CN107533259A

CN107533259A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element

Info

Publication number: CN107533259A
Application number: CN201680025645.8A
Authority: CN
Inventors: 芦泽亮; 芦泽亮一; 长尾将人; 野田尚宏; 后藤耕平; 杉山崇明
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2015-03-04
Filing date: 2016-03-02
Publication date: 2018-01-02
Also published as: TW201704342A; JP6635272B2; WO2016140288A1; KR20170125080A; TWI596158B; JPWO2016140288A1; KR102609036B1

Abstract

Aligning agent for liquid crystal containing following (A) compositions, (B) composition.(A) composition：At least one of polyimides polymer obtained from selected from the polyimide precursor as the side chain with the side chain for making liquid crystal vertical-tropism and with free radical generating unit and making its imidizate.(B) composition：Selected from using from polyimide precursor obtained from least one diamines of following middle selections and making polymer in polyimides obtained from its imidizate or selected from using from polyimide precursor obtained from least one tetracarboxylic dianhydride of following middle selections and making polymer in polyimides obtained from its imidizate.The definition of symbol in formula is as described in specification.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element

Technical field

The present invention relates to vertical orientated and what is made by irradiating ultraviolet in the state of voltage is applied to liquid crystal molecule The aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal that the liquid crystal of mode represents to use in element etc. represent element.

Background technology

For (also referred to as vertically being taken by way of responding the liquid crystal molecule vertical orientated relative to substrate electric field To (VA) mode) liquid crystal represent element, in its manufacturing process, sometimes include voltage is applied to liquid crystal molecule while shining The process for penetrating ultraviolet.

Element is represented for the liquid crystal of this vertical orientation mode, it is known to：By being added in advance into liquid-crystal composition Photopolymerizable compound, and using vertical alignment layers such as polyimides systems, voltage is applied to liquid crystal cells while irradiating Ultraviolet, so as to accelerate the technology of the response speed of liquid crystal (PSA (Polymer Sustained Alignment) mode element, Referring for example to patent document 1 and the reference of non-patent literature 1.).

In the PSA modes element, generally, the incline direction of the liquid crystal molecule responded to electric field on substrate by setting The projection put, expression with the control of the slit set on electrode etc., it is said that：By adding optical polymerism into liquid-crystal composition Compound, voltage is applied to liquid crystal cells while irradiating ultraviolet, remembered liquid crystal point so as to be formed on liquid crystal orientation film The polymer architecture thing of sub- incline direction, therefore, the method phase with controlling liquid crystal molecules tilt direction merely with projection, slit Than liquid crystal represents that the response speed of element accelerates.

On the other hand, the liquid crystal of the PSA modes is represented in element, the unreacted polymerizable compound that is remained in liquid crystal into For the impurity (pollution) in liquid crystal, therefore there is also liquid crystal is represented the problem of reliability of element reduces etc.In addition, for UV treatment with irradiation needed for PSA modes, if its exposure is more, the composition in liquid crystal is decomposed, and causes the drop of reliability It is low.

And then, it was recently reported that：By the way that photopolymerizable compound is added in liquid crystal orientation film without added to liquid crystal combination In thing, liquid crystal represents that the response speed of element accelerates (SC-PVA type liquid crystal displays, referring for example to non-patent literature 2).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2003-307720 publications

Non-patent literature

Non-patent literature 1：K.Hanaoka,SID 04 DIGEST、P.1200-1202

Non-patent literature 2：K.H Y.-J.Lee,SID 09 DIGEST、P.666-668

The content of the invention

Problems to be solved by the invention

In recent years, the quality for representing element with liquid crystal improves, and it is expected to further speed up the sound that liquid crystal applies for voltage Answer speed.For this reason, it may be necessary to irradiated by the ultraviolet for being not accompanied by the long wavelength of ingredient breakdown in liquid crystal to make polymerizable compound Efficiently react, play orientation immobilization ability.And then, it is necessary to ultraviolet irradiation after will not remained unreacted polymerism chemical combination Thing, the reliability for not representing element to liquid crystal have undesirable effect.

In addition, it is also desirable to resulting liquid crystal is represented that the electrical characteristics of element are good, especially make direct current charge accumulation special Property is good.

The problem of the present invention is solve above-mentioned problem of the prior art, even if being the ultraviolet irradiation for providing long wavelength Also polymerizable compound highly effective reaction is made, it is possible to increase the liquid crystal of vertical orientation mode represents the response speed of element, Jin Erneng Resulting liquid crystal is enough set to represent the electrical characteristics of element, the especially good aligning agent for liquid crystal of direct current electric charge accumulation characteristics, liquid crystal Alignment films, liquid crystal represent that element and liquid crystal represent the manufacture method of element.

The solution used to solve the problem

The present inventor etc. has made intensive studies, and as a result finds, by being imported in the polymer for forming aligning agent for liquid crystal The specific structure of free radical is produced because of ultraviolet irradiation, above-mentioned problem can be realized, so as to complete the present invention.

That is, the present invention has following main idea.

1. a kind of aligning agent for liquid crystal, it is characterised in that contain following (A) composition, (B) composition and organic solvents.

(A) composition：Selected from possess the side chain that makes liquid crystal vertical-tropism and with shown in following formula (I)s because ultraviolet irradiates And produce the polyimide precursor of the side chain at the position of free radical and make polyamides obtained from the polyimide precursor imidizate At least one of imines polymer.

R₁、R₂It is independently of one another the alkyl or alkoxy of carbon number 1~10, T₁、T₂It is singly-bound independently of one another Or-O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- ,-NH- ,-CH₂O-、-N(CH₃)-、-CON(CH₃)-、-N(CH₃) CO- company Connect group, S is singly-bound or the alkylidene of carbon number 1~20 that is unsubstituted or being replaced by fluorine atoms.Wherein, alkylidene- CH₂- or-CF₂--CH=CH- is arbitrarily optionally replaced with, in the case that any group being exemplified below is not adjacent to each other, appoint Choosing is replaced by these groups：- O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- ,-NH-, the carbocyclic ring of divalence, the heterocycle of divalence, Q Represent the structure from following middle selections.

R is the alkyl of hydrogen atom or carbon number 1~4.

(B) composition：Selected from the diamine component that will contain at least one diamines of selection from following formula (B-1)~(B-5) It is poly- as polyimide precursor obtained from raw material and in polyimides obtained from making the polyimide precursor imidizate Compound, or selected from the tetracarboxylic dianhydride's composition that will contain at least one tetracarboxylic dianhydride of selection from following formula (3) and (4) It is poly- as polyimide precursor obtained from raw material and in polyimides obtained from making the polyimide precursor imidizate Compound.

Y₁For the organic group of the monovalence with secondary amine, tertiary amine or heterocycle structure, Y₂For with secondary amine, tertiary amine or heterocycle knot The organic group of the divalence of structure.

N, m is 0 or 1, and X, y are singly-bound, carbonyl, ester group, phenylene, sulfonyl.

2. a kind of liquid crystal orientation film, it is characterised in that it is that the aligning agent for liquid crystal described in 1 is coated on substrate and burnt till Obtained from.

3. a kind of liquid crystal represents element, it is characterised in that with the aligning agent for liquid crystal described in 1 to be coated on substrate and burn till Obtained from liquid crystal orientation film liquid crystal layer is set in contact, voltage is applied to the liquid crystal layer while irradiating ultraviolet, from And possess liquid crystal cells.

4. a kind of liquid crystal represents the manufacture method of element, it is characterised in that with the aligning agent for liquid crystal described in 1 is coated on into base Liquid crystal orientation film sets liquid crystal layer in contact on plate and obtained from burning till, and applies voltage to the liquid crystal layer while irradiating Ultraviolet, so as to make liquid crystal cells.

The effect of invention

In accordance with the invention it is possible to provide can also be improved even if by the irradiation of the ultraviolet of long wavelength liquid crystal response speed, And the liquid crystal of the few vertical orientation mode of direct current charge accumulated represents element.

Embodiment

The aligning agent for liquid crystal of the present invention contains following (A) composition, (B) composition and organic solvents.

(B) composition：Selected from least one diamines of the selection from following formula (B-1)~(B-5) is obtained as raw material Polyimide precursor and polyimides obtained from making the polyimide precursor imidizate in polymer, or be selected from At least one tetracarboxylic dianhydride of selection as polyimide precursor obtained from raw material and it will make from following formula (3) and (4) Polymer in polyimides obtained from the polyimide precursor imidizate.

Aligning agent for liquid crystal refers to the solution for forming liquid crystal orientation film, and liquid crystal orientation film refers to be used to make liquid crystal along regulation The film of direction orientation.

Hereinafter, each constitutive requirements are described in detail.

<(A) composition>

The aligning agent for liquid crystal of the present invention is selected from possessing the side chain that makes liquid crystal vertical-tropism and with shown in above-mentioned formula (1) The polyimide precursor of the side chain at the position of free radical is produced because of ultraviolet irradiation and makes the polyimide precursor imidizate Obtained from least one of polyimides polymer.

Herein, polyimide precursor represents polyamic acid and poly amic acid ester.

In (A) composition contained in the aligning agent for liquid crystal of the present invention, there is the portion that free radical is produced because of ultraviolet irradiation Position is used as side chain.The position that free radical is produced because of ultraviolet irradiation can be represented with following formula (I)s.

In above-mentioned formula (I), the Ar that carbonyl is bonded can intervene the absorbing wavelength of ultraviolet, therefore in the situation of long wavelengthization It is preferably the structure that conjugate length as naphthylene, biphenylene is grown down.In addition, substituent is optionally substituted with Ar, it is described Substituent is preferably the organic group of electron as alkyl, hydroxyl, alkoxy, amino etc..

When Ar is structure as naphthylene, biphenylene, dissolubility is deteriorated, and the difficulty of synthesis also uprises.Ultraviolet When wavelength is 250nm~380nm scope, even phenyl can also obtain sufficient characteristic, therefore most preferably phenyl.

In addition, R₁、R₂It is independently of one another alkyl, alkoxy, benzyl or the phenethyl of carbon number 1~10, alkyl, alkane In the case of epoxide, optionally by R₁、R₂Form ring.

Q is preferably the organic group of electron, preferably following.

(R represents the alkyl of hydrogen atom or carbon number 1~4, R₃Expression-CH₂- ,-NR- ,-O- or-S-.)

In the case that Q is represented with-OR, R in order to increase coating after (A) composition surface existence rate purpose and it is preferred that setting For the alkyl of carbon number 1~4.Because by making Q be alkyl, polarity step-down, surface is easier to move to.And then, it is contemplated that close During into difficulty etc., preferably 1~2, most preferably 1.

In the case that Q is aminoderivative, during polymerization as the polyamic acid of the precursor of polyimides, generation institute be present Caused carboxylic acid group and possibility a problem that amino forming salt, therefore more preferably hydroxyl or alkoxy.

As the polymer containing aligning agent for liquid crystal, it is desirable to using polyimide precursor and or polyimides come by above-mentioned formula (I) when structure is directed into side chain, it is set to the side-chain structure of the formula (I) and holds from the synthesis of the treatability of raw material, polymer It is preferable that Yi Du, which sets out,.

The position that free radical is produced because of ultraviolet irradiation in above-mentioned formula (I) is preferably specifically following.Particularly From the viewpoint of the reliability for representing element from resulting liquid crystal, preferably (b), (c) or (d), from the surface of liquid crystal orientation film Free radical generating unit top layer existence rate from the viewpoint of, more preferably (d).

It should be noted that-T₁-S-T₂- have and enter diaminobenzene with producing the position of free radical because of ultraviolet irradiation The effect of the linking group of row connection.T₁、T₂Independently of one another for singly-bound ,-O- ,-S- ,-COO- ,-OCO- ,-NHCO- ,- CONH-、-NH-、-CH₂O-、-N(CH₃)-、-CON(CH₃)-or-N (CH₃)CO-.S is singly-bound or is optionally replaced by fluorine atoms Carbon number 1~20 alkylidene (the wherein ,-CH of alkylidene₂- or-CF₂- optionally replaced by arbitrarily use-CH=CH-, In the case that following any group is not adjacent to each other, these groups are optionally replaced with：-O-、-COO-、-OCO-、-NHCO-、- CONH- ,-NH-, the carbocyclic ring or heterocycle of divalence.).Particularly from the viewpoint of synthesis difficulty, T₂Most preferably-O-.Separately Outside, S is preferably 2~10, more preferably 4~8 alkylidene from the viewpoint of synthesis difficulty, dissolubility.

The polymer contained in the aligning agent for liquid crystal of the present invention preferably also has in addition to the side chain shown in above-mentioned formula (I) Make the side chain of liquid crystal vertical-tropism.The side chain of liquid crystal vertical-tropism is set to be represented with following formula [II-1] or formula [II-2].

X in formula [II-1]¹、X²、X³、X⁴、X⁵And n as described above defined in like that.

Wherein, X¹Availability from raw material, synthesis easness from the viewpoint of be preferably singly-bound ,-(CH₂)_a- (a be 1~ 15 integer) ,-O- ,-CH₂O- or-COO-, more preferably singly-bound ,-(CH₂)_a- (a is 1~10 integer) ,-O- ,-CH₂O- Or-COO-.Wherein, X²Preferably singly-bound or (CH₂)_b- (b is 1~10 integer).X³Especially from the viewpoint of the easness of synthesis Set out preferably singly-bound ,-(CH₂)_c- (c is 1~15 integer) ,-O- ,-CH₂O- or-COO-, more preferably singly-bound ,-(CH₂)_c- (c is 1~10 integer) ,-O- ,-CH₂O- or-COO-.

Wherein, X⁴It is preferably phenyl ring, cyclohexane ring or with steroid skeleton from the viewpoint of the easness of synthesis The organic group of carbon number 17~51.X⁵Especially preferably phenyl ring or cyclohexane ring.Availability, the appearances of synthesis of the n especially from raw material It is preferably 0~3, more preferably 0~2 from the viewpoint of Yi Du.

X⁶The especially preferably alkoxy or carbon containing fluoroalkyl, carbon number 1~18 of the alkyl of carbon number 1~18, carbon number 1~10 The fluoroalkoxy of number 1~10.The more preferably alkoxy of the alkyl of carbon number 1~12 or carbon number 1~12.Particularly preferably carbon number 1~9 alkyl or the alkoxy of carbon number 1~9.

As the X in formula [II-1]¹、X²、X³、X⁴、X⁵、X⁶And n preferred compositions, it can include and International Publication publication (2-1) described in 6~table of table 47 that page 13~page 34 of WO2011/132751 (2011.10.27 is disclosed)~(2-629) phase Same combination.It should be noted that in each table of International Publication publication, X of the invention¹~X⁶It is illustrated as Y1~Y6, but Y1~Y6 can be understood as X¹~X⁶。

In addition, in (2-605)~(2-629) described in each table of International Publication publication, of the invention has steroids The organic group of the carbon number 17~51 of skeleton is illustrated as the organic group of the carbon number 12~25 with steroid skeleton, but The organic group of carbon number 12~25 with steroid skeleton can be understood as having for the carbon number 17~51 with steroid skeleton Machine group.Wherein, preferably (2-25)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-268)~(2- 315), (2-364)~(2-387), (2-436)~(2-483) or (2-603)~(2-615) combination.Particularly preferred combination For (2-49)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-603)~(2-606), (2-607)~ (2-609), (2-611), (2-612) or (2-624).

-X⁷-X⁸ [II-2]

In formula [II-2], X⁷、X⁸Defined in as described above like that.Wherein, X⁷Preferably singly-bound ,-O- ,-CH₂O-、-CONH-、- CON(CH₃)-or-COO-, more preferably singly-bound ,-O- ,-CONH- or-COO-.X⁸The especially preferably alkyl of carbon number 8~18.

As the side chain for making liquid crystal vertical-tropism, go out from the viewpoint for the vertical orientated property that can obtain high and stable liquid crystal Hair, the structure shown in preferably using formula [II-1].

It should be noted that the polymer with the side chain for making liquid crystal vertical-tropism make the ability of liquid crystal vertical-tropism according to Make the structure of the side chain of liquid crystal vertical-tropism and different, generally, if making the quantitative change of the side chain of liquid crystal vertical-tropism more, make liquid crystal Vertical orientated ability rise, declines at least if becoming.In addition, when there is cyclic structure, with the situation phase without cyclic structure Than the tendency for making the ability of liquid crystal vertical-tropism high be present.

(A) composition contained in the aligning agent for liquid crystal of the present invention can also have in addition to the side chain shown in above-mentioned formula (I) There is photoreactivity side chain.Photoreactivity side chain has and can react and be formed covalently by the irradiation of the light such as ultraviolet (UV) Functional group's (hereinafter also referred to photoreactive group of key.).

Photoreactivity side chain can be bonded directly to the main chain of polymer, can also be bonded in addition by linking group. Photoreactivity side chain is for example represented with following formula (III)s.

-R⁸-R⁹-R¹⁰ [III]

In formula (III), R⁸、R⁹、R¹⁰Defined in as described above like that.Wherein, R⁸Preferably singly-bound ,-O- ,-COO- ,-NHCO-, Or-CONH-.R⁹It can be formed by the method for common organic synthesis, from the viewpoint of the easiness of synthesis, be preferably The alkylidene of singly-bound or carbon number 1~12.

In addition, replace R⁹Any-CH₂- divalence carbocyclic ring or heterocycle concrete example following group is shown.

R¹⁰It is preferably methylacryloyl, acryloyl group, vinyl or styryl from the viewpoint of photoreactivity.

The amount of photoreactivity side chain is reacted preferably by using ultraviolet irradiation and forms covalent bond and energy The scope of the response speed of liquid crystal is enough improved, in order to further speed up the response speed of liquid crystal, is not preferably influenceing other characteristics In the range of it is more as much as possible.

The diamines (hereinafter also referred to specific two used is formed in the manufacture of the above-mentioned polymer of the aligning agent for liquid crystal of the present invention Amine.) have and decomposed because of ultraviolet irradiation and produce the position of free radical as side chain.

Ar, R in above-mentioned formula (1)₁、R₂、T₁、T₂And Sn as described above defined in like that.

Diaminobenzene in formula (1) can be arbitrary structures in o-phenylenediamine, m-phenylene diamine (MPD) or p-phenylenediamine, from acid From the viewpoint of the reactivity of dianhydride, preferably m-phenylene diamine (MPD) or p-phenylenediamine.

As specific diamines, the viewpoint, most preferably following formula institute such as easness, versatility height, characteristic from synthesis The structure shown.It should be noted that n is 2~8 integer in formula.

In the present invention, specific diamines can obtain as follows：Dinitro matrix or sharp with energy is imparted is synthesized by each step The single nitro-body or diamines of the amino of the protection group removed with reduction process, nitro is turned using usually used reduction reaction Turn to amino or be deprotected protection group, so as to obtain.

The synthetic method of diamine precursor has various methods, such as described below：Synthesis is irradiated by ultraviolet to produce freely The position of base, import interval position, the method being then bonded with dinitro benzene.It should be noted that in formula n be 2~8 it is whole Number.

In the case of above-mentioned reaction, the material that hydroxyl at two be present has been used, can be by optimizing the kind of alkali (catalyst) Class, rate of charge and optionally synthesize.

It should be noted that the alkali used is not particularly limited, preferably the inorganic base such as potassium carbonate, sodium carbonate, cesium carbonate, Organic bases such as pyridine, dimethyl aminopyridine, trimethylamine, triethylamine, tri-n-butylamine etc..

The method of dinitro compound reduction as diamine precursor is not particularly limited, generally had using palladium carbon, oxygen Change platinum, Raney's nickel, platinum carbon, rhodium-aluminum oxide, vulcanization platinum carbon etc. and be used as catalyst, in ethyl acetate, toluene, tetrahydrofuran, two Evil The method reduced in alkane, alcohol system equal solvent using hydrogen, hydrazine, hydrogen chloride etc..Can also be as needed using autoclave etc..

On the other hand, when unsaturated bond position is included in structure, if using palladium carbon, platinum carbon etc., existing causes unsaturation Key position is reduced and forms the worry of saturated bond, therefore is used as optimum condition, it is preferable to use reduced iron and/or tin, chlorination The transition metal such as tin, the palladium carbon being poisoned and/or platinum carbon, doped with reducing condition as catalyst such as platinum carbon of iron etc..

In addition, by can similarly be carried out with the diamino benzene derivant of the protections such as benzyl by using above-mentioned reduction process It is deprotected and obtains the diamines of the present invention.

Specific diamines is preferably using preferably 10~80 moles of %, more excellent of the diamine component used in the synthesis of polyamic acid Elect 20~60 moles of %, particularly preferably 30~50 moles of % as.

Method on the side chain for making liquid crystal vertical-tropism to be directed into polyimides based polymer, will preferably have specific The diamines of side-chain structure is used for a part for diamine component.It is particularly preferably (also referred to as specific using the diamines shown in following formula [2] Side chain type diamine compound).

In formula [2], the structure shown in X expression previously described formula [II-1] or formula [II-2], n represents 1~4 integer, especially excellent Elect 1 as.

As specific side chain type diamine, from the viewpoint of the vertical orientated property that can obtain high and stable liquid crystal, preferably Use the diamines shown in following formula [2-1].

X in above-mentioned formula [2-1]¹、X²、X³、X⁴、X⁵And n is identical with respective definition in above-mentioned formula [II-1], in addition, respectively It is also identical with respective definition in above-mentioned formula [II-1] from preferable scheme.

It should be noted that in formula [2-1], m is 1~4 integer.Preferably 1 integer.

Specific side chain type diamine can specifically include the structure for example shown in following formula [2a-1]~formula [2a-31].

(R¹Expression-O- ,-OCH₂-、-CH₂O-、-COOCH₂- or-CH₂OCO-, R²For the straight-chain or branch of carbon number 1~22 Chain-like alkyl, carbon number 1~22 straight-chain either branched alkoxy, the straight-chain of carbon number 1~22 or branched, it is fluorine-containing Alkyl or fluoroalkoxy.)

(R³Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂- or- CH₂-, R⁴For straight-chain either branched-chain alkyl, the straight-chain of carbon number 1~22 or branched alkoxy, the carbon of carbon number 1~22 The straight-chain of number 1~22 or branched, containing fluoroalkyl or fluoroalkoxy).

(R⁵Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、- CH₂- ,-O- or-NH-, R⁶For fluorine-based, cyano group, fluoroform alkyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl Base).

(R⁷For the straight-chain or branched-chain alkyl of carbon number 3~12, the cis-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans different Structure body).

(R⁸For the straight-chain or branched-chain alkyl of carbon number 3~12, the cis-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans different Structure body).

(A₄For the straight-chain or branched-chain alkyl of the carbon number 3~20 being optionally replaced by fluorine atoms, A₃For 1,4- cyclohexylidenes Or Isosorbide-5-Nitrae-phenylene, A₂For oxygen atom or COO-* (wherein, the bonding keys and A of subsidiary " * "₃It is bonded), A₁For oxygen atom or COO-* (wherein, the bonding keys and (CH of subsidiary " * "₂)a₂It is bonded).In addition, a₁For 0 or 1 integer, a₂For 2~10 it is whole Number, a₃Integer for 0 or 1).

In above-mentioned formula [2a-1]~[2a-31], particularly preferably formula [2a-1]~formula [2a-6], formula [2a-9]~formula [2a- 13] or formula [2a-22]~formula [2a-31].

In addition, as the diamines with the specific side-chain structure shown in previously described formula [II-2], following formula [2b- can be included 1] diamines shown in~[2b-10].

(A¹Represent the alkyl of carbon number 1~22 or containing fluoroalkyl).

In above-mentioned formula [2b-5]~formula [2b-10], A¹Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂-、-O-、- CO- or-NH-, A²Represent the straight-chain either straight-chain or side chain of the alkyl of branched or carbon number 1~22 of carbon number 1~22 Shape contains fluoroalkyl.

Above-mentioned diamines can also be according to liquid crystal aligning when being made liquid crystal orientation film, pre-tilt angle, voltage retention performance, product The characteristics such as tired electric charge and using a kind or be mixed with two or more.

The above-mentioned diamines with the side chain for making liquid crystal vertical-tropism is preferably using the diamines used in the synthesis of polyamic acid 5~50 moles of % of composition, more preferably the 10~40 of diamine component mole %, particularly preferably 15~30 moles of %.

During using diamines with the side chain for making liquid crystal vertical-tropism, the orientation of raising, liquid crystal in response speed is fixed The aspect of change ability is especially excellent.

As the diamines with photoreactivity side chain, for example, diamines with the side chain shown in formula (3), specifically, The diamines shown in following formulas (3) can be included, but is not limited to this.

(the R in formula (3)⁸、R⁹And R¹⁰Definition it is identical with above-mentioned formula (III).)

Two amino (- NH in formula (3)₂) bonding position do not limit.Specifically, can include：Relative to side The linking group of chain is 2,3 position on phenyl ring, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,5 Position.Wherein, from synthesizing polyamides acid when reactivity from the viewpoint of, preferably 2,4 position, 2,5 position or 3,5 Position.If being additionally contemplates that easiness during synthesis diamines, more preferably 2,4 position or 3,5 position.

Diamines with photoreactivity side chain can specifically include following diamines.

(X⁹、X¹⁰The linking group for belonging to singly-bound ,-O- ,-COO- ,-NHCO- or-NH- is represented independently of one another, and Y is represented The alkylidene for the carbon number 1~20 being optionally replaced by fluorine atoms.)

In addition, as the diamines with photoreactivity side chain, can also include shown in following formula has meeting in side chain The diamines of the group that photodimerizationization reaction occurs and the group that photopolymerization reaction can occur.

In above-mentioned formula, Y₁Expression-CH₂- ,-O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH- or-CO-.Y₂For carbon The alkylidene of number 1~30, the carbocyclic ring of divalence or heterocycle, one or more hydrogen of the alkylidene, the carbocyclic ring of divalence or heterocycle are former Son is optionally substituted by fluorine atom or organic group.Y₂In the case where following group is not adjacent to each other, optional-CH₂- by for It is changed to these groups：-O-、-NHCO-、-CONH-、-COO-、-OCO-、-NH-、-NHCONH-、-CO-.Y₃Expression-CH₂-、- O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH- ,-CO- or singly-bound.Y₄Represent cinnamoyl.Y₅For singly-bound, carbon number 1~ 30 alkylidene, the carbocyclic ring of divalence or heterocycle, one or more hydrogen atoms of the alkylidene, the carbocyclic ring of divalence or heterocycle are appointed Choosing is substituted by fluorine atom or organic group.Y₅In the case where following group is not adjacent to each other, optional-CH₂- be replaced by These groups：-O-、-NHCO-、-CONH-、-COO-、-OCO-、-NH-、-NHCONH-、-CO-.Y₆It is denoted as acryloyl group Or the polymerism group of methylacryloyl.

There is the group that photodimerizationization reaction can occur in side chain and the diamines tool of the group of photopolymerization reaction can occur Following diamines can be included for body, but is not limited to these.

Above-mentioned diamines can be according to liquid crystal aligning when being made liquid crystal orientation film, pre-tilt angle, voltage retention performance, accumulation The characteristics such as electric charge, liquid crystal is made represents the response speed of liquid crystal etc. during element and using a kind or be mixed with two or more.

In addition, the diamines with photoreactivity side chain is preferably using the 10 of the diamine component used in the synthesis of polyamic acid ~70 moles of %, more preferably 20~60 moles of %, particularly preferably 30~50 moles of %.

It should be noted that when manufacture polyimide precursor and/or polyimides, as long as not damaging the effect of the present invention, Other diamines in addition to above-mentioned diamines can also then be applied in combination as diamine component.Specifically, it is for example right to include Phenylenediamine, 2,3,5,6- tetramethyl-para-phenylene diamines, 2,5- dimethyl-p-phenylenediamines, m-phenylene diamine (MPD), 2,4- dimethyl-m-phenylenediamines, 2,5- diaminotoluenes, 2,6- diaminotoluenes, 2,5- diaminophenols, 2,4- diaminophenols, 3,5- diaminophenols, 3, 5- diaminourea benzylalcohol, 2,4- diaminourea benzylalcohol, 4,6- diamino resorcins, 4,4 '-benzidine, 3,3 '-dimethyl -4, 4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy -4,4 '-benzidine, 3,3 ' - Dicarboxyl -4,4 '-benzidine, 3,3 '-two fluoro- 4,4 '-biphenyl, 3,3 '-trifluoromethyl -4,4 '-benzidine, 3, 4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminourea hexichol Methylmethane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2, 3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl Ether, 2,2 '-diamino-diphenyl ether, 2,3 '-diamino-diphenyl ether, 4,4 '-sulfonyldianiline, 3,3 '-sulfonyl hexichol Amine, double (4- aminophenyls) silane, double (3- aminophenyls) silane, dimethyl-bis- (4- aminophenyls) silane, dimethyl-bis- (3- aminophenyls) silane, 4,4 '-phenothiazine, 3,3 '-phenothiazine, 4,4 '-diamino-diphenyl amine, 3,3 '-two Amino-diphenyl-amine, 3,4 '-diamino-diphenyl amine, 2,2 '-diamino-diphenyl amine, 2,3 '-diamino-diphenyl amine, N- first Base (4,4 '-diamino-diphenyl) amine, N- methyl (3,3 '-diamino-diphenyl) amine, N- methyl (3,4 '-diamino-diphenyl) Amine, N- methyl (2,2 '-diamino-diphenyl) amine, N- methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminourea hexichol first Ketone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 1,4- diaminonaphthalenes, 2,2 '-diaminobenzophenone, 2,3 '-diaminobenzophenone, 1,5- diaminonaphthalenes, 1,6- diaminonaphthalenes, 1,7- diaminonaphthalenes, 1,8- diaminonaphthalenes, 2,5- Double (4- aminophenyls) ethane of diaminonaphthalene, 2,6 diaminonaphthalenes, 2,7- diaminonaphthalenes, 2,8- diaminonaphthalenes, 1,2-, 1,2- are double Double (4- aminophenyls) propane of (3- aminophenyls) ethane, 1,3-, double (3- aminophenyls) propane of 1,3-, double (the 4- amino of 1,4- Phenyl) butane, double (3- aminophenyls) butane of 1,4-, double (3,5- diethyl -4- aminophenyls) methane, double (the 4- amino of 1,4- Phenoxy group) benzene, double (4- amino-benzene oxygens) benzene of 1,3-, double (4- aminophenyls) benzene of 1,4-, 1,3- double (4- aminophenyls) benzene, 1, Double (4- aminobenzyls) benzene of 4-, 1,3- double (4- amino-benzene oxygens) benzene, 4,4 '-[1,4- phenylenes dimethylene] diphenylamines, 4, 4 '-[1,3- phenylenes dimethylene] diphenylamines, 3,4 '-[1,4- phenylenes dimethylene] diphenylamines, 3,4 '-[1,3- Asias benzene Base dimethylene] diphenylamines, 3,3 '-[1,4- phenylenes dimethylene] diphenylamines, 3,3 '-[1,3- phenylenes dimethylene] two Aniline, 1,4- phenylenes double [(4- aminophenyls) ketones], 1,4- phenylenes double [(3- aminophenyls) ketone], 1,3- phenylenes Double [(4- aminophenyls) ketones], 1,3- phenylenes double [(3- aminophenyls) ketones], the double (PABAs of 1,4- phenylenes Ester), 1,4- phenylenes double (3- Aminobenzoates), 1,3- phenylenes double (PABA esters), the double (3- of 1,3- phenylenes Aminobenzoate), double (4- aminophenyls) terephthalates, double (3- aminophenyls) terephthalates, double (4- amino Phenyl) isophthalic acid ester, double (3- aminophenyls) isophthalic acid esters, N, N '-(1,4- phenylenes) double (4- aminobenzoyls Amine), N, N '-(1,3- phenylenes) double (4- aminobenzamides), N, N '-(1,4- phenylenes) double (3-ABs), N, N '-(1,3- phenylenes) double (3-ABs), N, N '-bis- (4- aminophenyls) terephthalamide, N, N '-bis- (3- aminophenyls) terephthalamide, N, N '-bis- (4- aminophenyls) isophtalamide, N, N '-bis- (3- aminophenyls) Double (4- aminophenyls) anthracenes of isophtalamide, 9,10-, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfones, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] propane, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] HFC-236fas, 2,2 '-bis- (4- amino Phenyl) HFC-236fa, 2,2 '-bis- (3- aminophenyls) HFC-236fas, 2,2 '-bis- (3- amino -4- aminomethyl phenyls) HFC-236fas, 2,2 '-bis- (4- aminophenyls) propane, 2,2 '-bis- (3- aminophenyls) propane, 2,2 '-bis- (3- amino -4- aminomethyl phenyls) third Double (4- amino-benzene oxygens) propane of alkane, 3,5- diaminobenzoic acids, 2,5- diaminobenzoic acids, 1,3-, double (the 3- aminobenzenes of 1,3- Epoxide) propane, double (4- amino-benzene oxygens) butane of 1,4-, double (3- amino-benzene oxygens) butane of 1,4-, double (the 4- aminobenzene oxygen of 1,5- Base) pentane, double (3- amino-benzene oxygens) pentanes of 1,5-, double (4- amino-benzene oxygens) hexanes of 1,6-, double (the 3- aminobenzene oxygen of 1,6- Base) hexane, double (4- amino-benzene oxygens) heptane of 1,7-, 1,7- (3- amino-benzene oxygens) heptane, 1,8- be double (4- amino-benzene oxygens) Double (3- amino-benzene oxygens) octanes of octane, 1,8-, double (4- amino-benzene oxygens) nonanes of 1,9-, double (3- amino-benzene oxygens) nonyls of 1,9- Alkane, 1,10- (4- amino-benzene oxygens) decane, 1,10- (3- amino-benzene oxygens) decane, 1,11- (4- amino-benzene oxygens) hendecane, 1,11- (3- amino-benzene oxygens) hendecane, 1,12- (4- amino-benzene oxygens) dodecane, 1,12- (3- amino-benzene oxygens) dodecane Deng ester ring type diamines, 1 such as aromatic diamine, double (4- aminocyclohexyls) methane, double (4- amino -3- methylcyclohexyls) methane, 3- diaminopropanes, 1,4- diaminobutanes, 1,5- 1,5-DAPs, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- Diamino-octane, 1,9- diamino nonanes, 1,10- diamino decanes, 1,11- diamino undecanes, 1,12- diamino dodecanes Deng aliphatic diamine.

Above-mentioned other diamines also can according to liquid crystal aligning when being made liquid crystal orientation film, pre-tilt angle, voltage retention performance, The characteristics such as stored charge and using a kind or be mixed with two or more.

It is not particularly limited with tetracarboxylic dianhydride's composition of above-mentioned diamine component reaction.Specifically, can include by equal Benzenetetracarboxylic acid, 2,3,6,7- naphthalene tetracarboxylic acids, 1,2,5,6- naphthalene tetracarboxylic acids, 1,4,5,8- naphthalene tetracarboxylic acids, 2,3,6,7- anthracenes tetrabasic carboxylic acid, 1, 2,5,6- anthracenes tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4- biphenyltetracarboxyacid acids, double (3,4- dicarboxyphenyis) ethers, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, double (3,4- dicarboxyphenyis) sulfones, double (3,4- dicarboxyphenyis) methane, 2,2- are double (3,4- dicarboxyphenyis) propane, 1,1,1,3,3,3- hexafluoros -2,2- double (3,4- dicarboxyphenyis) propane, double (3,4- dicarboxyls Base phenyl) dimethylsilane, double (3,4- dicarboxyphenyis) diphenyl silanes, 2,3,4,5- pyridines tetrabasic carboxylic acid, the double (3,4- of 2,6- Dicarboxyphenyi) pyridine, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid, 3,4,9,10- tetrabasic carboxylic acids, 1,3- diphenyl -1,2,3, 4- cyclobutane tetrabasic carboxylic acid, two adjacent benzene tertacarbonic acid of oxygen, 1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2,3,4- pentamethylene tetrabasic carboxylic acid, 1,2, 4,5- cyclopentanetetracarboxylics, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2- dimethyl -1,2,3,4- ring fourths Alkane tetrabasic carboxylic acid, 1,3- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2,3,4- cycloheptane tetrabasic carboxylic acid, 2,3,4,5- tetrahydrochysene furans Mutter tetrabasic carboxylic acid, 3,4- dicarboxyl -1- cyclohexyl butanedioic acid, 2,3,5- tricarboxylic cyclopentyls acetic acid, 3,4- dicarboxyls -1,2,3,4- Tetrahydrochysene -1- naphthalene succinics, bicyclic [3,3,0] octane -2,4,6,8- tetrabasic carboxylic acids, bicyclic [4,3,0] nonane -2,4,7,9- tetracarboxylic acids Sour, bicyclic [4,4,0] decane -2,4,7,9- tetrabasic carboxylic acids, bicyclic [4,4,0] decane -2,4,8,10- tetrabasic carboxylic acids, three rings [6.3.0.0<2,6>] hendecane -3,5,9,11- tetrabasic carboxylic acids, 1,2,3,4- BTCAs, 4- (2,5- dioxotetrahydrol furans Mutter -3- bases) -1,2,3,4- naphthane -1,2- dicarboxylic acids, bicyclic [2,2,2] octyl- 7- alkene -2,3,5,6- tetrabasic carboxylic acids, 5- (2,5- Dioxotetrahydrol furyl) -3- methyl -3- hexamethylene -1,2- dicarboxylic acids, Fourth Ring [6,2,1,1,0,2,7] dodecane -4,5,9, 10- tetrabasic carboxylic acids, the carboxyl norbornanes -2 of 3,5,6- tri-:3,5:The tetracarboxylic acid that 6 dicarboxylic acids, 1,2,4,5- cyclopentanetetracarboxylics etc. obtain Acid dianhydride.Certainly, tetracarboxylic dianhydride can also be according to liquid crystal aligning when being made liquid crystal orientation film, voltage retention performance, product Using a kind or two or more is applied in combination in the characteristics such as tired electric charge.

<(B) composition>

As (B) composition, aligning agent for liquid crystal of the invention contains：Selected selected from that will contain from following formula (B-1)~(B-5) The diamine component at least one diamines selected is as polyimide precursor obtained from raw material and makes the polyimide precursor acyl sub- Polymer in polyimides obtained from amination, or selected from passing through at least one containing the selection from following formula (3) and (4) Tetracarboxylic dianhydride's composition of tetracarboxylic dianhydride and polyimide precursor obtained from diamine reactant and make the polyimide precursor acyl Polymer in polyimides obtained from imidization.

When at least one tetracarboxylic dianhydride that will be selected from above-mentioned formula (3) and (4) is as raw material, it may be possible to due to passing through Light irradiation and interacted between [liquid crystal-alignment films], stored charge characteristic can be improved.As from above-mentioned formula (3) and (4) tetracarboxylic dianhydride in shown in the chemical formula of selection, can include following compound, but be not limited to these.

At least one tetracarboxylic dianhydride of this selection from above-mentioned formula (1-1)~(1-4) is preferably used as polyamide 10~100% amount of the tetracarboxylic dianhydride's composition used in the synthesis of (B) composition of acid.More preferably using 10~60% compared with It is good.

As long as in addition, not damaging the effect of the present invention, then four in addition to above-mentioned formula (1-1)~(1-4) can also be used Raw material of the carboxylic acid dianhydride as (B) composition.Concrete example can include the tetracarboxylic dianhydride illustrated in (A) composition, but be not limited to These.

For example, when the tetracarboxylic dianhydride with aliphatic group, alicyclic group also serves as raw material, it is preferably used as gathering 0~90% amount of the tetracarboxylic dianhydride's composition used in the synthesis of (B) composition of amic acid.

(B) when at least one tetracarboxylic dianhydride of selection from above-mentioned formula (1-1)~(1-4) is used in composition, carry out anti- The diamine component answered is not particularly limited, and as their concrete example, can include the diamines enumerated in (A) composition, using from It is preferable from the viewpoint of stored charge characteristic in above-mentioned formula (B-1)~(B-5) during at least one kind of diamines of selection.

It should be noted that the polymer as (B) composition can also be selected from will contain from following formula (B-1)~(B- 5) diamine component of at least one diamines of selection is as polyimide precursor obtained from raw material and before making the polyimides in Polymer in polyimides obtained from body imidizate.

(Y in formula₁Represent the organic group of the monovalence with secondary amine, tertiary amine or heterocycle structure, Y₂Represent with secondary amine, tertiary amine Or the organic group of the divalence of heterocycle structure.)

Two with the high specific structure of polarity selected by using at least one from above-mentioned formula (B-1)~(B-5) Amine, or be further respectively combined using at least one diamines with carboxyl above and the diamines with nitrogenous heteroaromatic, So as to be formed by salt, the electrostatic interaction of hydrogen bond etc promotes electric charge to move, therefore can improve stored charge characteristic. As at least one diamines of the selection from above-mentioned formula (B-1)~(B-5), following diamines can be included, but be not limited to this A bit.

And then it will can also be used as the polymer of (B) composition in (A) composition with the side for making liquid crystal vertical-tropism The diamines of chain also serves as raw material.

At least one diamines of this selection from above-mentioned formula (B-1)~(B-5) is preferably used as (B) of polyamic acid 10 moles of %~80 mole % of the diamine component used in the synthesis of composition amount.

Using tetracarboxylic dianhydride during at least one diamines of selection, reacted from above-mentioned formula (B-1)~(B-5) into Point it is not particularly limited, as their concrete example, the tetracarboxylic dianhydride enumerated in (A) composition can be included, using from above-mentioned It is preferable from the viewpoint of stored charge is reduced in formula (3) and (4) during at least one kind of tetracarboxylic dianhydride of selection.

The present invention aligning agent for liquid crystal in, can also as needed contain more than 2 end have photopolymerization can occur Or the polymerizable compound of the group of photo-crosslinking.The polymerizable compound be possess two or more have can occur photopolymerization or The compound of the end of the group of photo-crosslinking.Herein, the polymerizable compound with the group that photopolymerization can occur refers to have The compound of functional group that can be by irradiation light to polymerize.In addition, the compound with the group that photo-crosslinking can occur is Refer to, having can be by irradiation light come the polymer with polymerizable compound, selected from polyimide precursor and before making the polyimides At least one of polyimides polymer reaction obtained from body imidizate and with they be crosslinked functional group compound. It should be noted that compound with the group that photo-crosslinking can occur and the compound with the group that photo-crosslinking can occur that It can also be reacted between this.

By the way that the aligning agent for liquid crystal of the invention containing above-mentioned polymerizable compound is used for into SC-PVA type liquid crystal displays Liquid crystal Deng vertical orientation mode represents element, so as to have this to make the side chain of liquid crystal vertical-tropism and light anti-with being used alone The polymer of answering property side chain, the situation of the polymerizable compound are compared, and can significantly improve response speed, even few polymerization The addition of property compound also can fully improve response speed.

As the group that photopolymerization or photo-crosslinking can occur, the group of the monovalence shown in following formula (IV)s can be included.

(R¹²Represent the alkyl of hydrogen atom or carbon number 1~4.Z¹Represent optionally by the alkyl of carbon number 1~12 or carbon number 1~12 Alkoxy substitution divalence aromatic rings or heterocycle.Z²Represent optionally by the alkyl of carbon number 1~12 or the alkane of carbon number 1~12 The aromatic rings or heterocycle of the monovalence of epoxide substitution.)

As the concrete example of polymerizable compound, can include having respectively 2 ends shown in following formula (V)s can send out The end possessed with the base that photopolymerization can occur shown in the compound of group of third contact of a total solar or lunar eclipse polymerization, following formula (VI)s and with meeting The compound of end of the group of photo-crosslinking occurs, photo-crosslinking can occur for having respectively 2 ends shown in following formula (VII)s Group compound.

It should be noted that in following formula (V)s~(VII), R¹²、Z¹And Z²With the R in above-mentioned formula (IV)¹²、Z¹And Z²Phase Together, Q¹For the organic group of divalence.Q¹It is preferred that there is phenylene (- C₆H₄-), biphenylene (- C₆H₄-C₆H₄-), cyclohexylidene (- C₆H₁₀-) etc. ring structure.Because easily become big with the interaction of liquid crystal.

The concrete example of polymerizable compound shown in formula (V) can include the polymerizable compound shown in following formula (4).Under State in formula (4), V, W are singly-bound or use-R¹O- is represented, R¹For straight-chain or the alkylidene of the carbon number 1~10 of branched, preferably For with-R¹O- is represented, R¹For straight-chain or the alkylidene of the carbon number 2~6 of branched.It should be noted that V, W can be with identical Can also be different, but it is identical when be readily synthesized.

It should be noted that even there is acrylate-based, methyl as the group that photopolymerization or photo-crosslinking can occur Acrylate-based rather than alpha-methylene-gamma-butyrolactone base polymerizable compound, there is the acrylate-based, methacrylic acid Ester group by oxyalkylene at equal intervals the polymerizable compound for the structure that group is bonded with phenylene and above-mentioned two end have α- The polymerizable compound of methylene-y-butyrolactone base similarly can particularly marked degree improve response speed.In addition, with third Olefin(e) acid ester group, methacrylic acid ester group by the oxyalkylene structure that group is bonded with phenylene at equal intervals polymerizable compound The stability of heat is improved, can substantially resistant to by high temperature, such as more than 200 DEG C of firing temperature.

During by the reaction of diamine component and tetracarboxylic dianhydride to obtain polyamic acid, known synthesis side can be used Method.Generally there is the method for making diamine component be reacted in organic solvent with tetracarboxylic dianhydride's composition.Diamine component and tetracarboxylic acid The reaction of acid dianhydride is easier to carry out in organic solvent, and does not produce accessory substance, is favourable on this point.

As the organic solvent used in above-mentioned reaction, just do not limited especially as long as generated polyamic acid can be dissolved It is fixed.And then even the organic solvent of insoluble polyamic acid, in the range of the polyamic acid generated will not separate out, It can mix to above-mentioned solvent to use.It should be noted that the moisture in organic solvent can suppress polymerisation, and then cause The polyamic acid generated hydrolyzes, and therefore, organic solvent preferably uses after dehydrating.

As the organic solvent used in above-mentioned reaction, such as DMF, N, N- dimethyl can be included Acetamide, N, N- diethylformamides, N-METHYLFORMAMIDE, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, 2- pyrroles Pyrrolidone, 1,3- dimethyl-2-imidazolinones, 3- methoxyl groups-N, N- dimethylpropane acid amides, N- methyl caprolactams, diformazan Base sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, isopropanol, methoxy amylalcohol, diamyl Alkene, ethyl pentyl group ketone, methyl nonyl ketone, MEK, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, the molten fibre of ethyl Agent, methylcellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, Ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propane diols, Propylene glycol monoacetate, the third two Alcohol monomethyl ether, propylene glycol monobutyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethyl two Alcohol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropyl Glycol monomethyl ether, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, DPG list second Acid esters list propyl ether, 3- methyl -3- methoxybutyls acetic acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanols, diisopropyl Ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, DIBK, methylcyclohexene, propyl ether, two oneself Ether, dioxanes, n-hexane, pentane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, Ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, glutaric acid methyl esters, pentanedioic acid diethyl ester, 3- methoxy methyl propionates, 3- ethoxy-propionic acids Methylethyl, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- methoxyl groups Propionic acid, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanones, 2- second Base -1- hexanols etc..These organic solvents may be used alone or in combination.

Allow the method that diamine component and tetracarboxylic dianhydride's composition are reacted in organic solvent for following method it In any means：Diamine component being dispersed or dissolved in, solution that organic solvent forms is stirred, and directly adds tetracarboxylic acid Acid dianhydride component makes tetracarboxylic dianhydride's composition be dispersed or dissolved in after organic solvent the method for row addition again；Conversely, to making Tetracarboxylic dianhydride's composition is dispersed or dissolved in the method that diamine component is added in the solution that organic solvent forms；Alternately add four Method of carboxylic acid dianhydride composition and diamine component etc..In addition, diamine component or tetracarboxylic dianhydride's composition are made up of multiple compounds When, it can be reacted, can also be reacted successively respectively in the state of being mixed in advance, and then, it can also make The low-molecular weight for reacting to obtain respectively carries out hybrid reaction HMW body is made.

Temperature when being reacted diamine component and tetracarboxylic dianhydride's composition is, for example, -20 DEG C~150 DEG C, is preferably -5 DEG C~100 DEG C of scope.In addition, for reaction, such as relative to reaction solution, diamine component and tetracarboxylic dianhydride's composition Total concentration is preferably 1~50 mass %, more preferably 5~30 mass %.

The total mole number of tetracarboxylic dianhydride's composition in above-mentioned polymerisation relative to the total mole number of diamine component ratio Rate can select according to the molecular weight of desired polyamic acid.In the same manner as common polycondensation reaction, the mol ratio is closer 1.0, the molecular weight of the polyamic acid of generation is bigger, is 0.8~1.2 if preferred scope is shown.

The synthetic method of the polyamic acid used in the present invention is not limited to the above method, the conjunction with common polyamic acid Into method similarly, above-mentioned four are replaced by using tetracarboxylic acid derivatives such as the tetrabasic carboxylic acid of counter structure or the carboxylic acid halides of tetrabasic carboxylic acid two Carboxylic acid dianhydride, and method known to utilization makes its reaction, can also obtain corresponding polyamic acid.

As the method for making above-mentioned polyamic acid carry out imidizate and polyimides being made, can include：By polyamide The direct-fired hot-imide of solution of acid；The catalysis imidizate of catalyst is added into the solution of polyamic acid.Need Illustrate, the acid imide rate of polyimides is changed into from polyamic acid one to be set to 100%.

Temperature when making the polyamic acid carry out hot-imide in the solution is 100 DEG C~400 DEG C, preferably 120 DEG C~ 250 DEG C, preferably while will be expelled to by imidization reaction and the water generated outside system while carrying out hot-imide.

The catalyst imidizate of polyamic acid can be by adding base catalyst and acid in the solution to polyamic acid Acid anhydride, and with -20~250 DEG C, be preferably stirred with 0~180 DEG C to carry out.The amount of base catalyst is the 0.5 of acid amides acidic group ~30 moles times, preferably 2~20 moles times, the amount of acid anhydrides is 1~50 mole times of acid amides acidic group, is preferably 3~30 moles Times.As base catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be included, wherein, pyridine possesses pair The appropriate alkalescence for reaction is promoted, so it is preferred that.As acid anhydrides, acetic anhydride, trimellitic anhydride, equal benzene four can be included Acid anhydrides etc., wherein, if using acetic anhydride, reaction is easily refined after terminating, so it is preferred that.Acyl based on catalysis imidizate Amination rate can be controlled by adjusting catalytic amount and reaction temperature, reaction time.

In addition, poly amic acid ester can be by making tetracarboxylic acid acid diesters diacid chloride and same with the synthesis of above-mentioned polyamic acid The reaction of diamines, make tetracarboxylic acid acid diesters and deposited with the same diamines of synthesis of above-mentioned polyamic acid in appropriate condensing agent, alkali Reacted inferior to manufacture.Alternatively, it is also possible to by the pre-synthesis polyamic acid of the above method, be incited somebody to action using high molecular weight reactive Carboxylic acid in amic acid is esterified, so as to obtain.Specifically, for example, make tetracarboxylic acid acid diesters diacid chloride and diamines in alkali and Reacted in the presence of organic solvent at -20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C 30 minutes~24 hours, preferably 1 hour~4 Hour, so as to synthesizing polyamides acid esters.Then, poly amic acid ester is heated at high temperature, promotes dealcoholysis to bring it about and close Ring, it can also obtain polyimides.

The polyimide precursor or polyimides of generated polyamic acid, poly amic acid ester etc. are reclaimed from reaction solution When, reaction solution can be put into poor solvent and make its precipitation.As poor solvent used in precipitation, first can be included Alcohol, acetone, hexane, butyl cellosolve, heptane, MEK, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc..Put into bad Solvent and make its precipitate polymer after being recovered by filtration, air drying or heat drying can be carried out under normal or reduced pressure. In addition, if the polymer for making recovery is dissolved in organic solvent again and reclaim again precipitation operation repeat 2~10 times, then The impurity in polymer can be reduced.As poor solvent now, it can include such as alcohols, ketone, hydrocarbon, if used More than the 3 kinds poor solvents selected among these, then purification efficiency further improve, so it is preferred that.

The aligning agent for liquid crystal of the present invention contains at least one polymer for having structure shown in above-mentioned formula (1) in side chain, institute The content for stating polymer is preferably 1~20 mass %, more preferably 3~15 mass %, particularly preferably 3~10 mass %.Separately Outside, containing more than 2 end respectively have photopolymerization or photo-crosslinking can occur group polymerizable compound when, its content It is preferably 1~50 mass parts, more preferably 5~30 mass parts relative to the above-mentioned mass parts of polymer 100.

In addition, the aligning agent for liquid crystal of the present invention can also contain other polymer in addition to above-mentioned polymer.Now, gather The content of other polymer in compound whole composition is preferably 0.5~80 mass %, more preferably 20~50 mass %.

The molecular weight of polymer possessed by aligning agent for liquid crystal is considering liquid crystal aligning obtained from coating of liquid crystalline alignment agent To pass through GPC (gel permeation chromatographies when operability when film strength and film formation, the uniformity of film；Gel Permeation Chromatography) the Weight-average molecular gauge of method measure is preferably 5000~1000000, more preferably 10000~150000.

The solvent contained in aligning agent for liquid crystal is not particularly limited, and can be dissolved in side chain has knot shown in above-mentioned formula (1) The polymer of structure and the end more than 2 contained as needed have gathering for the group that photopolymerization or photo-crosslinking can occur respectively The solvents containing composition such as conjunction property compound.For example, have as being illustrated during the synthesis of above-mentioned polyamic acid can be included Solvent.Wherein, from the viewpoint of dissolubility, preferably METHYLPYRROLIDONE, gamma-butyrolacton, N- ethyl -2- pyrroles Pyrrolidone, 1,3- dimethyl-2-imidazolinones, 3- methoxyl groups-N, N- dimethylpropionamide.It is of course also possible to it is of more than two kinds Mixed solvent.

Additionally, it is preferred that by for improving the uniformity of film, the solvent of flatness be mixed into aligning agent for liquid crystal contain into Point dissolubility high solvent in use.As the solvent, such as isopropanol, methoxy amylalcohol, first can be included Base cellosolve, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, butyl cellosolve acetate, ethyl cellosolve second Acid esters, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethylene glycol Dan Yi Propyl ether, ethylene glycol monobutyl ether, propane diols, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, glycol tertiary fourth Ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, two Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, DPE, dipropyl two Alcohol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyl second Acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanols, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, Butyl butyrate, butyl ether, DIBK, methylcyclohexene, propyl ether, hexyl ether, n-hexane, pentane, normal octane, diethyl Ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, glutaric acid first Ester, pentanedioic acid diethyl ester, 3- methoxy methyl propionates, 3- ethoxy-propionic acids Methylethyl, 3- methoxypropionates, 3- ethyoxyls Propionic acid, 3- methoxypropionic acids, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, 1- methoxy-2-propanols, 1- ethyoxyls- 2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propane diols - 1- monomethyl ether -2- acetic acid esters, propane diols -1- list ether -2- acetic acid esters, DPG, 2- (2- ethoxy-cs epoxide) propyl alcohol, breast Sour methyl esters, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, 2- ethyl -1- hexanols etc..These solvents can be with It is used in mixed way a variety of.These solvents are preferably 5~80 overall mass % of the solvent that contains in aligning agent for liquid crystal, and more preferably 20 ~60 mass %.

Composition in addition to that mentioned above can be contained in aligning agent for liquid crystal.As its example, can include for making coating There is the compound that film thickness uniformity during aligning agent for liquid crystal, surface smoothness improve；For improving liquid crystal orientation film and substrate Compound of adaptation etc..

As for improving film thickness uniformity, the compound of surface smoothness, fluorine system surfactant, silicone can be included It is surfactant, nonionic surfactants etc..More specifically, can include such as Eftop EF301, EF303, EF352 (Tohkem products Corporation systems), Megafac F171, F173, R-30 (big Japanese ink strain formula meeting Society's system), Fluorad FC430, FC431 (Sumitomo 3M company systems), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd's system) etc..The use ratio phase of these surfactants The mass parts of total amount 100 of polymer for containing in aligning agent for liquid crystal be preferably 0.01~2 mass parts, more preferably 0.01~ 1 mass parts.

As the concrete example of the compound of the adaptation for improving liquid crystal orientation film and substrate, can include containing functionality The compound of silane, compound containing epoxy radicals etc..Such as 3- TSL 8330s, 3- aminopropyls can be included Triethoxysilane, 2- TSL 8330s, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- TSL 8330, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, 3- urea propyl group trimethoxies Base silane, 3- ureas propyl-triethoxysilicane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyls - APTES, N- triethoxysilylpropyltetrasulfide triethylenes triamine, N- trimethoxysilyls third Base triethylene triamine, the azepine decane of 10- trimethoxysilyls -1,4,7- three, 10- triethoxysilyls -1,4,7- Three azepine decane, 9- trimethoxysilyl -3,6- diaza nonyls acetic acid esters, 9- triethoxysilyls -3,6- two Azepine nonyl acetic acid esters, N- benzyl -3- TSL 8330s, N- benzyls-APTES, N- Double (oxygen the ethylidene) -3- ammonia of phenyl -3- TSL 8330s, N- phenyl-APTES, N- Double (oxygen the ethylidene)-APTESs of base propyl trimethoxy silicane, N-, ethylene glycol diglycidylether, Polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol two shrink sweet Oily ether, neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromos are new Neopentyl glycol diglycidyl glycerin ether, 1,3,5,6- four glycidyl group -2,4- hexane diols, N, N, N ', N ',-four glycidyl group M-xylene diamine, 1,3- double (N, N- diglycidyl amino methyl) hexamethylene, N, N, N ', N ',-four glycidyl group -4, 4 '-diaminodiphenyl-methane, 3- (N- pi-allyl-N- glycidyls) TSL 8330, (N, N-'s 3- bis- contracts Water glyceryl) TSL 8330 etc..

In addition, in order to further improve the film-strength of liquid crystal orientation film, 2,2 ' can also be added-bis- (4- hydroxyls -3,5- bis- Hyd roxymethyl phenyl) phenolic compounds such as propane, four (methoxy) bis-phenols.These compound phases in aligning agent for liquid crystal for containing The mass parts of total amount 100 of some polymer are preferably 0.1~30 mass parts, more preferably 1~20 mass parts.

And then in aligning agent for liquid crystal, in addition to that mentioned above, in the range of effect of the present invention is not damaged, it can also add Dielectric, the conductive materials of the electrical characteristics such as dielectric constant, electric conductivity for changing liquid crystal orientation film.

By the way that the aligning agent for liquid crystal to be coated on substrate and burn till, the liquid crystal for making liquid crystal vertical-tropism can be formed Alignment films.By the use of the aligning agent for liquid crystal of the present invention, can accelerate to represent using the liquid crystal of resulting liquid crystal orientation film The response speed of element.In addition, on the present invention aligning agent for liquid crystal in can also contain, end has respectively more than 2 There is the polymerizable compound for the group that photopolymerization or photo-crosslinking can occur, by making it contain in liquid crystal not contain in liquid crystal Contain in alignment agent or together with aligning agent for liquid crystal in liquid crystal, so as to also make the sensitive of light reaction under so-called PSA patterns Degree is uprised, and inclination angle can be also assigned even with less ultraviolet irradiation amount.

For example, it is also possible to after the aligning agent for liquid crystal of the present invention is applied into substrate, dries and burn till as needed, will thus Obtained cured film is directly used as liquid crystal orientation film.Alternatively, it is also possible to by the cured film carry out brushing or irradiation polarised light or Light of specific wavelength etc. or carry out the processing of ion beam etc. and PSA alignment films are made, the liquid crystal after filling liquid crystal is represented Element irradiates UV in the state of voltage is applied.Especially, it is useful to be used as PSA alignment films.

Now, as used substrate, as long as transparent high substrate is just not particularly limited, glass can be used Plate, makrolon, poly- (methyl) acrylate, polyether sulfone, polyarylate, polyurethane, polysulfones, polyethers, polyether-ketone, trimethyl penta Alkene, polyolefin, polyethylene terephthalate, (methyl) acrylonitrile, tri acetyl cellulose, diacetyl cellulose, second Plastic base of sour cellulose butyrate etc. etc..In addition, from the viewpoint of the chemical industry skill that conforms to the principle of simplicity, preferably use formed with for driving liquid The substrate of brilliant ITO electrode etc..In addition, the liquid crystal of reflection-type is represented in element, if being only unilateral substrate, can also use The opaque substrate such as silicon wafer, electrode now can also use the material of the meeting reflected light such as aluminium.

The coating method of aligning agent for liquid crystal is not particularly limited, and can include：Silk-screen printing, intaglio printing, flexographic printing Etc. print process；Ink-jet method, spraying process, rolling method, dipping, roll coater, slit coater, spin coater etc..In terms of productivity ratio Set out, hectographic printing method is widely used in industry, can also compatibly use in the present invention.

The film formed using above method coating of liquid crystalline alignment agent can be burnt till and cured film is made.It is coated with Drying process after aligning agent for liquid crystal not necessarily, each substrate when time untill burning till is not fixed from after being coated with or When not burnt till immediately after coating, process is preferably dried.Will not to film shape as long as the drying removes solvent The degree deformed by carrying of substrate etc., is not particularly limited for its drying means.It can include for example in temperature To be dried in 40 DEG C~150 DEG C, preferably 60 DEG C~100 DEG C of heating plates 0.5 minute~30 minutes, preferably drying 1 minute~5 The method of minute.

Do not limited and the firing temperature of the film formed by coating of liquid crystalline alignment agent, for example, 100~350 DEG C, excellent Elect 120~300 DEG C, more preferably 150 DEG C~250 DEG C as.Firing time is 5 minutes~240 minutes, is preferably 10 minutes ~90 minutes, more preferably 20 minutes~90 minutes.Heating can be followed by generally well-known method, such as heating plate, hot blast Ring oven, infrared heating heating furnace etc. are carried out.

In addition, the thickness for the liquid crystal orientation film being fired into is not particularly limited, preferably 5~300nm, more preferably 10 ~100nm.

Liquid crystal on the present invention represents element, after liquid crystal orientation film can be formed on substrate by the above method, Liquid crystal cells are made using known method.The concrete example of element is represented as liquid crystal, to possess the vertical orientated of liquid crystal cells The liquid crystal of mode represents element, and the liquid crystal cells have：2 plate bases that configure in an opposing fashion, set between the substrates Liquid crystal layer and the above-mentioned liquid crystal aligning that is arranged between substrate and liquid crystal layer and is formed by the aligning agent for liquid crystal of the present invention Film.Specifically, it is the liquid crystal expression element for the vertical orientation mode for possessing the liquid crystal cells made as follows：By by the present invention Aligning agent for liquid crystal be coated on 2 plate bases and burn till and form liquid crystal orientation film, match somebody with somebody in a manner of the liquid crystal orientation film is relative 2 plate bases are put, the liquid crystal layer being made up of liquid crystal is clamped between 2 plate base, liquid crystal layer is set with contacting liquid crystal orientation film, Ultraviolet is irradiated when applying voltage to liquid crystal orientation film and liquid crystal layer, so as to make liquid crystal cells.

The liquid crystal orientation film formed by using the aligning agent for liquid crystal by the present invention, is applied to liquid crystal orientation film and liquid crystal layer side Power-up flanging irradiates ultraviolet and polymerize polymerizable compound, also, makes photoreactivity side chain possessed by polymer Reacted each other, reacted photoreactivity side chain and polymerizable compound possessed by polymer, so as to taking for liquid crystal Element is represented to by more effectively immobilization, the obvious excellent liquid crystal of formation response speed.

Liquid crystal as the present invention represents the substrate used in element, as long as transparent high substrate does not just limit especially Determine, usually the substrate formed with the transparency electrode for driving liquid crystal on substrate.As concrete example, can include with it is above-mentioned Substrate identical substrate described in liquid crystal orientation film.It can also use provided with existing electrode pattern, the substrate of projection pattern, But liquid crystal of the invention represents aligning agent for liquid crystal of the element due to having used the invention described above, therefore even in single sided substrate It is upper formed such as 1~10 μm line/gap electrode pattern and do not form the knot of slit pattern or projection pattern on opposite substrate It can also be worked under structure, technique when can represent element using the liquid crystal of the structure to simplify manufacture, obtain high-transmission rate.

In addition, in the high function element of TFT type elements etc, can use in the electrode and substrate for driving liquid crystal Between form product obtained from the element of transistor etc.

In the case where transmission-type liquid crystal represents element, usually using above-mentioned etc substrate, but reflective liquid crystal represents In element, if being only unilateral substrate, the opaque substrates such as silicon wafer can also be used.Now, it is formed at the electricity of substrate Pole can also use the material of the aluminium of meeting reflected light etc.

The liquid crystal for forming the present invention represents that the liquid crystal material of the liquid crystal layer of element is not particularly limited, and can use and exist in the past The liquid crystal material used in vertical orientation mode, such as MLC-6608, MLC-6609 of MERCK Corporation manufactures etc. are negative Type liquid crystal.In addition, under PSA patterns, such as the liquid crystal containing such polymerizable compound shown in following formula can be used.

In the present invention, as the method liquid crystal layer being clamped between 2 plate bases, can include known method.Can Include for example following methods：Prepare 1 pair of substrate formed with liquid crystal orientation film, spread on the liquid crystal orientation film of a substrate Pearl thing at equal intervals, another substrate is pasted in a manner of the surface of the side formed with liquid crystal orientation film turns into inner side, is depressurized Inject liquid crystal and the method sealed.In addition, liquid crystal cells can also be made by following method：Prepare formed with liquid crystal aligning 1 pair of substrate of film, on the liquid crystal orientation film of a substrate spread pearl is added dropwise liquid crystal after thing at equal intervals, then with formed with liquid The mode that the surface of the side of brilliant alignment films turns into inner side pastes the method that another substrate is sealed.The thickness of above-mentioned sept Degree is preferably 1~30 μm, more preferably 2~10 μm.

By applying voltage to liquid crystal orientation film and liquid crystal layer while irradiating ultraviolet to make the work of liquid crystal cells Sequence can include for example applies electricity by applying voltage between the electrode to being set on substrate to liquid crystal orientation film and liquid crystal layer , the method for irradiation ultraviolet under conditions of the electric field is kept.Herein, as the voltage applied between electrode, for example, 5~ 30Vp-p, it is preferably 5~20Vp-p.Ultraviolet irradiation amount is, for example, 1~60J, is preferably below 40J, ultraviolet irradiation amount Can suppress when few because form liquid crystal represent element component destruction and caused by reliability reduce, and reduce ultraviolet photograph The time is penetrated, is suitable so as to which manufacture efficiency improves.

If as described above, applied voltage to liquid crystal orientation film and liquid crystal layer while irradiating ultraviolet, polymerism Compound is reacted and forms polymer, and the incline direction of liquid crystal molecule is remembered by the polymer, so as to accelerate Gained liquid crystal represents the response speed of element.In addition, voltage is applied to liquid crystal orientation film and liquid crystal layer while irradiating ultraviolet During line, selected from the side chain for making liquid crystal vertical-tropism and the polyimide precursor of photoreactivity side chain and making the polyimides Photoreactivity side chain possessed by least one of polyimides polymer obtained from precursor imidizate occurs instead each other Should, photoreactivity side chain reacts with polymerizable compound possessed by polymer, therefore can accelerate resulting liquid crystal Represent the response speed of element.

Embodiment

Hereinafter, it is further described based on embodiment, but the present invention is not by any restriction of the embodiment.

The abbreviation used in the preparation of following aligning agent for liquid crystal is as described below.

(acid dianhydride)

BODA：Bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydrides

CBDA：1,2,3,4- cyclobutane tetracarboxylic dianhydrides

PMDA：Pyromellitic acid dianhydride

TCA：2,3,5- tricarboxylic cyclopentyl acetic acid -1,4,2,3- dianhydrides

(diamines)

p-PDA：P-phenylenediamine

DBA：3,5- diaminobenzoic acids

3AMPDA：It is photosensitive shown in 3,5- diamino-Ns-(pyridin-3-yl methyl) benzamide following formula DA-1~DA-3 Property diamines

Polymerism diamines shown in following formula DA-4

Vertical orientated property side chain diamines shown in following formula DA-5~DA-7

Diamines shown in following formula DA-8~9

NMP：METHYLPYRROLIDONE

BCS：Butyl cellosolve

3AMP：3- pyridyl-methanamines

Polymerizable compound shown in following formula RM1

In addition, the molecule measuring fixed condition of polyimides is as shown below.

Device：Normal temperature gel permeation chromatography (GPC) device (SSC- of Senshu Scientific co., ltd. manufactures 7200)

Post：The post (KD-803, KD-805) of Shodex companies manufacture

Column temperature：50℃

Eluent：N, N '-dimethyl formamide is (as additive, lithium bromide monohydrate (LiBrH₂O) it is 30mmol/L, phosphoric acid anhydrous crystalline (orthophosphoric acid) are 30mmol/L, tetrahydrofuran (THF) is 10ml/L)

Flow velocity：1.0ml/ minute

Standard curve making standard sample：(molecular weight is about the TSK standards PEO of TOSOH Co., Ltd's manufacture 9000000th, 150000,100000,30000) and Polymer Laboratories Ltd. manufactures polyethylene glycol (molecular weight About 12000,4000,1000).

In addition, the acid imide rate of polyimides determines as follows.Polyimide powder 20mg is put into NMR samples Pipe (wasteland's science Co., Ltd. manufacture NMR sampling pipe standards φ 5), addition deuterated dimethyl sulfoxide (DMSO-d₆, 0.05%TMS Melange) 1.0ml, applying ultrasonic wave is completely dissolved it.The NMR manufactured for the solution with JEOL DATUM LTD. is determined Device (JNW-ECA500) determines 500MHz proton NMR.Acid imide rate is by from the knot not changed before and after imidizate The proton of structure determines as reference proton, uses the peak integrated value of the proton and the acyl from 9.5~10.0ppm appearance nearby The proton peak integrated value of the NH bases of amino acid is obtained using following formula.It should be noted that in following formula, x is from amic acid NH bases proton peak integrated value, the peak integrated value of proton on the basis of y, base when α is polyamic acid (acid imide rate is 0%) Quasi- proton relative to 1 proton of the NH bases of amic acid number ratio.

Acid imide rate (%)=(1- α x/y) × 100

(synthesis example 1)

By BODA (10.01g, 40.0mmol), 3AMPDA (4.85g, 20.0mmol), DA-2 (13.22g, 40.0mmol), DA-5 (15.22g, 40.0mmol) is dissolved in NMP (164.6g), after being reacted 5 hours at 60 DEG C, addition CBDA (11.57g, 59.0mmol) with NMP (54.9g), reacted 10 hours at 40 DEG C, obtain polyamic acid solution.

After being diluted to 6.5 mass % to the middle addition NMP of the polyamic acid solution (250g), add and urged as imidizate The acetic anhydride (46.4g) and pyridine (14.4g) of agent, react 3 hours at 70 DEG C.The reaction solution is put into methanol In (3300ml), leaching gained sediment.The sediment is cleaned with methanol, and is dried under reduced pressure at 100 DEG C, so as to be gathered Acid imide powder (A).The acid imide rate of the polyimides is 72%, number-average molecular weight 14000, and weight average molecular weight is 38000。

The addition NMP (44.0g) into resulting polyimide powder (A) (6.0g), being stirred 20 hours at 70 DEG C makes It dissolves.3AMP (1 mass %NMP solution) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, is stirred at room temperature Mix 5 hours, so as to obtain aligning agent for liquid crystal (U1).

(synthesis example 2)

By BODA (10.01g, 40.0mmol), 3AMPDA (4.85g, 20.0mmol), DA-1 (14.34g, 40.0mmol), DA-5 (15.22g, 40.0mmol) is dissolved in NMP (168.0g), after being reacted 5 hours at 60 DEG C, addition CBDA (11.57g, 59.0mmol) with NMP (55.98g), reacted 10 hours at 40 DEG C, obtain polyamic acid solution.

After being diluted to 6.5 mass % to the middle addition NMP of the polyamic acid solution (250g), add and urged as imidizate The acetic anhydride (45.4g) and pyridine (14.0g) of agent, react 3 hours at 70 DEG C.The reaction solution is put into methanol (3300ml), leaching gained sediment.The sediment is cleaned with methanol, and is dried under reduced pressure at 100 DEG C, so as to obtain polyamides Imines powder (B).The acid imide rate of the polyimides is 73%, number-average molecular weight 18000, weight average molecular weight 37000.

The addition NMP (44.0g) into resulting polyimide powder (B) (6.0g), being stirred 20 hours at 70 DEG C makes It dissolves.3AMP (1 mass %NMP solution) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, is stirred at room temperature Mix 5 hours, so as to obtain aligning agent for liquid crystal (U2).

(synthesis example 3)

By BODA (10.01g, 40.0mmol), 3AMPDA (4.85g, 20.0mmol), DA-3 (13.78g, 40.0mmol), DA-5 (15.22g, 40.0mmol) is dissolved in NMP (166.2g), after being reacted 5 hours at 60 DEG C, addition CBDA (11.57g, 59.0mmol) with NMP (55.42g), reacted 10 hours at 40 DEG C, obtain polyamic acid solution.

After being diluted to 6.5 mass % to the middle addition NMP of the polyamic acid solution (250g), add and urged as imidizate The acetic anhydride (45.49g) and pyridine (14.3g) of agent, react 3 hours at 70 DEG C.The reaction solution is put into methanol (3300ml), leaching gained sediment.The sediment is cleaned with methanol, and is dried under reduced pressure at 100 DEG C, so as to obtain polyamides Imines powder (C).The acid imide rate of the polyimides is 72%, number-average molecular weight 21000, weight average molecular weight 82000.

The addition NMP (44.0g) into resulting polyimide powder (C) (6.0g), being stirred 20 hours at 70 DEG C makes It dissolves.3AMP (1 mass %NMP solution) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, is stirred at room temperature Mix 5 hours, so as to obtain aligning agent for liquid crystal (U3).

(synthesis example 4)

By TCA (11.21g, 50.0mmol), p-PDA (4.33g, 40.0mmol), DA-3 (6.89g, 20.0mmol), DA- 5 (7.61g, 20.0mmol), DA-7 (9.90g, 20.0mmol) are dissolved in NMP (148.6g), are reacted 5 hours at 80 DEG C Afterwards, CBDA (9.61g, 49.0mmol) and NMP (49.54g) is added, is reacted 10 hours at 40 DEG C, obtains polyamic acid solution.

After being diluted to 6.5 mass % to the middle addition NMP of the polyamic acid solution (220g), add and urged as imidizate The acetic anhydride (35.1g) and pyridine (10.9g) of agent, react 3 hours at 50 DEG C.The reaction solution is put into methanol (2900ml), leaching gained sediment.The sediment is cleaned with methanol, and is dried under reduced pressure at 100 DEG C, so as to obtain polyamides Imines powder (D).The acid imide rate of the polyimides is 51%, number-average molecular weight 11000, weight average molecular weight 25000.

The addition NMP (44.0g) into resulting polyimide powder (D) (6.0g), being stirred 20 hours at 70 DEG C makes It dissolves.3AMP (1 mass %NMP solution) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, is stirred at room temperature Mix 5 hours, so as to obtain aligning agent for liquid crystal (U4).

(synthesis example 5)

By BODA (10.01g, 40.0mmol), DA-4 (7.93g, 30.0mmol), DA-3 (10.33g, 30.0mmol), DA-5 (7.61g, 20.0mmol), DA-6 (8.69g, 20.0mmol) are dissolved in NMP (168.4g), and it is small that 5 are reacted at 80 DEG C Shi Hou, addition CBDA (11.57g, 49.0mmol) and NMP (56.14g), react 10 hours at 40 DEG C, it is molten to obtain polyamic acid Liquid.

After being diluted to 6.5 mass % to the middle addition NMP of the polyamic acid solution (250g), add and urged as imidizate The acetic anhydride (27.2g) and pyridine (70.2g) of agent, react 3 hours at 50 DEG C.The reaction solution is put into methanol (3500ml), leaching gained sediment.The sediment is cleaned with methanol, and is dried under reduced pressure at 100 DEG C, so as to obtain polyamides Imines powder (E).The acid imide rate of the polyimides is 59%, number-average molecular weight 14000, weight average molecular weight 51000.

The addition NMP (44.0g) into resulting polyimide powder (E) (6.0g), being stirred 20 hours at 70 DEG C makes It dissolves.3AMP (1 mass %NMP solution) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, is stirred at room temperature Mix 5 hours, so as to obtain aligning agent for liquid crystal (U5).

(synthesis example 6)

By BODA (18.77g, 75.0mmol), DBA (3.04g, 20.0mmol), DA-8 (9.96g, 50.0mmol), DA-5 (11.42g, 30.0mmol) is dissolved in NMP (143.7g), after being reacted 5 hours at 60 DEG C, addition CBDA (4.12g, 21.0mmol) with NMP (47.89g), reacted 10 hours at 40 DEG C, obtain polyamic acid solution.

After being diluted to 6.5 mass % to the middle addition NMP of the polyamic acid solution (180g), add and urged as imidizate The acetic anhydride (19.1g) and pyridine (14.8g) of agent, react 4 hours at 80 DEG C.The reaction solution is put into methanol (2200ml), leaching gained sediment.The sediment is cleaned with methanol, and is dried under reduced pressure at 100 DEG C, so as to obtain polyamides Imines powder (E).The acid imide rate of the polyimides is 57%, number-average molecular weight 12000, weight average molecular weight 39000.

The addition NMP (44.0g) into resulting polyimide powder (E) (6.0g), being stirred 20 hours at 70 DEG C makes It dissolves.3AMP (1 mass %NMP solution) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, is stirred at room temperature Mix 5 hours, so as to obtain aligning agent for liquid crystal (L1).

(synthesis example 7)

By BODA (12.51g, 50.0mmol), DBA (12.93g, 85.0mmol), DA-9 (6.16g, 15.0mmol) dissolvings In NMP (123.3g), after being reacted 3 hours at 60 DEG C, addition CBDA (9.51g, 48.5mmol) and NMP (41.11g), Reacted 10 hours at 40 DEG C, obtain polyamic acid solution.

After being diluted to 6.5 mass % to the middle addition NMP of the polyamic acid solution (180g), add and urged as imidizate The acetic anhydride (44.4g) and pyridine (13.8g) of agent, react 2 hours at 80 DEG C.The reaction solution is put into methanol (2400ml), leaching gained sediment.The sediment is cleaned with methanol, and is dried under reduced pressure at 100 DEG C, so as to obtain polyamides Imines powder (F).The acid imide rate of the polyimides is 70%, number-average molecular weight 12000, weight average molecular weight 31000.

The addition NMP (44.0g) into resulting polyimide powder (F) (6.0g), being stirred 20 hours at 70 DEG C makes It dissolves.3AMP (1 mass %NMP solution) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, is stirred at room temperature Mix 5 hours, so as to obtain aligning agent for liquid crystal (L2).

(synthesis example 8)

By BODA (5.00g, 20.0mmol), DBA (6.09g, 40.0mmol), 3AMPDA (7.27g, 30.0mmol), DA- 5 (11.42g, 30.0mmol) are dissolved in NMP (136.5g), after being reacted 3 hours at 60 DEG C, addition PMDA (4.36g, 48.5mmol) with CBDA (11.37g, 58.0mmol) and NMP (45.51g), reacted 10 hours at 40 DEG C, obtain polyamic acid Solution.

After being diluted to 6.5 mass % to the middle addition NMP of the polyamic acid solution (180g), add and urged as imidizate The acetic anhydride (40.0g) and pyridine (12.4g) of agent, react 3 hours at 50 DEG C.The reaction solution is put into methanol (2300ml), leaching gained sediment.The sediment is cleaned with methanol, and is dried under reduced pressure at 100 DEG C, so as to obtain polyamides Imines powder (G).The acid imide rate of the polyimides is 78%, number-average molecular weight 9000, weight average molecular weight 20000.

The addition NMP (44.0g) into resulting polyimide powder (G) (6.0g), being stirred 20 hours at 70 DEG C makes It dissolves.3AMP (1 mass %NMP solution) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, is stirred at room temperature Mix 5 hours, so as to obtain aligning agent for liquid crystal (L3).

[table 1]

(embodiment 1)

Using as obtained in the synthesis example 1 of the 1st composition aligning agent for liquid crystal (U1) 3.0g, the embodiment 5 as the 2nd composition In obtain aligning agent for liquid crystal (L1) 7.0g mixing, stir 1 hour, so as to prepare aligning agent for liquid crystal (A1).

The system of liquid crystal cells is carried out by such as following shown steps using the aligning agent for liquid crystal (A1) obtained in embodiment 1 It is standby.It is 300 μm of 100 μ m and line/interval that the aligning agent for liquid crystal (A1) obtained in embodiment 1, which is spin-coated on formed with Pixel Dimensions, The ito surface of the ITO electrode substrate of respectively 5 μm of ITO electrode pattern, after carrying out drying in 90 seconds using 80 DEG C of hot plates, utilize 200 DEG C of heated air circulation type baking oven burn till within 30 minutes, forms thickness 100nm liquid crystal orientation film.

In addition, aligning agent for liquid crystal (A1) to be spin-coated on to the ito surface for not forming electrode pattern, 90 are carried out using 80 DEG C of hot plates After second is dried, using 200 DEG C of heated air circulation type baking ovens burn till within 30 minutes, form thickness 100nm liquid crystal orientation film.

For above-mentioned 2 plate base, after spreading 4 μm of pearl sept on the liquid crystal orientation film of a substrate, from it Square printing and sealing agent (epoxy resin of solvent type heat-curing type).Then, there is liquid crystal orientation film with the formation of another substrate The face of side is as medially with after foregoing substrate sticking, making sealant cures, preparing dummy cell.Pass through into the dummy cell Injection method is depressurized to inject the liquid crystal MLC-3023 (business that MERCK Corporation are manufactured containing PSA with polymerizable compound The name of an article), prepare liquid crystal cells.

Pass through the response speed of the liquid crystal cells obtained by following methods measure.Then, applying for the liquid crystal cells In the state of 15V D/C voltage 10J/cm is irradiated from the outside of the liquid crystal cells²The bandpass filter that have passed through 365nm UV.It should be noted that the UV illumination UV-MO3A that is manufactured using ORC Co., Ltd. is determined.Then, so that liquid crystal cells For the purpose of the unreacted polymerizable compound inactivation of middle residual, Toshiba is used in the state of no applied voltage The UV-FL irradiation units of Lightec Co., Ltd. manufacture irradiate 30 minutes UV (UV lamps：FLR40SUV32/A-1).Then, again Response speed is determined, compares the response speed after UV pre-irradiations.In addition, the unit after being irradiated for UV determines the pre- of pixel portion Inclination angle.

In addition, the remanant DC voltages of measure each unit.Show the result in table.

" assay method of response speed "

First, in the survey being made up of successively one group of polarizer, light quantity detector of backlight, orthogonal thereto Nicol state Determine in device, liquid crystal cells are configured between one group of polarizer.Now, the pattern for making to be formed the ITO electrode at wired/interval is relative In Nicol crossed be in 45 ° of angle.Then, above-mentioned liquid crystal cells are applied with voltage ± 7V, frequency 1kHz square wave, The change untill the luminance saturation observed using light quantity detector is collected with oscillograph, brightness during no applied voltage is set For 0%, by application ± 6V voltage, the value of the brightness of saturation is set to 100%, by brightness from 10% be changed to 90% untill institute The time of consuming is set to response speed.

" measure of pre-tilt angle "

The LCD analyzers LCA-LUV42A manufactured using Meiryo Technica Corporation.

" evaluations of remanant DC voltages "

For the liquid crystal cells of above-mentioned manufacture, apply 100 hours 30Hz, 7.8Vpp for being superimposed with direct current 2V at 23 DEG C Square wave, by flash null method obtain just cut-out DC voltage after liquid crystal cells in remain voltage (residual DC electricity Pressure).The value turn into because DC accumulation and caused by image retention index, when the value is about below 30mV, judge image retention excellent.

(embodiment 2)

Aligning agent for liquid crystal (L1) is changed into aligning agent for liquid crystal (L2), in addition carries out operation similarly to Example 1, So as to prepare aligning agent for liquid crystal (A2).And then operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, residual D/C voltage.

(embodiment 3)

Aligning agent for liquid crystal (L1) is changed into aligning agent for liquid crystal (L3), in addition carries out operation similarly to Example 1, So as to prepare aligning agent for liquid crystal (A3).And then operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, residual D/C voltage.

(embodiment 4)

Aligning agent for liquid crystal (U1) is changed into aligning agent for liquid crystal (U2), in addition carries out operation similarly to Example 1, So as to prepare aligning agent for liquid crystal (A4).And then operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, residual D/C voltage.

(embodiment 5)

Aligning agent for liquid crystal (L1) is changed into aligning agent for liquid crystal (L2), in addition carries out operation similarly to Example 4, So as to prepare aligning agent for liquid crystal (A5).And then operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, residual D/C voltage.

(embodiment 6)

Aligning agent for liquid crystal (L1) is changed into aligning agent for liquid crystal (L3), in addition carries out operation similarly to Example 4, So as to prepare aligning agent for liquid crystal (A6).And then operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, residual D/C voltage.

(embodiment 7)

Aligning agent for liquid crystal (U1) is changed into aligning agent for liquid crystal (U3), in addition carries out operation similarly to Example 1, So as to prepare aligning agent for liquid crystal (A7).And then operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, residual D/C voltage.

(embodiment 8)

Aligning agent for liquid crystal (L1) is changed into aligning agent for liquid crystal (L2), in addition carries out operation similarly to Example 7, So as to prepare aligning agent for liquid crystal (A8).And then operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, residual D/C voltage.

(embodiment 9)

Aligning agent for liquid crystal (L1) is changed into aligning agent for liquid crystal (L3), in addition carries out operation similarly to Example 7, So as to prepare aligning agent for liquid crystal (A9).And then operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, residual D/C voltage.

(embodiment 10)

Aligning agent for liquid crystal (U1) is changed into aligning agent for liquid crystal (U4), in addition carries out operation similarly to Example 1, So as to prepare aligning agent for liquid crystal (A10).And then operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, residual Stay D/C voltage.

(embodiment 11)

Aligning agent for liquid crystal (L1) is changed into aligning agent for liquid crystal (L2), in addition carries out behaviour similarly to Example 10 Make, so as to prepare aligning agent for liquid crystal (A11).And then carry out operation similarly to Example 1 come determine response speed, pre-tilt angle, Remanant DC voltages.

(embodiment 12)

Aligning agent for liquid crystal (L1) is changed into aligning agent for liquid crystal (L3), in addition carries out behaviour similarly to Example 10 Make, so as to prepare aligning agent for liquid crystal (A12).And then carry out operation similarly to Example 1 come determine response speed, pre-tilt angle, Remanant DC voltages.

(embodiment 13)

Aligning agent for liquid crystal (U1) is changed into aligning agent for liquid crystal (U5), in addition carries out operation similarly to Example 1, So as to prepare aligning agent for liquid crystal (A13).And then operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, residual Stay D/C voltage.

(embodiment 14)

Aligning agent for liquid crystal (L1) is changed into aligning agent for liquid crystal (L2), in addition carries out behaviour similarly to Example 13 Make, so as to prepare aligning agent for liquid crystal (A14).And then carry out operation similarly to Example 1 come determine response speed, pre-tilt angle, Remanant DC voltages.

(embodiment 15)

Aligning agent for liquid crystal (L1) is changed into aligning agent for liquid crystal (L3), in addition carries out behaviour similarly to Example 13 Make, so as to prepare aligning agent for liquid crystal (A15).And then carry out operation similarly to Example 1 come determine response speed, pre-tilt angle, Remanant DC voltages.

(embodiment 16)

Using as aligning agent for liquid crystal (U5) 5.0g of the 1st composition, aligning agent for liquid crystal (L1) 5.0g as the 2nd composition, enter And the 0.06g (solid constituent relative to aligning agent for liquid crystal is 10 mass %) as polymerizable compound is mixed, stirring 1 is small When, so as to prepare aligning agent for liquid crystal (A16).And then as the liquid crystal without PSA polymerizable compounds, using MLC-6608, In addition operation similarly to Example 1 is carried out to determine response speed, pre-tilt angle, remanant DC voltages.

(comparative example 1)

As aligning agent for liquid crystal, using aligning agent for liquid crystal (U1), operation similarly to Example 1 is in addition carried out to survey Provisioning response speed, pre-tilt angle, remanant DC voltages.

(comparative example 2)

As aligning agent for liquid crystal, using aligning agent for liquid crystal (U2), operation similarly to Example 1 is in addition carried out to survey Provisioning response speed, pre-tilt angle, remanant DC voltages.

(comparative example 3)

As aligning agent for liquid crystal, using aligning agent for liquid crystal (U3), operation similarly to Example 1 is in addition carried out to survey Provisioning response speed, pre-tilt angle, remanant DC voltages.

(comparative example 4)

As aligning agent for liquid crystal, using aligning agent for liquid crystal (U4), operation similarly to Example 1 is in addition carried out to survey Provisioning response speed, pre-tilt angle, remanant DC voltages.

(comparative example 5)

As aligning agent for liquid crystal, using aligning agent for liquid crystal (U5), operation similarly to Example 1 is in addition carried out to survey Provisioning response speed, pre-tilt angle, remanant DC voltages.

[table 2]

Understood as described above shown in result, in embodiment 1~12, produce the composition 1 of structure with free radical by importing, from And irradiated using UV and impart inclination angle, improve response speed.And then understand, remanant DC voltages characteristic is also good, when long Between DC apply after also there is no the accumulation of remanant DC voltages.

On the other hand, comparative example is due to non-imported ingredient 2, therefore confirms and have accumulated residual because prolonged DC applies D/C voltage.

As above, the first composition of structure is produced and with the effect for suppressing remanant DC voltages with free radical by being applied in combination The second composition of fruit, the ultraviolet irradiation so as to provide even with long wavelength (such as 365nm) can also improve response The liquid crystal of speed and image retention excellent represents element.

Claims

A kind of 1. aligning agent for liquid crystal, it is characterised in that containing following (A) composition, (B) composition and organic solvents,

(A) composition：Selected from possessing the side chain that makes liquid crystal vertical-tropism and with being produced shown in following formula (1) because ultraviolet irradiates Give birth to the polyimide precursor of the side chain at the position of free radical and make polyimides obtained from the polyimide precursor imidizate At least one of polymer,

R₁、R₂Independently of one another be carbon number 1~10 alkyl or alkoxy, T1, T2 independently of one another for singly-bound or- O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂O-、-N(CH₃)-、-CON(CH₃)-、-N(CH₃) CO- connection Group, S is singly-bound or the alkylidene of carbon number 1~20 that is unsubstituted or being replaced by fluorine atoms；Wherein, alkylidene- CH₂- or-CF₂--CH=CH- is arbitrarily optionally replaced with, in the case that any group being exemplified below is not adjacent to each other, appoint Choosing is replaced by these groups：- O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- ,-NH-, the carbocyclic ring of divalence, the heterocycle of divalence, Q The structure from following middle selections is represented,

-OR

R is the alkyl of hydrogen atom or carbon number 1~4；

(B) composition：Selected from the diamine component conduct that will contain at least one diamines of selection from following formula (B-1)~(B-5) Polyimide precursor obtained from raw material and the polymerization in polyimides obtained from making the polyimide precursor imidizate Thing, or selected from the tetracarboxylic dianhydride of at least one tetracarboxylic dianhydride of selection from following formula (3) and (4) will be contained into being allocated as Polymerization for polyimide precursor obtained from raw material and in polyimides obtained from making the polyimide precursor imidizate Thing,

Y₁For the organic group of the monovalence with secondary amine, tertiary amine or heterocycle structure, Y₂For with secondary amine, tertiary amine or heterocycle structure The organic group of divalence,

N, m is 0 or 1, and X, y are singly-bound, carbonyl, ester group, phenylene, sulfonyl.
2. a kind of liquid crystal orientation film, it is characterised in that it is to be coated on the aligning agent for liquid crystal described in claim 1 on substrate simultaneously Obtained from burning till.
3. a kind of liquid crystal represents element, it is characterised in that with the aligning agent for liquid crystal described in claim 1 is coated on substrate simultaneously Liquid crystal orientation film sets liquid crystal layer in contact obtained from burning till, and applies voltage to the liquid crystal layer while irradiating ultraviolet Line, so as to possess liquid crystal cells.
4. a kind of liquid crystal represents the manufacture method of element, it is characterised in that with the aligning agent for liquid crystal described in claim 1 is coated with Liquid crystal orientation film sets liquid crystal layer in contact on substrate and obtained from burning till, voltage is applied to the liquid crystal layer while Ultraviolet is irradiated, so as to make liquid crystal cells.