the side chain 4 of film 3Random alignment, the liquid crystal ultimate constituent of side chain 4 and photonasty group also randomly orientation, this film 2 is isotropic.

In the 2nd mode of the present invention, by film being imported to anisotropic processing, application has been used has photoisomerizationWhen the high molecular liquid crystal orientation film of side chain type of the structure of the light fries' rearrangement group shown in property group or above-mentioned formula (18),The ultraviolet irradiation amount of [II] operation in the time making Δ A reach in 1%～70% scope of maximum ultraviolet irradiation amount, headFirst, on substrate, form film 5. As shown in Fig. 3 (a), in the film 5 forming on substrate, there are side chain 6 random alignmentStructure. According to the random alignment of the side chain 6 of film 5, the liquid crystal ultimate constituent of side chain 6 and photonasty group are also orientated randomly,This side chain type polymeric membrane 5 is isotropic.

In the 2nd mode of the present invention, by film being imported to anisotropic processing, application has been used has above-mentioned formula(19) when the high molecular liquid crystal orientation film of side chain type of the structure of the light fries' rearrangement group shown in, the ultraviolet ray of [II] operationExposure, in the time making Δ A reach in 1%～70% scope of maximum ultraviolet irradiation amount, first, forms and is coated with on substrateFilm 7. As shown in Fig. 4 (a), in the film 7 forming on substrate, there is the structure of side chain 8 random alignment. According to film 7The random alignment of side chain 8, also orientation randomly of the liquid crystal ultimate constituent of side chain 8 and photonasty group, this film 7 is isotropism.

In the 1st mode of this enforcement, the ultraviolet irradiation amount of [II] operation makes Δ A reach maximum ultraviolet irradiation amount1%～15% scope in time, this isotropic film 1 is irradiated to polarized UV rays. Thus, as shown in Fig. 1 (b) thatSample, side chain 2a's among the side chain 2 of arranging along the direction parallel with ultraviolet polarization direction, that there is photonasty groupPreferentially there is the light reactions such as dimerization reaction in photonasty group. Its result, the density that the side chain 2a of light reaction has occurred is being irradiatedOn ultraviolet polarization direction, slightly uprise, its result, gives very little anisotropy to film 1.

In the 1st mode of this enforcement, the ultraviolet irradiation amount of [II] operation makes Δ A reach maximum ultraviolet irradiation amount15%～70% scope in time, this isotropic film 3 is irradiated to polarized UV rays. Thus, as shown in Fig. 2 (b)Side chain 4a among the side chain 4 of arranging along the direction parallel with ultraviolet polarization direction like that,, that there is photonasty groupPhotonasty group preferentially there is the light reactions such as dimerization reaction. Its result, the density that the side chain 4a of light reaction has occurred is being shonePenetrate on ultraviolet polarization direction and uprise, its result, gives little anisotropy to film 3.

In the 2nd mode of this enforcement, application has been used has the light shown in photoisomerization group or above-mentioned formula (18)The high molecular liquid crystal orientation film of side chain type of the structure of fries' rearrangement group, the ultraviolet irradiation amount of [II] operation makes Δ AWhile reaching in 1%～15% scope of maximum ultraviolet irradiation amount, this isotropic film 5 is irradiated to polarization ultravioletLine. Thus, as shown in Fig. 3 (b), among the side chain 6 of arranging along the direction parallel with ultraviolet polarization direction,Preferentially there is the light reactions such as light fries' rearrangement in the photonasty base with the side chain 6a of photonasty group. Its result, has occurredThe density of the side chain 6a of light reaction slightly uprises on the polarization direction of irradiation ultraviolet radiation, and its result is given very little to film 5Anisotropy.

In the 2nd mode of this enforcement, application has been used the light fries' rearrangement group that has shown in above-mentioned formula (19)The high molecular film of side chain type of structure, the ultraviolet irradiation amount of [II] operation makes Δ A reach maximum ultraviolet irradiation amount1%～70% scope in time, this isotropic film 7 is irradiated to polarized UV rays. Thus, as shown in Fig. 4 (b) thatSample, side chain 8a's among the side chain 8 of arranging along the direction parallel with ultraviolet polarization direction, that there is photonasty groupPreferentially there is the light reactions such as light fries' rearrangement in photonasty group. Its result, the density that the side chain 8a of light reaction has occurred existsOn the polarization direction of irradiation ultraviolet radiation, uprise, its result, gives little anisotropy to film 7.

Then,, in the 1st mode of this enforcement, the ultraviolet irradiation amount of [II] operation makes Δ A reach maximum ultraviolet rayIn 1%～15% scope of exposure time, heat and make mesomorphic state irradiating film 1 after polarised light. Thus, as figureShown in 1 (c), in film 1, be parallel to irradiation ultraviolet radiation polarization direction direction with perpendicular to irradiation ultraviolet radiationBetween the direction of polarization direction, the amount difference of the cross-linking reaction of generation. Now, be parallel to the side of the polarization direction of irradiation ultraviolet radiationAmount to the cross-linking reaction producing is very little, and therefore work as plasticizer in this cross-linking reaction position. Therefore, perpendicular to photographPenetrate the liquid crystal liquid crystal property of direction of ultraviolet polarization direction higher than the liquid crystal liquid crystal property of direction of polarization direction that is parallel to irradiation ultraviolet radiation,Be parallel to the direction generation self assembly of the polarization direction of irradiation ultraviolet radiation, the side chain 2 that comprises liquid crystal ultimate constituent carries out reorientation.Its result, the very little anisotropy of the film 1 bringing out because of photo-crosslinking is amplified because of heat, gives larger to film 1Anisotropy.

Similarly, in the 1st mode of this enforcement, the ultraviolet irradiation amount of [II] operation makes Δ A reach maximum ultravioletIn 15%～70% scope of line exposure time, the film after polarizing light irradiation 3 is heated and make mesomorphic state. Thus,As shown in Fig. 2 (c), in side chain type polymeric membrane 3, in the direction of polarization direction that is parallel to irradiation ultraviolet radiation with verticalBetween the direction of the polarization direction of irradiation ultraviolet radiation, the amount difference of the cross-linking reaction of generation. Therefore, be parallel to irradiation ultraviolet radiationThe direction generation self assembly of polarization direction, the side chain 4 that comprises liquid crystal ultimate constituent carries out reorientation. Its result, because of photo-crosslinkingAmplifying because of heat compared with little anisotropy of the film 3 reacting and bring out, gives larger anisotropy to film 3.

Similarly, in the 2nd mode of this enforcement, application has been used to be had shown in photoisomerization group or above-mentioned formula (18)The high molecular film of side chain type of structure of light fries' rearrangement group, the ultraviolet irradiation amount of [II] operation reaches Δ ATo in 1%～70% scope of maximum ultraviolet irradiation amount time, the film after polarizing light irradiation 5 is heated and makeMesomorphic state. Thus, as shown in Fig. 3 (c), in film 5, be parallel to irradiation ultraviolet radiation polarization direction direction withBetween direction perpendicular to the polarization direction of irradiation ultraviolet radiation, the amount difference of the light Fries rearrangement of generation. Now, verticalSide chain before the liquid crystal aligning force rate reaction of the light fries' rearrangement body producing in the direction of the polarization direction of irradiation ultraviolet radiationLiquid crystal aligning power is strong, therefore, perpendicular to the direction generation self assembly of the polarization direction of irradiation ultraviolet radiation, comprises liquid crystal ultimate constituentSide chain 6 carry out reorientation. Its result, the very little anisotropy of the film 5 bringing out because of light Fries rearrangement because ofHeat and amplify, give larger anisotropy to film 5.

Similarly, in the 2nd mode of this enforcement, application has been used the light fries' rearrangement base having shown in above-mentioned formula (19)The high molecular film of side chain type of the structure of group, the ultraviolet irradiation amount of [II] operation makes Δ A reach maximum ultraviolet ray photographIn 1%～70% scope of the amount of penetrating time, the film 7 after polarizing light irradiation is heated and makes mesomorphic state. Thus, asShown in Fig. 4 (c), in side chain type polymeric membrane 7, be parallel to irradiation ultraviolet radiation polarization direction direction with perpendicular toBetween the direction of the polarization direction of irradiation ultraviolet radiation, the amount difference of the light Fries rearrangement of generation. Light fries' rearrangement body 8(a) anchor force, than the side chain Final 8 before resetting, while therefore producing certain a certain amount of above light fries' rearrangement body, is parallel to photographPenetrate the direction generation self assembly of ultraviolet polarization direction, the side chain 8 that comprises liquid crystal ultimate constituent carries out reorientation. Its result,Amplifying because of heat compared with little anisotropy of the film 7 bringing out because of light Fries rearrangement, gives larger each to film 7Anisotropy.

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

And, for the film using in method of the present invention, optimize the photograph of the polarized UV rays that film is irradiatedThe heating-up temperature of the amount of penetrating and heat treated. Can realize film is imported to anisotropy efficiently thus.

The irradiation of best polarized UV rays for the film using in the present invention imports anisotropy efficientlyAmount is corresponding to making photonasty group generation photo-crosslinking in this film, photoisomerization reaction or light Fries rearrangementAmount reaches best polarized UV rays exposure. The film using in the present invention is irradiated to the result of polarized UV rays, carry out lightWhen the photonasty group of the side chain of cross-linking reaction, photoisomerization reaction or light Fries rearrangement lacks, do not reach sufficient lightReacting dose. Now, even if heating and also can not carry out sufficient self assembly thereafter. On the other hand, in the present inventionThe film using, to having the result of structured illumination polarized UV rays of photocrosslinking reaction group, carries out the side of cross-linking reactionWhen the photonasty group of chain is excessive, the cross-linking reaction between side chain can excessively advance. Now, gained film becomes upright and outspoken, sometimes hindersThe propelling of the self assembly of passing through heating thereafter. In addition, for the film using in the present invention, to thering is light Fu LisiThe result of resetting the structured illumination polarized UV rays of group, the photonasty group that carries out the side chain of light Fries rearrangement becomesWhen excessive, the liquid crystal liquid crystal property of film can too reduce. Now, the liquid crystal liquid crystal property of gained film also reduces, sometimes hinder thereafter pass through addThe propelling of the self assembly of heat. And then, when thering is the structured illumination polarized UV rays of light fries' rearrangement group, if ultravioletExposure too much, side chain type macromolecule generation light decomposes, and sometimes hinders the propelling of self assembly of heating pass through thereafter.

Therefore,, in film used in the present invention, the photonasty group of side chain occurs because of the irradiation of polarized UV raysThe optimised quantity of photo-crosslinking, photoisomerization reaction or light Fries rearrangement is preferably made as this side chain type polymeric membrane institute tool0.1 % by mole～40 % by mole of some photonasty groups, be more preferably made as 0.1 % by mole～20 % by mole. Undertaken by makingThe amount of the photonasty group of the side chain of light reaction is this scope, and the self assembly meeting in heat treated thereafter efficiently advances,Can form the efficient anisotropy in film.

In the film that method of the present invention is used, the optimization of the exposure by polarized UV rays, thus optimize side chainPhoto-crosslinking, photoisomerization reaction or the light Fries rearrangement of the photonasty group in the side chain of type polymeric membraneAmount. And, realize in the lump in film used in the present invention and import efficiently anisotropy with heat treated thereafter. ThisTime, for applicable polarized UV rays amount, the evaluation of UV absorption that can be based on film used in the present invention is carried out.

That is, for the film using in the present invention, be determined at respectively polarized UV rays postradiation, be parallel to polarization ultravioletThe ultraviolet radiation absorption of the direction of the polarization direction of line and perpendicular to the ultraviolet radiation absorption of the direction of the polarization direction of polarized UV rays.Measurement result by UV absorption is evaluated Δ A, and described Δ A is the side of the polarization direction that is parallel to polarized UV rays in this filmTo ultraviolet absorbance poor of ultraviolet absorbance and the direction perpendicular to the polarization direction of polarized UV rays. And, askGo out the maximum (Δ Amax) of the Δ A realizing in film used in the present invention and realize the exposure of its polarized UV rays.In manufacture method of the present invention, using this polarized UV rays exposure that realizes Δ Amax as benchmark, can determine at liquid crystal and getTo the polarized UV rays amount of the preferred amounts of irradiating in the manufacture of film.

In manufacture method of the present invention, preferably by the exposure of the polarized UV rays that film used in the present invention is irradiatedBe made as the scope that in 1%～70% the scope of amount of the polarized UV rays that can realize Δ Amax, is more preferably made as 1%～50%In. In film used in the present invention, can realize in 1%～50% the scope of amount of the polarized UV rays of Δ Amax partiallyThe ultraviolet irradiation amount of shaking is equivalent to make 0.1 % by mole～20 of photonasty integrated group that this side chain type polymeric membrane has% by mole there is the amount of polarized UV rays of photo-crosslinking.

As mentioned above, in manufacture method of the present invention, in order to realize, film is imported to anisotropy efficiently, with this sideThe high molecular liquid crystal temperature range of chain, as benchmark, is determined applicable heating-up temperature as described above. Therefore, for example thisWhen the high molecular liquid crystal temperature range of bright used side chain type is 100 DEG C～200 DEG C, expect to make polarized UV rays postradiationHeating-up temperature is 90 DEG C～190 DEG C. By such setting, give larger anisotropy to film used in the present invention.

By such operation, the liquid crystal providing by the present invention represents that element shows that to the external stress such as light, heat height canLean on property.

As above operation, the driving liquid crystal of transverse electric field of manufacturing by the inventive method represent element substrate orThe driving liquid crystal of transverse electric field that person has this substrate represents the reliability excellence of element, can be compatibly for large picture and high definitionClear LCD TV etc.

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

Embodiment

The methacrylic monomer M A1, the MA2 that in embodiment, use are below shown; As the list with epoxy radicals side chainGMA, HBAGE, G1 and the additive T1 of body.

It should be noted that, MA1 and MA2 are following synthetic respectively. , MA1 is by patent documentation (WO2011-084546)Described synthetic method and synthetic. MA2 is by synthetic method patent documentation (Japanese kokai publication hei 9-118717) Suo ShuSynthesize.

G1 is synthetic by the synthetic method described in following synthesis example 1.

GMA (GMA), HBAGE (acrylic acid hydroxyl butyl ester glycidol ether), additive T1 (3-Aminomethyl pyridine) used can commercially available purchase material.

Synthesizing of specific glycidyl compound (G1)

In THF (oxolane) solution (184g) of carboxylic acid derivates (MA2) (18.4g, 60mmol), add (COCl)₂2 of (oxalyl chloride) (11.4g, 90mmol) and DMF (dimethyl formamide), at room temperature react them 2 hours. By dense this solutionThe THF for solid (350g) contracting and obtain dissolves. Expend 1 hour this solution is dropped to glycidol (8.89g, 120mmol)And the THF solution (88g) of triethylamine (13.4g, 132mmol), make its reaction 18 hours. , add ethyl acetate (500g) thereafter,Water (300g) cleans 3 times organic phase, makes it dry with magnesium sulfate. Remove after magnesium sulfate by filtering, concentrate andObtain crude product. Use ethyl acetate and hexane to carry out silica gel column chromatography to gained crude product, obtain the G1 of white solid form.(receipts amount: 14.9g, yield: 69%).

Glycidol radical derivative (G1):

¹H-NMR(CDCl₃,δppm)：8.01(d,2H),7.01(d,2H),6.01(s,1H),5.56(s,1H),4.65-4.61(m,1H),4.18-4.12(m,3H),4.02(t,2H),3.36-3.32(m,1H),2.91-2.89(m,1H),2.74-2.72(m,1H),1.95-1.94(m,3H),1.86-1.79(m,2H),1.76-1.69(m,2H),1.57-1.44(m,4H).

Synthesizing of specific oxetane compound (G2)

To carboxylic acid derivates (MA2) (21.4g, 70mmol), dimethylamino naphthyridine (0.85g, 7mmol), 1-ethyl-3-In THF (oxolane) solution (107g) of (3-dimethylamino-propyl) carbodiimide hydrochloride (14.8g, 77mmol), add 3-Ethyl-3-oxetane methanol (8.58g, 73.5mmol), at room temperature reacts them 18 hours. Thereafter, by filtrationRemove the insoluble matter of separating out, add after ethyl acetate (500g), water (200g) cleans 3 times, makes it dry with magnesium sulfate. LogicalFilter and remove after magnesium sulfate, concentrate and obtain G2 (receipts amount: 27.3g, the yield: 96%) of colourless liquid form.

Oxetane compound (G2):

¹H-NMR(CDCl₃,δppm)：7.97(d,2H),6.91(d,2H),6.10(s,1H),5.55(s,1H),4.60(d,2H),4.48(d,2H),4.43(s,2H),4.16(t,2H),4,02(t,2H),1.94(s,3H),1.88-1.79(m,4H),1.76-1.69(m,2H),1.57-1.43(m,4H),0.97(t,3H).

Synthesizing of specific oxetane compound (G3)

Operate same with above-mentioned synthesis example, synthetic following oxetane compound (G3).

Oxetane compound (G3):

¹H-NMR(CDCl₃,δppm)：7.98(d,2H),6.90(d,2H),6.10(s,1H),5.55(s,1H),4.45(d,2H),4.39(d,2H),4.31(t,2H),4.16(t,2H),4,01(t,2H),4.01(t,2H),3.54-3.50(m,4H),1.87-1.66(m,10H)1.56-1.44(m,4H),0.89(t,3H).

In addition, below illustrate that the reagent using in the present embodiment is called for short.

(organic solvent)

THF: oxolane.

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

BC: butyl cellosolve.

(polymerization initiator)

AIBN:2,2 '-azobis isobutyronitrile.

MA1 (9.67g, 29.1mmol), GMA (0.13g, 0.9mmol) are dissolved in THF (56.3g), enter with membrane pumpAfter row is degassed, adds AIBN (0.15g, 3mmol) and again carry out degassed. With 60 DEG C reactions 12 hour, obtain methyl-prop thereafterThe polymer solution of olefin(e) acid ester. This polymer solution is dropped to diethyl ether (1000ml), filter gained sediment. By this precipitationThing cleans with diethyl ether, carries out drying under reduced pressure in the baking oven of 40 DEG C, obtains methacrylate polymers powder P1.

According to the composition shown in table 1, use the method identical with polymer synthesis example 1 to synthesize.

[table 1]

In the methacrylate polymers powder P1 (6.0g) that utilizes polymer synthesis example 1 to obtain, add NMP(54.0g), at room temperature stir 5 hours and make its dissolving. By adding BC (40.0g) and stir in this solution, gatheredCompound solution A 1. This polymer solution is directly as the aligning agent for liquid crystal that is used to form liquid crystal orientation film.

According to the composition shown in table 2, use the method identical with embodiment 1 to be prepared, obtain the liquid of embodiment 2～12Brilliant alignment agent A2～A12.

[table 2]

MA1 (9.97g, 30mmol) is dissolved in THF (57.5g), with membrane pump carry out degassed after, add AIBN(0.15g, 3mmol) also carries out degassed again. Thereafter with 60 DEG C of reactions 12 hours, the polymer that obtains methacrylate was moltenLiquid. This polymer solution is dropped to diethyl ether (1000ml), filter gained sediment. This sediment is cleaned with diethyl ether,In the baking oven of 40 DEG C, carry out drying under reduced pressure, obtain methacrylate polymers powder CP1.

Utilize MA1 (5.9g, 18mmol), MA2 (3.7g, 12mmol), THF (55.5g), AIBN (0.15g, 3mmol)Composition, uses the method identical with contrast 1, obtains methacrylate polymers powder CP2.

Use CP1, utilize the method identical with embodiment 1, obtain contrasting 1 aligning agent for liquid crystal B1. Similarly, useCP2 obtains contrasting 2 aligning agent for liquid crystal B2.

The preparation of<<liquid crystal cells>>

Use the aligning agent for liquid crystal A1 obtaining in embodiment 1, carry out the making of liquid crystal cells according to the following step illustrating.Substrate is to be of a size of the glass substrate that 30mm × 40mm and thickness are 0.7mm, uses to dispose ITO film patterning is formedThe substrate of comb teeth-shaped pixel electrode.

Pixel electrode has the broach that " < " font electrode key element that middle body bends forms through multiple arrangementsShape shape. The width of the width of each electrode key element is 10 μ m, between electrode key element, is spaced apart 20 μ m. Form the picture of each pixelThe electrode key element of " < " font that element electrode is bent by middle body forms the therefore shape of each pixel through multiple arrangementsNot oblong-shaped, but possess " < " word similarly bending at middle body with electrode key element, be similar to runicShape.

Each pixel is cut apart as boundary up and down taking its central sweep, have sweep upside the 1st region andThe 2nd region of downside. While contrasting the 1st region of each pixel and the 2nd region, form the shape of the electrode key element of their pixel electrodeBecome direction difference. , using the orientation process direction of aftermentioned liquid crystal orientation film during as benchmark, in the 1st region of pixel, to beThe mode of the angle (clockwise) of existing+15 ° forms the electrode key element of pixel electrode, in the 2nd region of pixel, to present-15 °The mode of angle (clockwise) form the electrode key element of pixel electrode. , the 1st region of each pixel and the 2nd following structure in regionBecome: by apply spinning movement (plane liquid crystal that voltage brings out, in real estate between pixel electrode and counter electrodeSwitch) direction rightabout each other.

The aligning agent for liquid crystal A1 obtaining in embodiment 1 is spin-coated on prepared above-mentioned electroded substrate. Then, useDry 90 seconds of hot plate of 70 DEG C, the liquid crystal orientation film that formation thickness is 100nm. Then, across polarization plates with 20mJ/cm²RightCoated surface irradiates after the ultraviolet ray of 313nm, with the hot plate heating of 150 DEG C 10 minutes, obtains the substrate with liquid crystal orientation film. SeparatelyOutward, to not forming electrode and thering is the glass substrate landform too of the column spacer that is highly 4 μ m as subtend substrateBecome film, implementation orientation processing. Printing and sealing agent on the liquid crystal orientation film of a substrate (Xie Li KCC system, XN-1500T). Then, with liquid crystal aligning face relatively and differently-oriented directivity reach the mode of 0 ° and paste after another substrate, make sealantHeat cure and make dummy cell. In this dummy cell, inject liquid crystal MLC-2041 (MERCK by decompression injection methodCORPORATION system), sealing inlet, the liquid crystal of (In-PlanesSwitching, the plane switch) pattern that obtains possessing IPSRepresent the liquid crystal cells that element forms.

Aligning agent for liquid crystal A2～the A12 obtaining in use embodiment 2～12, the aligning agent for liquid crystal B1 obtaining in contrast 1,2,B2, similarly makes liquid crystal cells.

<<voltage retention (VHR) is evaluated>>

Use the liquid crystal cells of above-mentioned making, at the temperature of 70 DEG C, apply the 5V voltage of 60 μ s, measure after 16.67msWhich kind of degree voltage, can remain using voltage and calculate as voltage retention (VHR1). And then by unit after measuredUnder the isoperibol of 70 DEG C, apply the 16Vpp alternating voltage of 168 hours with the frequency of 30Hz. ,, make the picture of liquid crystal cells thereafterBetween element electrode and counter electrode, present short-circuit condition, directly at room temperature place 1 hour. Under the condition identical with VHR1, surveyWhich kind of degree fixed this gained unit, can remain using voltage and calculate as voltage retention (VHR2). Need to illustrateThat the mensuration of voltage retention has been used the voltage retention determinator VHR-1 of TOYOCorporation system.

By the table 3 that the results are shown in of the composition of the aligning agent for liquid crystal of embodiment and contrast and VHR.

[table 3]

	Aligning agent for liquid crystal	VHR1	VHR2
				Embodiment 1	A1	97.1	95.8
Embodiment 2	A2	96.5	94.9
				Embodiment 3	A3	96.2	95.2
Embodiment 4	A4	96.9	95.4
				Embodiment 5	A5	96.4	96.4
Embodiment 6	A6	96.5	96.6
				Embodiment 7	A7	96.3	96.3 46 -->
Embodiment 8	A8	97	97.1
				Embodiment 9	A9	96.6	95
Embodiment 10	A10	96.5	94.8
				Embodiment 11	A11	96.6	96.5
Embodiment 12	A12	96.4	96.5
				Contrast 1	B1	94.5	93.2
Contrast 2	B2	94	92.8

As shown in Table 3: 1,2 compare with not carrying out contrasting of copolymerization, in embodiment 1～12 by thering is the list of epoxy radicalsBody carries out copolymerization, thereby VHR1 improves. In addition we know: in embodiment 5～8,11 and 12 by further adding additive T1, fromAnd the result of VHR2 is good.

The IPS pattern of preparing in embodiment 1～8 is arranged on and is configured in the vertical mode of polarizing axis with liquid crystal cellsBetween 2 polarization plates, under alive state, light backlightly not executing, adjust the arrangement angles of liquid crystal cells so that transmitted lightIt is minimum that brightness reaches. And, reach to the 1st region making liquid crystal cells reach the darkest angle rotation from the 2nd region of pixelThe anglec of rotation till the darkest angle time calculates as initial stage orientation azimuth.

Then, in the baking oven of 60 DEG C, apply the 16V of 168 hours with the frequency of 30Hz_PPAlternating voltage. ,, make liquid crystal thereafterBetween the pixel electrode of unit and counter electrode, present short-circuit condition, directly at room temperature place 1 hour. After placement, behaviour equallyDo and measure orientation azimuth, the difference that exchanges the orientation azimuth before and after driving is calculated as angle delta (deg.).

Similarly measure in other embodiments.

Its result, in all embodiment, angle delta is below 0.1.

After the side chain type polymeric membrane irradiation ultraviolet radiation to showing liquid crystal liquid crystal property, in the scope of liquid crystal performance temperatureHeating, is perhaps that macromolecule entirety is given liquid crystal aligning ability efficiently because of self assembly, and therefore long-term AC drivesAfter moving, almost do not observe the skew in orientation orientation yet.

Description of reference numerals

Fig. 1

1 side chain type polymeric membrane

2,2a side chain

Fig. 2

3 side chain type polymeric membranes

4,4a side chain

Fig. 3

5 side chain type polymeric membranes

6,6a side chain

Fig. 4

7 side chain type polymeric membranes

8,8a side chain

Claims

1. a side chain type macromolecule, it for showing the photonasty side chain type high score of liquid crystal liquid crystal property in specific temperature rangeSon, also has the side chain shown in following formula (0),

In formula (0), A, B represent singly-bound ,-O-,-CH independently of one another₂-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH＝CH-CO-O-or-O-CO-CH=CH-;

P and Q are independently of one another for selecting phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, the pyrrole ring of free divalent, the alicyclic ring of carbon number 5～8Group in the group of formula hydrocarbon and their combination composition; Wherein, X is-when CH=CH-CO-O-,-O-CO-CH=CH-,-CH=P or the Q of one side of CH-institute bonding are aromatic rings, and the quantity of P is 2 when above, and P is optionally same to each other or different to each other, and the quantity of Q is 2When above, Q is optionally same to each other or different to each other;

L1 is 0 or 1;

L2 is 0～2 integer;

L1 is 1 o'clock, and when T is singly-bound, B also represents singly-bound;

Formula (G-1), (G-2), (G-3) and (G-4) in, dotted line represents connecting key; R⁵⁰Represent to be selected from hydrogen atom, halogen atom, carbon, there are multiple R in the group in several 1～3 alkyl, phenyl⁵⁰Time, be optionally same to each other or different to each other; T is 1～7 integer; J representsO, S, NH or NR⁵¹，R⁵¹Represent to be selected from the group in alkyl and the phenyl of carbon number 1～3.

2. side chain type macromolecule according to claim 1, it is heavy that it has meeting generation photo-crosslinking, photoisomerization or light Fu LisiRow's photonasty side chain.

3. side chain type macromolecule according to claim 1 and 2, it has in the choosing group that freely following formula (1)～(6) formAny photonasty side chain,

In formula, A, B, D represent singly-bound ,-O-,-CH independently of one another₂-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH＝CH-CO-O-or-O-CO-CH=CH-;

Y₁Represent the ring in the ester ring type hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8 of 1 valency that is selected from, orPerson is selected from the group that 2～6 the identical or different rings in these substituting groups form by binding groups B bonding, is bonded toTheir hydrogen atom is independently of one another optionally by-COOR₀、-NO₂、-CN、-CH＝C(CN)₂,-CH=CH-CN, halogen group, carbonThe alkoxyl of several 1～5 alkyl or carbon number 1～5 replaces, in formula, and R₀Represent the alkyl of hydrogen atom or carbon number 1～5;

Y₂For selecting phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the ester ring type hydrocarbon of carbon number 5～8 and their group of free divalentGroup in the group being combined into, the hydrogen atom that is bonded to them is independently of one another optionally by-NO₂、-CN、-CH＝C(CN)₂、-CHThe alkyl of=CH-CN, halogen group, carbon number 1～5 or the alkoxyl of carbon number 1～5 replace;

Cou represents Coumarin-6-Ji or coumarin-7-Ji, and the hydrogen atom that is bonded to them is independently of one another optionally by-NO₂、-CN、-CH＝C(CN)₂The alkyl of ,-CH=CH-CN, halogen group, carbon number 1～5 or the alkoxyl of carbon number 1～5 replace;

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

Q3 is 0 or 1;

L1 is 0 or 1;

L2 is 0～2 integer;

L1 is 1 o'clock, and when T is singly-bound, B also represents singly-bound;

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

4. according to the side chain type macromolecule described in any one in claim 1～3, it has freely following formula (7)～(10) of choosingAny photonasty side chain in the group of composition,

L represents 1～12 integer;

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

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

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

5. according to the side chain type macromolecule described in any one in claim 1～3, it has freely following formula (11)～(13) of choosingAny photonasty side chain in the group of composition,

In formula, A represents singly-bound ,-O-,-CH independently of one another₂-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH＝CH-CO-O-or-O-CO-CH=CH-;

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

R represents to be selected from the ring in the ester ring type hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8 of 1 valency, orPerson is selected from the group that 2～6 the identical or different rings in these substituting groups form by binding groups B bonding, is bonded toTheir hydrogen atom is independently of one another optionally by-COOR₀、-NO₂、-CN、-CH＝C(CN)₂,-CH=CH-CN, halogen group, carbonThe alkoxyl of several 1～5 alkyl or carbon number 1～5 replaces, in formula, and R₀Represent the alkyl of hydrogen atom or carbon number 1～5, or R tableShow the alkoxyl of hydroxyl or carbon number 1～6.

6. according to the side chain type macromolecule described in any one in claim 1～3, it has shown in following formula (14) or (15)Photonasty side chain,

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

7. according to the side chain type macromolecule described in any one in claim 1～3, it has shown in following formula (16) or (17)Photonasty side chain,

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

X represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-,-CH=CH-CO-O-or-O-CO-CH=CH-, XQuantity be 2 o'clock, X is optionally same to each other or different to each other;

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

8. according to the side chain type macromolecule described in any one in claim 1～3, it has freely following formula (18) or (19) of choosingAny photonasty side chain in the group of composition,

In formula, A, B represent singly-bound ,-O-,-CH independently of one another₂-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH＝CH-CO-O-or-O-CO-CH=CH-;

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

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

R₁Represent hydrogen atom ,-NO₂、-CN、-CH＝C(CN)₂Alkyl or the carbon number of ,-CH=CH-CN, halogen group, carbon number 1～51～5 alkoxyl.

9. according to the side chain type macromolecule described in any one in claim 1～3, it has the photonasty shown in following formula (20)Side chain,

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

10. according to the side chain type macromolecule described in any one in claim 1～9, its have freely following formula (21) of choosing～(31) any liquid crystal liquid crystal property side chain in the group of composition,

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

Y₃For selecting the ester ring type hydrocarbon of freely phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring and the carbon number 5～8 of 1 valency and itThe group of combination composition in group, the hydrogen atom that is bonded to them is independently of one another optionally by-NO₂,-CN, halogen group,The alkoxyl of the alkyl of carbon number 1～5 or carbon number 1～5 replaces;

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

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

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

R₂Represent hydrogen atom ,-NO₂,-CN, halogen group, phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring and the carbon number of 1 valency5～8 ester ring type hydrocarbon, and alkyl or alkoxyl;

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

11. 1 kinds of polymer compositions, it contains in (A) claim 1～10 the side chain type macromolecule described in any one and (B)Organic solvent.

12. compositions according to claim 11, wherein, polymer composition also contains (C) amines, described aminationCompound has 1 primary amino radical and nitrogenous heteroaromatic in molecule, and described primary amino radical is bonded to aliphatic alkyl or non-Aromatic series ring type alkyl.

13. compositions according to claim 12, wherein, described (C) composition is following formula A-[1] shown in amine compoundsThing,

In formula, Y₁₁For thering is the divalent organic group of aliphatic alkyl or non-aromatic ring type alkyl, Y₁₂For nitrogenous aromatic series is mixedRing.

14. 1 kinds have the manufacture method that the driving liquid crystal of transverse electric field represents the substrate of element liquid crystal orientation film, and it passes throughPossess following operation and obtained being endowed the described liquid crystal orientation film that is orientated control ability:

[I] is coated on the composition described in any one in claim 11～13 in the base with transverse electric field driving conducting filmOn plate and form the operation of film;

The operation that [III] heats the film obtaining in [II].

15. 1 kinds have the substrate that the driving liquid crystal of transverse electric field represents element liquid crystal orientation film, and it is to pass through claimMethod described in 14 is manufactured.

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

17. 1 kinds of driving liquid crystal of transverse electric field represent the manufacture method of element, and it obtains this liquid by possessing following operationThe brilliant element that represents:

The i.e. operation of the 1st substrate of substrate described in preparation claim 15;

[IV], with the liquid crystal orientation film of described the 1st substrate and the 2nd substrate across the right mode of liquid crystalline phase, subtend configures the described the 1stSubstrate and the 2nd substrate, thus the operation that liquid crystal represents element obtained,

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

[I '] on the 2nd substrate, be coated with claim 11～13 in polymer composition described in any one and form the work of filmOrder;

The operation that [III '] heats the film obtaining in [II '].

18. 1 kinds of driving liquid crystal of transverse electric field represent element, and it is to manufacture by the method described in claim 17.