CN105492965B

CN105492965B - Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal indicate element

Info

Publication number: CN105492965B
Application number: CN201480047157.8A
Authority: CN
Inventors: 芦泽亮; 芦泽亮一; 森内正人; 后藤耕平; 南悟志; 山口智裕
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2013-06-25
Filing date: 2014-06-25
Publication date: 2019-04-09
Anticipated expiration: 2034-06-25
Also published as: TWI642725B; KR20160024949A; KR102303303B1; JP6478052B2; WO2014208609A1; CN105492965A; JPWO2014208609A1; TW201518407A

Abstract

A kind of aligning agent for liquid crystal; it is characterized in that; it contains polymer and polymerizable compound; the polymer is selected from polyimide precursor and to be carried out at least one kind of in polyimides obtained from imidizate; the polyimide precursor is as obtained from the reacting of diamine component and tetracarboxylic dianhydride's ingredient, and the diamine component includes: in side chain skeleton containing cinnamoyl and in acryloyl group, methylacryloyl the polymerism group of any one diamine compound；And the diamine compound with the side chain for making liquid crystal vertical-tropism.

Description

Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal indicate element

Technical field

The present invention relates to aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal to indicate element.

Background technique

By electric field make the liquid crystal molecule relative to substrate vertical orientation generate response in the way of it is (also referred to as vertically oriented Mode) liquid crystal indicate element in, include the process for irradiating ultraviolet light when applying voltage to liquid crystal molecule in manufacturing process.

It is known that the liquid crystal of this vertical orientation mode indicates in element, by adding in advance into liquid-crystal composition Photopolymerizable compound is used together with the vertical alignment layer of polyimides etc., irradiates purple when applying voltage to liquid crystal cells Outside line, to accelerate the technology of liquid crystal response speed (referring for example to patent document 1 and non-patent literature 1.) (PSA type liquid crystal Show device).In general, being set by the protrusion that is arranged on substrate, expression in electrode in response to the inclined direction of the liquid crystal molecule of electric field The control of the slit set etc., and by adding photopolymerizable compound into liquid-crystal composition and applying voltage to liquid crystal cells side Ultraviolet light is irradiated on side, thus the polymer architecture object that the inclined direction that liquid crystal molecule is formed on liquid crystal orientation film is remembered, because This is compared with merely with the method for protrusion, the inclined direction of slit control liquid crystal molecule, it is said that liquid crystal indicates the response speed of element Degree becomes faster.

The liquid crystal of the PSA mode indicates in element that the dissolubility of the polymerizable compound added in liquid crystal is low, increases addition There are problems that it is precipitated in low temperature when amount.On the other hand, it when reducing the additive amount of polymerizable compound, can not obtain good State of orientation.In addition, remaining unreacted polymerizable compound can become the impurity (pollution) in liquid crystal in liquid crystal, therefore There is also reduce the problem of liquid crystal indicates component reliability.In addition, when the exposure of UV treatment with irradiation needed for PSA mode is more, Ingredient in liquid crystal decomposes and reliability is caused to reduce.

It reports herein: by the way that photopolymerizable compound is added in liquid crystal orientation film rather than in liquid-crystal composition, Can accelerate liquid crystal indicates the response speed (SC-PVA type liquid crystal display) (referring for example to non-patent literature 2) of element.

Existing technical literature

Patent document

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

Non-patent literature

04 DIGEST of non-patent literature 1:K.Hanaoka, SID, P.1200-1202

09 DIGEST of non-patent literature 2:K.HY.-J.Lee, SID, P.666-668

Summary of the invention

Problems to be solved by the invention

Using the aligning agent for liquid crystal for being added to photopolymerizable compound in this SC-PVA mode, but photopolymerizable compound Dissolubility in aligning agent for liquid crystal is simultaneously less high, therefore, increases the photopolymerizable compound added into aligning agent for liquid crystal Additive amount when, adverse effect is caused to the storage stability of aligning agent for liquid crystal.In addition, unreacted photopolymerizable compound at The reason for becoming ghost etc. for impurity, increases ultraviolet irradiation amount to reduce unreacted photopolymerizable compound When, will lead to liquid crystal, other components damage and become reduce liquid crystal indicate component reliability the reason of.

Problem of the present invention is that solve above-mentioned problem of the prior art point, provide even if not adding photopolymerization into liquid crystal Property compound also can be improved liquid crystal and indicate that the aligning agent for liquid crystal of response speed, liquid crystal orientation film, liquid crystal of element indicate element And diamine compound.

The solution to the problem

Inventors etc. have made intensive studies in order to solve the above problems, as a result, it has been found that: by using containing selected from poly- Imide precursor and the aligning agent for liquid crystal at least one of being carried out polyimides obtained from imidizate, are able to solve The above subject, so as to complete the present invention, the polyimide precursor are by containing novel diamine compound (hereinafter also referred to Specific diamine compound.) the reacting of diamine component and tetracarboxylic dianhydride's ingredient obtained from, the novel diamine compound The group that side chain has the group that photo-induced dimerization reaction can occur and photopolymerization reaction can occur.That is, the present invention has following master Purport.

1. a kind of aligning agent for liquid crystal, containing polymer and polymerizable compound, the polymer is selected from polyimides Precursor and carried out it is at least one kind of in polyimides obtained from imidizate, the polyimide precursor be by the inclusion of The diamine component and four of diamine compound shown in following formula [1] and the diamine compound with the side chain for making liquid crystal vertical-tropism Obtained from the reaction of carboxylic acid dianhydride ingredient.

(in formula, R³It indicates to be selected from-CH₂,-O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH-, the group in-CO-. R⁴Carbocyclic ring or heterocycle for the alkylidene, divalent that are formed by 1~carbon number of carbon number 30, the alkylidene, divalent carbocyclic ring or heterocycle on One or more hydrogen atoms optionally replaced by fluorine atom or organic group.In addition, in any group being exemplified below not phase each other In the case where neighbour, R⁴In-CH₂Optionally replaced by these groups, the group be-O- ,-NHCO- ,-CONH- ,-COO- ,- OCO-、-NH-、-NHCONH-、-CO-。R⁵Expression-CH₂,-O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH- ,-CO-, list Any one of key.R⁶Indicate cinnamoyl.R⁷For singly-bound or the carbocyclic ring of the alkylidene, divalent that are formed by 1~carbon number of carbon number 30 Or heterocycle, the alkylidene, the carbocyclic ring of divalent or one or more hydrogen atoms on heterocycle are optionally taken by fluorine atom or organic group Generation.In addition, in the case where any group being exemplified below is not adjacent to each other, R⁷In-CH₂Optionally replaced by these groups, The group is-O- ,-NHCO- ,-CONH- ,-COO- ,-OCO- ,-NH- ,-NHCONH- ,-CO-.R⁸It indicates to be selected from acryloyl The polymerism group of any one in base, methylacryloyl.)

2. the aligning agent for liquid crystal according to 1, which is characterized in that diamine compound shown in formula [1] is in diamine component 10 moles of %~90 mole %.

3. according to aligning agent for liquid crystal described in 1 or 2, which is characterized in that have the diamines for the side chain for making liquid crystal vertical-tropism Compound is 10 moles of %~70 mole % in diamine component.

4. the aligning agent for liquid crystal according to any one of 1~3, which is characterized in that polymerizable compound is shown in following formula Polymerizable compound.

5. a kind of liquid crystal orientation film, which is characterized in that it is that the aligning agent for liquid crystal as described in any one of 1~4 obtains.

6. a kind of liquid crystal indicates element, which is characterized in that it have 5 described in liquid crystal orientation film.

7. a kind of diamine compound, which is characterized in that it is indicated with following formula [DA-4].

8. a kind of diamine compound, which is characterized in that it is indicated with following formula [DA-10].

9. a kind of diamine compound, which is characterized in that it is indicated with following formula [DA-11].

10. a kind of diamine compound, which is characterized in that it is indicated with following formula [DA-13].

The effect of invention

According to the present invention, it is possible to provide even if in liquid crystal be free of photopolymerizable compound can be improved liquid crystal indicate element, The especially aligning agent for liquid crystal of the response speed of the liquid crystal expression element of vertical orientation mode.Also, the aligning agent for liquid crystal is unlimited Liquid crystal due to PSA mode indicates element, such as the liquid crystal that can be used for irradiating polarized UV rays and carry out orientation process indicates Element can obtain the orientation of liquid crystal well and be effectively improved the liquid crystal orientation film of exchange (AC) afterimage.

Specific embodiment

Hereinafter, the present invention is described in detail for needle.

Aligning agent for liquid crystal of the invention contains polymer and polymerizable compound, and the polymer is before polyimides Body and carried out at least one kind of in polyimides obtained from imidizate, the polyimide precursor is by the inclusion of upper State the diamine component and tetracarboxylic acid of diamine compound shown in formula [1] and the diamine compound with the side chain for making liquid crystal vertical-tropism Obtained from the reaction of acid dianhydride component.It should be noted that aligning agent for liquid crystal refers to the solution for making liquid crystal orientation film, Liquid crystal orientation film refers to the film for being orientated liquid crystal along prescribed direction.Contain in aligning agent for liquid crystal of the invention described below Each ingredient etc..

Contain in aligning agent for liquid crystal of the invention selected from polyimide precursor and being carried out obtained from imidizate Raw material, that is, diamine component of at least one kind of polymer in polyimides includes diamine compound shown in above-mentioned formula [1].

R in formula [1]³-R⁴-R⁵It is in side chain for linking diaminobenzene skeleton and cinnamoyl i.e. R⁶Spacer portion Position, R³Indicate the binding groups being bonded with diaminobenzene skeleton in the interval position.Binding groups R³Selected from-CH₂It is (i.e. sub- Methyl) ,-O- (i.e. ether) ,-CONH- (i.e. amide) ,-NHCO- (i.e. reverse amide) ,-COO- (i.e. ester) ,-OCO- it is (i.e. reverse Ester) ,-NH- (i.e. amino) ,-CO- (i.e. carbonyl).These binding groups R³Common methodology of organic synthesis be can use to be formed, But from the viewpoint of synthesizing easiness, preferably-CH₂-、-O-、-COO-、-NHCO-、-NH-。

R in formula [1]⁴Be as interval position center part, be the alkylidene formed by 1~carbon number of carbon number 30, The carbocyclic ring or heterocycle of divalent.Wherein, the alkylidene, the carbocyclic ring of divalent or any hydrogen atom on heterocycle optionally by fluorine atom or have Machine group replaces.In addition, wanting substituted hydrogen atom can be is also possible to many places at 1.In addition, in any key being exemplified below In the case that conjunction group is not adjacent to each other, the alkylidene, the carbocyclic ring of divalent or one or more-CH in heterocycle₂Optionally by this A little binding groups displacements, the binding groups are-O- ,-NHCO- ,-CONH- ,-COO- ,-OCO- ,-NH- ,-NHCONH- ,- NH,-CO-.This means that: R⁴The optionally carbon comprising alkylidene, the carbocyclic ring of divalent or heterocycle-binding groups-alkylidene, divalent Ring or heterocycle this structure.In addition, R³For-CH₂When, it is meant that R⁴In R³Side end can be the binding groups.Similarly, R⁵For-CH₂When, it is meant that R⁴In R⁵Side end can be the binding groups.Therefore, R³For-CH₂And R⁵For-CH₂When, meaning Taste R can be presented⁴For the binding groups-alkylidene, the carbocyclic ring of divalent or the heterocycle-binding groups this structures；R⁴For the key Close this structure of any of group.It should be noted that-the CH replaced by the binding groups₂It can be at 1, as long as should Binding groups not adjacent to each other then may be many places.Carbocyclic ring, heterocycle as divalent, specifically, can enumerate it is following that The structure of sample, but not limited thereto.

R in formula [1]⁵Indicate in the position of interval and R⁶The binding groups of bonding.Binding groups R⁵Selected from-CH₂-、- O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH- ,-CO-, singly-bound.These binding groups R⁵Using common organic conjunction It is formed at method, but from the viewpoint of synthesizing easiness, preferably-CH₂-、-O-、-COO-、-NHCO-、-NH-。

R in formula [1]⁷It is for linking cinnamoyl i.e. R⁶With in acryloyl group, methylacryloyl any one Polymerism group, that is, R⁸Position, R⁷For the carbocyclic ring of singly-bound or the alkylidene, divalent that are formed by 1~carbon number of carbon number 30 or miscellaneous Ring.Wherein, the alkylidene, the carbocyclic ring of divalent or any hydrogen atom on heterocycle are optionally replaced by fluorine atom or organic group.Separately Outside, it substituted hydrogen atom can be and is also possible to many places at 1.In addition, any binding groups being exemplified below each other not In the case where adjacent, the alkylidene, the carbocyclic ring of divalent or one or more-CH in heterocycle₂Optionally set by these binding groups It changes, the binding groups are-O- ,-NHCO- ,-CONH- ,-COO- ,-OCO- ,-NH- ,-NHCONH- ,-NH- ,-CO-.This meaning Such as R⁷Optionally comprising alkylidene, the carbocyclic ring of divalent or heterocycle-binding groups-alkylidene, the carbocyclic ring of divalent or heterocycle this One structure；Binding groups-the alkylidene, the carbocyclic ring of divalent or heterocycle this structure.It should be noted that will be by the binding groups - the CH of displacement₂Can be can be many places as long as the binding groups are not adjacent to each other at 1.Carbocyclic ring, miscellaneous as divalent Ring, specifically, structure as following can be enumerated, but not limited thereto.

R in formula [1]⁸Indicate any one the polymerism group in acryloyl group, methylacryloyl.Photopolymerization Property group refers to the functional group that polymerization reaction occurs by light stimulus.

Contained as being made selected from sub- using diamine compound shown in this above-mentioned formula [1] as polyamides obtained from raw material Amine precursor and the aligning agent for liquid crystal for being carried out at least one kind of polymer in polyimides obtained from imidizate, by being originated from The polymerism group of diamine compound shown in above-mentioned formula [1] and carry out cross-linking reaction and by the group of generation photo-induced dimerization and Dimerization reaction is carried out, as a result, the inclined direction of liquid crystal molecule has been remembered by cross-linking part generated, dimerization position, Thus, it is possible to accelerate gained liquid crystal to indicate the response speed of element.

Contain in aligning agent for liquid crystal of the invention selected from polyimide precursor and being carried out obtained from imidizate The ratio of diamines shown in formula [1] that include in raw material, that is, diamine component of at least one kind of polymer in polyimides, above-mentioned does not have It is particularly limited to, from the viewpoint of improving response speed, preferably to reach the diamine component for synthesis of polyimides precursor In the amount of 10 moles of %~90 mole % carry out using, more preferably the 10 of diamine component mole %~60 mole %, especially Preferably 10 moles of %~40 mole %.

The synthetic method of diamine compound shown in above-mentioned formula [1] is not particularly limited, such as can be by by following formula The nitro of dinitro compound shown in [1a] restores and is converted to amino to obtain.

(in formula [1a], R³、R⁴、R⁵、R⁶、R⁷And R⁸With the definition meaning having the same of formula [1].)

When restoring dinitro compound shown in above-mentioned formula [1a], using double bond will not be hydrogenated such catalyst come into Row reduction.About reduction reaction, in ethyl acetate, toluene, tetrahydrofuran, dioxanes, alcohol system equal solvent, preferably by zinc, tin, Stannic chloride, Tie Dengyu ammonium chloride, hydrogen chloride etc. are used together.

Dinitro compound shown in above-mentioned formula [1a] can be by by R³Make-the R as side chain position⁴-R⁵-R⁶-R⁷-R⁸ Method being bonded with dinitrobenzene etc. obtains.For example, R³When for amido bond (- CONH-), it can enumerate: make dinitro Benzoyl chloride and include-R⁴-R⁵-R⁶-R⁷-R⁸The method that reacts in the presence of base of amino-compound.

R³When for reverse amido bond (- HNCO-), can enumerate: make the dinitrobenzene containing amino with comprising-R⁴-R⁵-R⁶- R⁷-R⁸The method that reacts in the presence of base of acyl chlorides.

R³When for ester bond (- COO-), can enumerate: make dinitrobenzoyl chloride with comprising-R⁴-R⁵-R⁶-R⁷-R⁸Alcohol compound The method that object reacts in the presence of base.In addition, R³When for reverse ester bond (- OCO-), it can enumerate: make containing hydroxyl Dinitrobenzene and include-R⁴-R⁵-R⁶-R⁷-R⁸The method that reacts in the presence of base of chloride compounds.

R³When for ehter bond (- O-), can enumerate: make the dinitrobenzene containing halogen group with comprising-R⁴-R⁵-R⁶-R⁷-R⁸ The method that reacts in the presence of base of alcoholic compound.

R³When for amino bond (- NH-), can enumerate: make the dinitrobenzene containing halogen group with comprising-R⁴-R⁵-R⁶-R⁷- R⁸The method that reacts in the presence of base of amino-compound.

R³When for carbonyl bond (- CO-), can enumerate: make the dinitrobenzene containing aldehyde radical with comprising-R⁴-R⁵-R⁶-R⁷-R⁸'s The method that boronic acid compounds carry out coupling reaction in the presence of palladium, copper catalyst.

R³For carbon key (- CH₂) when, it can enumerate: make the dinitrobenzene containing halogen group and-R⁴-R⁵-R⁶-R⁷-R⁸R⁴ The method that there is the compound of unsaturated bond He Ke (HECK) reaction, Yuan cross-coupling reactions occurs for side end.

As above-mentioned dinitrobenzoyl chloride, 3,5- dinitrobenzoyl chloride, 3,5- dinitrobenzoic acid, 2,4- can be enumerated Dinitrobenzoyl chloride, 2,4- dinitrobenzoic acid, 3,5- dinitrobenzyl chlorine, 2,4- dinitrobenzyl chlorine, in addition, as containing There is the nitrobenzene of amino, 2,4- dinitroaniline, 3,5- dinitroaniline, 2,6- dinitroaniline etc. can be enumerated.As containing There is the nitrobenzene of hydroxyl, 2,4-DNP, 3,5- dinitrophenol, 2,6- dinitrophenol etc. can be enumerated.As containing There is the dinitrobenzene of halogen group, 2,4-dinitrofluorobenzene, 3,5- dinitrofluorobenzene, 2,6- dinitrofluorobenzene, 2 can be enumerated, 4- dinitro iodobenzene, 3,5- dinitro iodobenzene, 2,6- dinitro iodobenzene etc..As the dinitrobenzene containing aldehyde radical, can enumerate 2,4- dinitro aldehyde, 3,5- dinitro aldehyde, 2,6- dinitro aldehyde etc..

It is-R as side chain position⁴-R⁵-R⁶-R⁷-R⁸Synthetic method, can enumerate and be synthesized by the method being exemplified below Method etc..For example,-R⁴-R⁵-R⁶-R⁷-R⁸Structure in when there is amido bond (- CONH-), can enumerate: make comprising-R⁴Acyl Chlorine compound and-R⁶-R⁷-R⁸Amino-compound makes comprising-R⁴-R⁵-R⁶Chloride compounds and include-R⁷-R⁸Amino chemical combination Object or make comprising-R⁴-R⁵-R⁶-R⁷Chloride compounds and include-R⁸Amino-compound react in the presence of base Method.

-R⁴-R⁵-R⁶-R⁷-R⁸Structure in when there is reverse amido bond (- HNCO-), can enumerate: make comprising-R⁴Ammonia Based compound and include-R⁶-R⁷-R⁸Chloride compounds, make comprising-R⁴-R⁵-R⁶Amino-compound and include-R⁷-R⁸Acyl Chlorine compound or make comprising-R⁴-R⁵-R⁶-R⁷Amino-compound and include-R⁸Chloride compounds send out in the presence of base The method of raw reaction.

-R⁴-R⁵-R⁶-R⁷-R⁸Structure in when there is ester bond (- COO-), can enumerate: make comprising-R⁴Chloride compounds With include-R⁶-R⁷-R⁸Alcoholic compound, make comprising-R⁴-R⁵-R⁶Chloride compounds and include-R⁷-R⁸Alcoholic compound or Make comprising-R⁴-R⁵-R⁶-R⁷Chloride compounds and include-R⁸The method that reacts in the presence of base of alcoholic compound.

-R⁴-R⁵-R⁶-R⁷-R⁸Structure in when there is reverse ester bond (- OCO-), can enumerate: make comprising-R⁴Alcohol compound Object and include-R⁶-R⁷-R⁸Chloride compounds, make comprising-R⁴-R⁵-R⁶Alcoholic compound and include-R⁷-R⁸Chloride compounds, Or make comprising-R⁴-R⁵-R⁶-R⁷Alcoholic compound and include-R⁸The side that reacts in the presence of base of chloride compounds Method.

-R⁴-R⁵-R⁶-R⁷-R⁸Structure in when there is ehter bond (- O-), can enumerate: make comprising-R⁴Halogen compounds with Comprising-R⁶-R⁷-R⁸Alcoholic compound, make comprising-R⁴-R⁵-R⁶Halogen compounds and include-R⁷-R⁸Alcoholic compound, make to wrap Containing-R⁴-R⁵-R⁶-R⁷Halogen compounds and include-R⁸Alcoholic compound, make comprising-R⁴Alcoholic compound and include-R⁶-R⁷-R⁸ Halogen compounds, make comprising-R⁴-R⁵-R⁶Alcoholic compound and include-R⁷-R⁸Halogen compounds or make comprising-R⁴- R⁵-R⁶-R⁷Alcoholic compound and include-R⁸The method that reacts in the presence of base of halogen compounds.

-R⁴-R⁵-R⁶-R⁷-R⁸Structure in when there is amino bond (- NH-), can enumerate: make comprising-R⁴Halogen chemical combination Object and include-R⁶-R⁷-R⁸Amino-compound, make comprising-R⁴-R⁵-R⁶Halogen compounds and include-R⁷-R⁸Amino chemical combination Object makes comprising-R⁴-R⁵-R⁶-R⁷Halogen compounds and include-R⁸Amino-compound, make comprising-R⁴Amino-compound with Comprising-R⁶-R⁷-R⁸Halogen compounds, make comprising-R⁴-R⁵-R⁶Amino-compound and include-R⁷-R⁸Halogen compounds or Person makes comprising-R⁴-R⁵-R⁶-R⁷Amino-compound and include-R⁸The side that reacts in the presence of base of halogen compounds Method.

-R⁴-R⁵-R⁶-R⁷-R⁸Structure in when there is carbonyl bond (- CO-), can enumerate: make comprising-R⁴Aldehyde compound With include-R⁶-R⁷-R⁸Boronic acid compounds, make comprising-R⁴-R⁵-R⁶Aldehyde compound and include-R⁷-R⁸Boronic acid compounds, make Comprising-R⁴-R⁵-R⁶-R⁷Aldehyde compound and include-R⁸Boronic acid compounds, make comprising-R⁴Boronic acid compounds and include-R⁶- R⁷-R⁸Aldehyde compound, make comprising-R⁴-R⁵-R⁶Boronic acid compounds and include-R⁷-R⁸Aldehyde compound or make comprising-R⁴- R⁵-R⁶-R⁷Boronic acid compounds and include-R⁸The method that reacts in the presence of base of aldehyde compound.

In addition, contain in aligning agent for liquid crystal of the invention selected from polyimide precursor and being carried out imidizate and obtained To polyimides at least one kind of polymer raw material, that is, diamine component in, in addition to diamine compound shown in above-mentioned formula [1] Except, also comprising the diamine compound with the side chain for making liquid crystal vertical-tropism.As with the side chain for making liquid crystal vertical-tropism Diamine compound, can exemplify: as side chain have following group diamines: chain alkyl has in the way of chain alkyl The group of circular structure and/or apparatus derivatorius, steroids group, part or all of hydrogen atom on these groups are by fluorine atom Diamines shown in substituted group, for example, following formula [A-1]~formula [A-24], but it is not limited to them.

(in formula [A-1]~formula [A-5], A₁For the alkyl of carbon number 2~24 or containing fluoroalkyl.)

(in formula [A-6] and formula [A-7], A₂Expression-O- ,-OCH₂-、-CH₂O-、-COOCH₂Or-CH₂OCO-, A₃For carbon number 1~22 alkyl, contains fluoroalkyl or fluoroalkoxy at alkoxy.)

(in formula [A-8]~formula [A-10], A₄Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂Or-CH₂, A₅For the alkyl of carbon number 1~22, alkoxy, contain fluoroalkyl or fluoroalkoxy.)

(in formula [A-11] and formula [A-12], A₆Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂,-O- or-NH-, A₇For fluorine-based, cyano, fluoroform alkyl, nitro, azo group, formyl Base, acetyl group, acetoxyl group or hydroxyl.)

(in formula [A-13] and formula [A-14], A₈For the alkyl of carbon number 3~12, Isosorbide-5-Nitrae-cyclohexylene Sys-trans isomerism It is each other transisomer.)

(in formula [A-15] and formula [A-16], A₉For the alkyl of carbon number 3~12, Isosorbide-5-Nitrae-cyclohexylene Sys-trans isomerism It is each other transisomer.)

In addition, the concrete example as the diamine compound with the side chain for making liquid crystal vertical-tropism, can also enumerate following Diamines shown in formula [A-25]~formula [A-30].

(in formula [A-25]~formula [A-30], A₁₂Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂-、-O-、-CO- Or-NH-, A₁₃It indicates the alkyl of carbon number 1~22 or contains fluoroalkyl.)

In addition, the concrete example as the diamine compound with the side chain for making liquid crystal vertical-tropism, can also enumerate following Diamines shown in formula [A-31]~formula [A-32].

Wherein, from the viewpoint of making the ability of liquid crystal vertical-tropism, liquid crystal response speed, preferably [A-1], [A-2], [A-3], [A-4], [A-5], [A-25], [A-26], [A-27], [A-28], [A-29], [A-30] diamines.

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 charge and using a kind or be mixed with two or more.

Contain in aligning agent for liquid crystal of the invention selected from polyimide precursor and being carried out obtained from imidizate It is including in raw material, that is, diamine component of at least one kind of polymer in polyimides, with the side chain for making liquid crystal vertical-tropism The ratio of diamines is not particularly limited, preferably with reach 10 moles of % in the diamine component for synthesis of polyimides precursor~ The amount of 70 moles of % is carried out using more preferably 10 in diamine component mole %~50 mole %, particularly preferably 20 rub You are %~40 mole %.Like this, having reaches the diamines use of the side chain of liquid crystal vertical-tropism for synthesis of polyimides When the amount of 20 moles of %~40 mole % in the diamine component of precursor, from the orientation immobilization energy for improving response speed, liquid crystal It is especially excellent from the perspective of power.

In addition, contain in aligning agent for liquid crystal of the invention selected from polyimide precursor and being carried out imidizate and obtained To polyimides at least one kind of polymer raw material, that is, diamine component in, within the scope of the effect of the invention, also May include diamine compound shown in above-mentioned formula [1], it is above-mentioned have make liquid crystal vertical-tropism side chain diamines except its Its diamines.As other diamines, such as p-phenylenediamine, 2,3,5,6- tetramethyl-para-phenylene diamines, 2,5- dimethyl pair can be enumerated Phenylenediamine, m-phenylene diamine (MPD), 2,4- dimethyl-m-phenylenediamine, 2,5- diaminotoluene, 2,6- diaminotoluene, 2,5- diaminobenzene Phenol, 2,4- diaminophenol, 3,5- diaminophenol, 3,5- diamino benzylalcohol, 2,4- diamino benzylalcohol, 4,6- diamino isophthalic Diphenol, 4,4 '-benzidines, 3,3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 's, 4 '-diamino connection Benzene, 3,3 '-dihydroxy -4,4 '-benzidine, 3,3 '-dicarboxyls -4,4 '-benzidine, 3,3 '-two fluoro- 4,4 '-connection Benzene, 3,3 '-trifluoromethyls -4,4 '-benzidine, 3,4 '-benzidines, 3,3 '-benzidines, 2,2 '-diamino Biphenyl, 2,3 '-benzidines, 4,4 '-diaminodiphenyl-methanes, 3,3 '-diaminodiphenyl-methanes, 3,4 '-diamino Diphenyl methane, 2,2 '-diaminodiphenyl-methanes, 2,3 '-diaminodiphenyl-methanes, 4,4 '-diaminodiphenyl ethers, 3, 3 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, 2,2 '-diaminodiphenyl ethers, 2,3 '-diaminodiphenyl ethers, 4,4 '-sulphurs Acyl group diphenylamines, 3,3 '-sulfonyldianilines, bis- (4- aminophenyl) silane, bis- (3- aminophenyl) silane, dimethyl-are bis- Bis- (3- aminophenyl) silane of (4- aminophenyl) silane, dimethyl-, 4,4 '-phenothiazines, 3,3 '-phenothiazines, 4, 4 '-diamino-diphenyl amine, 3,3 '-diamino-diphenyl amine, 3,4 '-diamino-diphenyl amine, 2,2 '-diamino-diphenyls Amine, 2,3 '-diamino-diphenyl amine, N- methyl (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 '-diaminobenzophenones, 3,3 '-diaminobenzophenones, 3,4 '-diaminobenzophenones, 1,4- bis- Amino naphthalenes, 2,2 '-diaminobenzophenones, 2,3 '-diaminobenzophenones, 1,5- diaminonaphthalene, 1,6- diaminonaphthalene, 1,7- Diaminonaphthalene, 1,8- diaminonaphthalene, 2,5- diaminonaphthalene, 2,6- diaminonaphthalene, 2,7- diaminonaphthalene, 2,8- diaminonaphthalene, 1, Bis- (4- aminophenyl) ethane of 2-, bis- (3- aminophenyl) ethane of 1,2-, bis- (4- aminophenyl) propane of 1,3-, the bis- (3- of 1,3- Aminophenyl) propane, bis- (4- aminophenyl) butane of 1,4-, bis- (3- aminophenyl) butane of 1,4-, bis- (3,5- diethyl -4- Aminophenyl) methane, bis- (4- amino-benzene oxygen) benzene of 1,4-, bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (the 4- aminobenzenes of 1,4- Base) benzene, bis- (4- aminophenyl) benzene of 1,3-, bis- (4- aminobenzyl) benzene of 1,4-, 1,3- bis- (4- amino-benzene oxygen) benzene, 4,4 '- [1,4- phenylene is bis- (methylene)] diphenylamines, 4,4 '-[1,3- phenylene is bis- (methylene)] diphenylamines, 3,4 '-[Asia 1,4- benzene Base is bis- (methylene)] diphenylamines, 3,4 '-[1,3- phenylene is bis- (methylene)] diphenylamines, 3,3 '-[bis- (methylenes of 1,4- phenylene Base)] diphenylamines, 3,3 '-[1,3- phenylene is bis- (methylene)] diphenylamines, 1,4- phenylene bis- [(4- aminophenyl) ketones], 1,4- phenylene bis- [(3- aminophenyl) ketones], 1,3- phenylene bis- [(4- aminophenyl) ketones], 1,3- phenylene are double [(3- aminophenyl) ketone], 1,4- phenylene bis- (4-aminobenzoic acid esters), 1,4- phenylene bis- (3- Aminobenzoates), 1,3- phenylene bis- (4-aminobenzoic acid esters), 1,3- phenylene bis- (3- Aminobenzoates), bis- (4- aminophenyls) are to benzene Dicarboxylic acid esters, bis- (3- aminophenyl) terephthalates, bis- (4- aminophenyl) isophthalic acid esters, bis- (3- aminophenyls) Isophthalic acid ester, N, N '-(1,4- phenylene) bis- (4- aminobenzamides), N, N '-(1,3- phenylene) bis- (4- aminobenzenes Formamide), N, N '-(1,4- phenylene) bis- (3-ABs), N, N '-(1,3- phenylene) bis- (3- aminobenzoyls Amine), N, N '-bis- (4- aminophenyl) terephthalamides, N, N '-bis- (3- aminophenyl) terephthalamides, N, N '-is bis- (4- aminophenyl) isophtalamide, N, bis- (3- aminophenyl) isophtalamides of N '-, 9,10- bis- (4- aminophenyls) Anthracene, 4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulfones, 2,2 '-bis- [4- (4- amino-benzene oxygen) phenyl] propane, 2,2 '-bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane, 2,2 '-bis- (4- aminophenyl) hexafluoropropane, 2,2 '-bis- (3- aminophenyls) six Fluoro-propane, 2,2 '-bis- (3- amino -4- aminomethyl phenyl) hexafluoropropane, 2,2 '-bis- (4- aminophenyl) propane, 2,2 '-bis- (3- Aminophenyl) propane, 2,2 '-bis- (3- amino -4- aminomethyl phenyl) propane, 3,5- diaminobenzoic acid, 2,5- diaminobenzene first Acid, bis- (4- amino-benzene oxygen) propane of 1,3-, bis- (3- amino-benzene oxygen) propane of 1,3-, bis- (4- amino-benzene oxygen) fourths of 1,4- Bis- (3- amino-benzene oxygen) butane of alkane, 1,4-, bis- (4- amino-benzene oxygen) pentanes of 1,5-, bis- (the 3- amino-benzene oxygens) penta of 1,5- Bis- (4- amino-benzene oxygen) hexanes of alkane, 1,6-, bis- (3- amino-benzene oxygen) hexanes of 1,6-, 1,7- bis- (4- amino-benzene oxygen) heptan Alkane, 1,7- (3- amino-benzene oxygen) heptane, bis- (4- amino-benzene oxygen) octanes of 1,8-, bis- (3- amino-benzene oxygen) octanes of 1,8-, Bis- (4- amino-benzene oxygen) nonanes of 1,9-, bis- (3- amino-benzene oxygen) nonanes of 1,9-, 1,10- (4- amino-benzene oxygen) decane, 1, 10- (3- amino-benzene oxygen) decane, 1,11- (4- amino-benzene oxygen) hendecane, 1,11- (3- amino-benzene oxygen) hendecane, 1, The aromatic diamine, bis- (4- aminocyclohexyls of 12- (4- amino-benzene oxygen) dodecane, 1,12- (3- amino-benzene oxygen) dodecane etc. Base) methane, bis- (4- amino -3- methylcyclohexyl) methane etc. ester ring type diamines, 1,3- diaminopropanes, 1,4- diamino fourth Alkane, 1,5- 1,5-DAP, 1,6- diamino hexane, 1,7- diaminoheptane, 1,8- diamino-octane, 1,9- diamino nonyl The aliphatic diamines such as alkane, 1,10- diamino decane, 1,11- diamino undecane, 1,12- diamino dodecane.

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

In order to which the tetracarboxylic dianhydride's ingredient for obtaining polyimide precursor and reacting with above-mentioned diamine component is not special It limits.Specifically, pyromellitic acid, 2 can be enumerated, and 3,6,7- naphthalene tetracarboxylic acids, 1,2,5,6- naphthalene tetracarboxylic acids, Isosorbide-5-Nitrae, 5,8- naphthalenes four Carboxylic acid, 2,3,6,7- anthracene tetrabasic carboxylic acid, 1,2,5,6- anthracene tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acids, 2,3,3 ', 4- biphenyl tetracarboxylic acid Sour, bis- (3,4- dicarboxyphenyi) ethers, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids, bis- (3,4- dicarboxyphenyi) sulfones, bis- (3,4- Dicarboxyphenyi) methane, bis- (3,4- dicarboxyphenyi) propane of 2,2-, bis- (the 3,4- dicarboxyls of 1,1,1,3,3,3- hexafluoro -2,2- Phenyl) propane, bis- (3,4- dicarboxyphenyi) dimethylsilanes, bis- (3,4- dicarboxyphenyi) diphenyl silanes, 2,3,4,5- Pyridine tetrabasic carboxylic acid, 2,6- bis- (3,4- dicarboxyphenyi) pyridines, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acids, 3,4,9,10- tetra- Carboxylic acid, 1,3- diphenyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid, oxygen double phthalic acids, 1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2, 3,4- pentamethylene tetrabasic carboxylic acid, 1,2,4,5- cyclopentanetetracarboxylic, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1, 2- dimethyl -1,2,3,4- cyclobutane 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- tetrahydrofuran tetrabasic carboxylic acid, 3,4- dicarboxyl -1- cyclohexyl succinic acid, 2,3,5- tricarboxylic cyclopentyl vinegar Acid, 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic, bicyclic [3,3,0] octane -2,4,6,8- tetrabasic carboxylic acid, it is bicyclic [4, 3,0] nonane -2,4,7,9- tetrabasic carboxylic acid, bicyclic [4,4,0] decane -2,4,7,9- tetrabasic carboxylic acid, bicyclic [4,4,0] decane -2,4,8, 10- tetrabasic carboxylic acid, tricyclic [6.3.0.0<2,6>] hendecane -3,5,9,11- tetrabasic carboxylic acid, 1,2,3,4- butane tetracarboxylic acid, 4- (2,5- Dioxotetrahydrol furans -3- base) -1,2,3,4- naphthane -1,2- dicarboxylic acids, bicyclic [2,2,2] octyl- 7- alkene -2,3,5,6- four Carboxylic acid, 5- (2,5- dioxotetrahydrol furfuryl group) -3- methyl -3- hexamethylene -1,2- dicarboxylic acids, Fourth Ring [6,2,1,1,0,2,7] ten Dioxane -4,5,9,10- tetrabasic carboxylic acid, tri- carboxyl norbornane -2:3,5:6- dicarboxylic acids of 3,5,6-, 1,2,4,5- cyclopentanetetracarboxylic Deng.Needless to say, tetracarboxylic dianhydride can also according to when being made liquid crystal orientation film liquid crystal aligning, voltage retention performance, store The characteristics such as accumulated charge and be applied in combination one kind or two or more.

The polyimide precursor contained in aligning agent for liquid crystal of the invention refers to polyamic acid or poly amic acid ester.

When reacting to obtain polyamic acid, public affairs are able to use with above-mentioned tetracarboxylic dianhydride's ingredient by above-mentioned diamine component The synthetic method known.Typically, it is the method for making diamine component and tetracarboxylic dianhydride's ingredient react in organic solvent. From the viewpoint of being easier to carry out in organic solvent and do not generate by-product, diamine component is anti-with tetracarboxylic dianhydride's ingredient It should be advantageous.

As organic solvent used in above-mentioned reaction, do not have as long as the solvent that polyamic acid generated can dissolve It is particularly limited to.In turn, even the organic solvent of insoluble polyamic acid, in the range that polyamic acid generated will not be precipitated It is interior, can also mix to above-mentioned solvent come using.It should be noted that the moisture in organic solvent can hinder polymerization reaction, also It will lead to polyamic acid hydrolysis generated, therefore it is preferable to use the organic solvents after dehydration and drying.As used in reaction Organic solvent can enumerate such as n,N-Dimethylformamide, n,N-dimethylacetamide, N, N- diethylformamide, N- first Base formamide, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, 2-Pyrrolidone, 1,3- dimethyl -2- imidazoline Ketone, 3- methoxyl group-N, N- dimethylpropionamide, N- methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl Sulfone, hexamethyl sulfoxide, gamma-butyrolacton, isopropanol, methoxy amylalcohol, cinene, ethylpentyl ketone, methyl nonyl ketone, first Ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, butyl are molten Fine agent acetic acid esters, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, second two Alcohol list isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, the third two The tertiary butyl ether of alcohol, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, two Propylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxyl group fourth Yl acetate, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, acetic acid penta Ester, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, dioxanes, n-hexane, pentane, normal octane, Diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid N-butyl, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid first Base ethyl ester, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl Acid butyl ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanone, 2- ethyl -1- hexanol etc..These organic solvents can be independent It uses, can also be used in mixed way.

When reacting diamine component in organic solvent with tetracarboxylic dianhydride's ingredient, the following methods can be enumerated: stirring makes Diamine component is dispersed or dissolved in solution made of organic solvent, directly adds tetracarboxylic dianhydride's ingredient or makes its dispersion or molten Solution is in organic solvent and the method for addition；Conversely, molten made of organic solvent to tetracarboxylic dianhydride's ingredient is dispersed or dissolved in The method of diamine component is added in liquid；Tetracarboxylic dianhydride's ingredient and the method for diamine component etc. are alternatively added, this can be used Method either among a little.In addition, can be pre-mixed when diamine component or tetracarboxylic dianhydride's ingredient include multiple compounds In the state of react, can also successively react respectively, low-molecular weight made of reacting respectively can also be made to occur mixed It closes reaction and high molecular weight body is made.

Temperature when diamine component and tetracarboxylic dianhydride's ingredient being made to react can choose arbitrary temperature, for example,- 20 DEG C~150 DEG C, preferably -5 DEG C~100 DEG C of range.In addition, reaction can be carried out with any concentration, for example, diamines at Dividing with the total amount of tetracarboxylic dianhydride's ingredient is 1~50 mass %, preferably 5~30 mass % relative to reaction solution.

Ratio of the total mole number of tetracarboxylic dianhydride's ingredient in above-mentioned polymerization reaction relative to the total mole number of diamine component Rate can select arbitrary value according to the molecular weight of the polyamic acid gone for.In the same manner as common polycondensation reaction, this rubs You are than closer to 1.0, then the molecular weight of the polyamic acid generated becomes bigger.If having to show preferred scope, for 0.8~ 1.2。

The synthetic method of polyamic acid used in the present invention is not limited to the above method, the conjunction with general polyamic acid Similarly at method, by using the tetracarboxylic acid derivatives such as the tetrabasic carboxylic acid of counter structure or tetracarboxylic acid acid ihalide as above-mentioned four Carboxylic acid dianhydride ingredient makes its reaction using well known method, can also obtain corresponding polyamic acid.

Poly amic acid ester can utilize method (1) shown below~(3) Lai Hecheng.

(1) when being synthesized by polyamic acid

Poly amic acid ester can be synthesized by the way that the polyamic acid obtained by tetracarboxylic dianhydride and diamine component to be esterified. Specifically, can be by making polyamic acid and esterifying agent in presence of organic solvent with -20 DEG C~150 DEG C, preferably with 0 DEG C ~50 DEG C are reacted 30 minutes~24 hours, react 1~4 hour preferably to synthesize.

It as esterifying agent, can be preferably readily removable by purification, n,N-Dimethylformamide dimethyl can be enumerated Acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide two Neopentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1- methyl -3- p-methylphenyl triazenes, 1- ethyl -3- P-methylphenyl triazenes, 1- propyl -3- p-methylphenyl triazenes, 4- (4,6- dimethoxy -1,3,5- triazine -2- base) -4- first Base morpholinyl chloride etc..The additive amount of esterifying agent is worked as relative to 1 mole of repetitive unit of polyamic acid preferably 2~6 moles Amount.

Dissolubility preferably N,N-dimethylformamide, N- first of the solvent used in above-mentioned reaction from polymer Base -2-Pyrrolidone or gamma-butyrolacton, they can be used a kind or are mixed with two or more.It is difficult to happen from polymer It is precipitated and is easy to get high molecular weight body this viewpoint and set out, concentration when synthesis is preferably 1~30 mass %, more preferably 5 ~20 mass %.

(2) by tetracarboxylic acid acid diesters dichloride and diamine component react synthesized when

Poly amic acid ester can be synthesized by tetracarboxylic acid acid diesters dichloride with diamine component.Specifically, can lead to Crossing makes tetracarboxylic acid acid diesters dichloride and diamine component in the presence of alkali and organic solvent with -20 DEG C~150 DEG C, preferably with 0 DEG C~50 DEG C react 30 minutes~24 hours, preferably react 1~4 hour and synthesize.

Pyridine, triethylamine, 4-dimethylaminopyridine etc. can be used in aforementioned bases, in order to carry out reaction leniently, preferably For pyridine.From the viewpoint of in the amount easily removed and being easy to get high molecular weight body, the additive amount of alkali is relative to tetracarboxylic acid Acid diesters dichloride is preferably 2~4 times moles.

Solvent used in above-mentioned reaction is from the dissolubility of monomer and polymer preferably N- methyl -2- pyrrolidines Ketone, gamma-butyrolacton, they can be used a kind or are mixed with two or more.Precipitation is difficult to happen from polymer and is easy to obtain It secures satisfactory grades from the perspective of sub- amount body, polymer concentration when synthesis is preferably 1~30 mass %, more preferably 5~20 matter Measure %.In addition, the hydrolysis of tetracarboxylic acid acid diesters dichloride in order to prevent, the solvent for synthesizing polyamides acid esters is preferably as far as possible Dehydration, is preferably in nitrogen atmosphere and prevents being mixed into for atmosphere.

(3) by tetracarboxylic acid acid diesters and diamine component react synthesized when

Poly amic acid ester can be synthesized by the way that tetracarboxylic acid acid diesters are carried out polycondensation with diamine component.Specifically, can be with By making tetracarboxylic acid acid diesters and diamine component in the presence of condensing agent, alkali, organic solvent with 0 DEG C~150 DEG C, preferably with 0 DEG C ~100 DEG C are reacted 30 minutes~24 hours, react 3~15 hours preferably to synthesize.

Triphenyl phosphite, dicyclohexylcarbodiimide, 1- ethyl -3- (3- dimethylamino can be used in aforementioned condensation agent Propyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-cyanuro 1,3,5 methyl morpholine, O- (benzo three Azoles -1- base)-N, N, N ', N '-tetramethylurea tetrafluoro boric acid ester, O- (benzotriazole -1- base)-N, N, N ', N '-tetramethylurea six Fluorophosphoric acid ester, (thio -3- benzoxazolyl of 2,3- dihydro -2-) phosphonic acid diphenyl ester etc..The additive amount of condensing agent is relative to tetracarboxylic acid Acid diesters are preferably 2~3 times moles.

The tertiary amines such as pyridine, triethylamine can be used in aforementioned bases.From in the amount that easily removes and being easy to get high molecular weight From the perspective of body, the additive amount of alkali is preferably 2~4 times moles relative to diamine component.

In addition, by addition lewis acid as additive, reaction can be effectively performed in above-mentioned reaction.As Louis This acid, the preferably halogenated lithium such as lithium chloride, lithium bromide.Lewis acidic additive amount is preferably 0~1.0 times relative to diamine component Mole.

Among the synthetic method of above-mentioned 3 kinds of poly amic acid esters, since the poly amic acid ester of high molecular weight can be obtained, The synthetic method of particularly preferably above-mentioned (1) or above-mentioned (2).

It is above-mentioned it is such operate obtained from poly amic acid ester solution it is bad molten by being injected into while being sufficiently stirred Agent can be such that polymer is precipitated.After being precipitated and being cleaned for several times with poor solvent, air drying or heat drying, energy are carried out It is enough to obtain the poly amic acid ester powder through refining.Poor solvent is not particularly limited, can enumerate water outlet, methanol, ethyl alcohol, hexane, Butyl cellosolve, acetone, toluene etc..

As the method for making above-mentioned polyamic acid carry out imidizate and polyimides being made, can enumerate: by polyamide The direct-fired hot-imide of solution of acid；The catalysis imidizate of catalyst is added into the solution of polyamic acid.It needs Illustrate be not necessarily required to be 100% from polyamic acid to the acid imide rate that polyimides carries out imidizate.

100 DEG C~400 DEG C of temperature when polyamic acid being made to carry out hot-imide in the solution, preferably 120 DEG C~ 250 DEG C, it is preferred that the water generated in imidization reaction is removed to outside system on one side, carries out hot-imide on one side.

The catalysis imidizate of polyamic acid can by adding basic catalyst and acid anhydrides in the solution to polyamic acid, It is stirred with -20~250 DEG C, preferably with 0~180 DEG C to carry out.The amount of basic catalyst is that 0.5~30 times of amide acidic group rubs That, preferably 2~20 times moles, the amount of acid anhydrides are 1~50 times mole, preferably 3~30 times moles of amide acidic group.As alkali Property catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated, wherein pyridine have be suitble to promote reaction Alkalinity, so it is preferred that.As acid anhydrides, acetic anhydride, trihemellitic acid acid anhydride, benzenetetrahydride etc. can be enumerated, wherein use acetic acid When acid anhydride, it is easy purification after reaction, so it is preferred that.Acid imide rate based on catalysis imidizate can be by adjusting catalysis Dosage and reaction temperature, reaction time control.

It, can be with from when recycling polyamic acid or polyimides generated in the reaction solution of polyamic acid or polyimides Reaction solution, which is put into, makes its precipitating into poor solvent.As the poor solvent for precipitating, can enumerate methanol, acetone, Hexane, butyl cellosolve, heptane, methyl ethyl ketone, methylisobutylketone, ethyl alcohol, toluene, benzene, water etc..Investment is to poor solvent and makes it The polymer of precipitating can carry out air drying or heat drying after being recovered by filtration under normal or reduced pressure.In addition, will make to sink When the polymer recycled that forms sediment is dissolved in organic solvent again and carries out operation repetition 2~10 times of reprecipitation recycling, it can reduce Impurity in polymer.As poor solvent at this time, it can enumerate such as alcohols, ketone, hydrocarbon, be selected using among these When 3 kinds or more the poor solvents selected, purification efficiency is further increased, so it is preferred that.

As described above, aligning agent for liquid crystal of the invention contains selected from polyimide precursor and carries out the polyimide precursor At least one kind of polymer in polyimides obtained from imidizate, the polyimide precursor are by diamine component and four Obtained from the reaction of carboxylic acid dianhydride ingredient, the diamine component includes: diamine compound shown in above-mentioned formula [1] and have make The diamine compound of the side chain of liquid crystal vertical-tropism.Contain in aligning agent for liquid crystal selected from polyimide precursor and by the polyamides Asia The total amount that amine precursor carries out at least one kind of polymer in polyimides obtained from imidizate is preferably 1~10 (quality) %, The polyimide precursor is the diamine component packet as obtained from the reacting of diamine component and tetracarboxylic dianhydride's ingredient Contain: diamine compound and the diamine compound with the side chain for making liquid crystal vertical-tropism shown in above-mentioned formula [1].

In addition, aligning agent for liquid crystal of the invention can contain selected from polyimide precursor and carry out the polyimide precursor Other polymer other than at least one of polyimides polymer obtained from imidizate, the polyimide precursor are As obtained from the reacting of diamine component and tetracarboxylic dianhydride's ingredient, the diamine component includes: two shown in above-mentioned formula [1] Amine compounds and diamine compound with the side chain for making liquid crystal vertical-tropism.At this point, being selected from polyamides in the total ingredient of polymer Imines precursor and the ratio that the polyimide precursor is carried out at least one of polyimides obtained from imidizate polymer Example is preferably 10 (quality) % or more, and the polyimide precursor is reacting by diamine component and tetracarboxylic dianhydride's ingredient It obtains, the diamine component includes: diamine compound shown in above-mentioned formula [1] and with the side chain for making liquid crystal vertical-tropism Diamine compound.

The molecular weight of the polymer possessed by aligning agent for liquid crystal, it is contemplated that liquid crystal obtained from coating of liquid crystalline alignment agent Be orientated film strength and formed film when workability, apply film uniformity when, utilize GPC (gel permeation chromatography, Gel Permeation Chromatography) weight average molecular weight of method measurement is preferably 5,000~1,000,000, more preferably 10,000~150,000.

The solvent contained in aligning agent for liquid crystal is not particularly limited, as long as can dissolve or disperse selected from polyimide precursor Contain ingredient just with the polyimide precursor is carried out at least one of polyimides obtained from imidizate polymer etc. It is not particularly limited, the polyimide precursor is the diamine component and four by the inclusion of diamine compound shown in above-mentioned formula [1] Obtained from the reaction of carboxylic acid dianhydride ingredient.Such as can enumerate illustrated in the synthesis of above-mentioned polyamic acid it is such organic molten Agent.Wherein, from the viewpoint of dissolubility, preferably n-methyl-2-pyrrolidone, gamma-butyrolacton, N- ethyl -2- pyrrolidines Ketone, 1,3- dimethyl-2-imidazolinone, 3- methoxyl group-N, N- dimethylpropionamide.It can be used needless to say of more than two kinds Mixed solvent.

Additionally, it is preferred that painting film uniformity will be used to improve, the solvent of flatness to mix to aligning agent for liquid crystal and contains ingredient The high solvent of dissolubility and use.As for improving the solvent for applying film uniformity, flatness, such as isopropyl can be enumerated Alcohol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, the molten fibre of butyl Agent acetic acid esters, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, second two Alcohol monoacetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, third Glycol monobutyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol diformazan Ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, two Dihydroxypropane single-ether, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- Methyl -3- methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, Diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, n-hexane, positive penta Alkane, normal octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid propylene glycol list Ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionic acid Ethyl ester, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, 1- methoxyl group -2- Propyl alcohol, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene glycol two Acetic acid esters, propylene glycol -1- monomethyl ether -2- acetic acid esters, propylene glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethyoxyl Propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, 2- ethyl -1- hexanol Deng.These solvents can mix multiple types.When using these solvents, the solvent for preferably including in aligning agent for liquid crystal is whole 5~80 mass %, more preferably 20~60 mass %.

Aligning agent for liquid crystal of the invention contains the polymerization for having photopolymerizable group or photo-crosslinking group 1 or more end Property compound.That is, the polymerizable compound contained in aligning agent for liquid crystal of the invention with 1 or more, have photopolymerization The compound of the end of group or photo-crosslinking group.Herein, the polymerizable compound with photopolymerizable group refers to have and pass through Light irradiates and the compound of functional group that polymerize.Lead in addition, the polymerizable compound with photo-crosslinking group refers to have Cross light irradiation and can with polymer reaction of the invention to they be crosslinked functional group compound.It needs to illustrate It is that the polymerizable compound with photo-crosslinking group can react each other with the polymerizable compound with photo-crosslinking group.

By make in aligning agent for liquid crystal together containing this polymerizable compound and selected from polyimide precursor and by its into At least one kind of polymer in polyimides obtained from row imidizate, and hang down for manufacturing SC-PVA type liquid crystal display etc. Straight aligned liquid crystal indicates element, has the side chain and photoreactivity side chain for making the liquid crystal vertical-tropism with being used alone It is compared when polymer, the polymerizable compound, can also significantly improve response speed, even if the additive amount of polymerizable compound is few Also response speed can sufficiently be improved, the polyimide precursor is reacting by diamine component and tetracarboxylic dianhydride's ingredient It obtains, the diamine component includes: diamine compound shown in above-mentioned formula [1] and with the side chain for making liquid crystal vertical-tropism Diamine compound.

As photopolymerizable group or photo-crosslinking group, univalent perssad shown in following formula (II)s can be enumerated.

As the concrete example of polymerizable compound, can enumerate: such two ends shown in following formula (III)s have respectively Have and such shown in the polymerizable compound of photopolymerizable group, following formula (IV)s have the end with photopolymerizable group and have Such two ends shown in the polymerizable compound of the end of photo-crosslinking group, following formula (V)s are respectively provided with photo-crosslinking group Polymerizable compound.It should be noted that in following formula (III)s~(V), R¹²、Z¹And Z²With the R in above-mentioned formula (II)¹²、Z¹ And Z²It is identical, Q¹For the organic group of divalent.Q¹It is preferred that having phenylene (- C₆H₄), diphenylene (- C₆H₄-C₆H₄), ring it is sub- Hexyl (- C₆H₁₀) etc. ring structures.This is because the interaction with liquid crystal tends to get bigger.

As the concrete example of polymerizable compound shown in formula (III), following polymerizable compounds can be enumerated.Formula In, V is singly-bound or use-R¹O- is indicated and R¹For straight chain or the alkylidene of the carbon number 1~10 of branch ,-R is preferably used¹O- indicate and R¹For straight chain or the alkylidene of the carbon number 2~6 of branch.In addition, W is singly-bound or use-OR²Expression and R²For straight chain or branch The alkylidene of carbon number 1~10 preferably uses-OR²Expression and R²For straight chain or the alkylidene of the carbon number 2~6 of branch.It needs to illustrate It is that V and W can be identical structure can not also be identical, is readily synthesized when identical.

Polymerizable compound shown in the above-mentioned formula is two ends with alpha-methylene-γ-fourth as polymerizable group The compound of the specific structure of lactone group, therefore, polymer presentation rigid structure, the orientation immobilization ability of liquid crystal are excellent, or Shown in person's embodiment as be described hereinafter like that, sub- using acyl is carried out selected from polyimide precursor and by the polyimide precursor for manufacturing SC-PVA type liquid crystal display of at least one of polyimides polymer obtained from amination as liquid crystal aligning membrane material The liquid crystal of equal vertical orientation modes indicates element, can particularly obviously improve response speed.In addition, in general, liquid crystal takes Into the forming process of film, process in order to completely remove solvent including being burnt into high temperature has acrylate-based, first When the compounds of polymerizable groups such as base is acrylate-based, vinyl, vinethene (vinyloxy) base, epoxy group, it is steady to lack heat It is qualitative, be difficult to be resistant to high temperature firing.On the other hand, two ends have shown in the above-mentioned formula of alpha-methylene-gamma-butyrolactone base like that Polymerizable compound be presented the structure for lacking thermal polymerization, or can substantially resistant to by high temperature, such as 200 DEG C or more of firing Temperature.

It should be noted that be not alpha-methylene-gamma-butyrolactone base as photopolymerizable group or photo-crosslinking group, even if It is that there is acrylate-based, methacrylate polymerizable compound, if it is with the acrylate-based, metering system Perester radical is by oxyalkylene object and the polymerizable compound of structure that is bonded with phenylene at equal intervals, it will be able to above-mentioned two end The polymerizable compound that end is respectively provided with alpha-methylene-gamma-butyrolactone base similarly particularly obviously improves response speed.Separately Outside, if it is with acrylate-based, methacrylate by oxyalkylene object and the knot that is bonded with phenylene at equal intervals The polymerizable compound of structure, then thermal stability improves, or can substantially resistant to by high temperature, such as 200 DEG C or more of firing temperature.

In addition, other concrete examples as polymerizable compound shown in formula (III), can enumerate the polymerism of following formula Compound.

(in formula, V is singly-bound or use-R¹O- is indicated and R¹For straight chain or the alkylidene of the carbon number 1~10 of branch, preferably with- R¹O- is indicated and R¹For straight chain or the alkylidene of the carbon number 2~6 of branch.In addition, W is singly-bound or use-OR²Expression and R²It is straight The alkylidene of the carbon number 1~10 of chain or branch preferably uses-OR²Expression and R²For straight chain or the alkylidene of the carbon number 2~6 of branch. V and W can be identical structure and can also be different, and be readily synthesized when identical.In addition, R¹²For H or the alkyl of carbon number 1~4.)

From the viewpoint of showing the ability of dissolubility and pre-tilt angle, these polymerizable compounds are relative to liquid crystal aligning Solid component in agent is preferably 1 weight of weight %~30 %, more preferably 1 weight of weight %~20 %, further preferably 1 The weight of weight %~10 %.

The manufacturing method of this polymerizable compound is not particularly limited, such as can manufacture according to aftermentioned synthesis example. For example, polymerizable compound shown in following formula (1) can be synthesized by the way that the method in Synthetic Organic Chemistry to be combined. For example, can be by Te Lage shown in following reaction equations etc. in P.Talaga, M.Schaeffer, C.Benezra and The method proposed in J.L.Stampf, Synthesis, 530 (1990), uses SnCl₂Make 2- (bromomethyl) acrylic acid (2- (bromomethyl) propenoic acid) it is reacted with aldehydes or ketones to synthesize.It should be noted that Amberlyst 15 It is the strong-acid ion exchange resin of Rohm&Hass Co. manufacture.

(in formula, R ' indicates the organic group of monovalence.)

In addition, 2- (bromomethyl) acrylic acid can use shown in following reaction equations drawing kalimeris etc. in K.Ramarajan, K.Kamalingam,D.J.O'Donnell and K.D.Berlin,Organic Synthesis,vol.61,56-59 (1983) method proposed in synthesizes.

It is-R in synthesis V as specific synthesis example¹O-, W are-OR²And R¹With R²Shown in identical above-mentioned formula (1) When polymerizable compound, two methods shown in following reaction equations can be enumerated.

In addition, synthesis R¹With R²When polymerizable compound shown in different above-mentioned formulas (1), following reaction equations can be enumerated Shown in method.

In addition, following reaction equations can be enumerated when synthesis V and W is polymerizable compound shown in the above-mentioned formula (1) of singly-bound Shown in method.

Aligning agent for liquid crystal can contain ingredient other than the above.It as its example, can enumerate: make coating of liquid crystalline alignment agent When film thickness uniformity, surface smoothness improve compound；The compound for improving the adaptation of liquid crystal orientation film and substrate Deng.

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

As the concrete example for the compound for improving the adaptation of liquid crystal orientation film and substrate, silicon containing functionality can be enumerated The compound of alkane, compound containing epoxy group etc..Such as 3- TSL 8330,3- aminopropyl three can be enumerated Ethoxysilane, 2- TSL 8330,2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- ammonia Base propyl trimethoxy silicane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- urea propyl trimethoxy Silane, 3- urea propyl-triethoxysilicane, N- ethoxy carbonyl -3- TSL 8330, N- ethoxy carbonyl -3- Aminopropyltriethoxywerene werene, three second triamine of N- triethoxysilylpropyltetrasulfide, N- trimethoxy-silylpropyl three Second triamine, three azepine decane of 10- trimethoxysilyl -1,4,7-, three azepine of 10- triethoxysilyl -1,4,7- Decane, 9- trimethoxysilyl -3,6- diaza nonyl acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyl Yl acetate, N- benzyl -3- TSL 8330, N- benzyl -3-aminopropyltriethoxysilane, N- phenyl - Bis- (oxygen the ethylidene) -3- aminopropans of 3- TSL 8330, N- phenyl -3-aminopropyltriethoxysilane, N- Bis- (oxygen the ethylidene) -3-aminopropyltriethoxysilane of base trimethoxy silane, N-, ethylene glycol diglycidylether, poly- second Hexanediol diglycidyl ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromo new penta Hexanediol diglycidyl ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycol, N, N, N ', N '-four glycidyl group isophthalic two Methylamine, 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N ', N '-four glycidyl group -4,4 '-diamino Base diphenyl methane, 3- (N- allyl-N- glycidyl) TSL 8330,3- (N, N- 2-glycidyl Base) TSL 8330 etc..In addition, 2,2 '-can be added in order to further increase the film-strength of liquid crystal orientation film The phenolic compounds such as bis- (4- hydroxyl -3,5- bishydroxymethyl phenyl) propane, four (methoxy) bis-phenols.Use these compounds When, relative to 100 mass parts of total amount of the polymer contained in aligning agent for liquid crystal, preferably 0.1~30 mass parts are more preferably 1~20 mass parts.

In turn, it in aligning agent for liquid crystal, in addition to that mentioned above, if the range for not damaging effect of the present invention, then can add Dielectric substance, 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 be burnt into, it is capable of forming the liquid crystal for making liquid crystal vertical-tropism Alignment films.

At this point, being not particularly limited as long as the high substrate of the transparency as substrate used, glass base can be used Plastic bases such as plate, acrylic compounds substrate, polycarbonate substrate etc..In addition, it is preferable to use shape from the perspective of the chemical industry skill that conforms to the principle of simplicity At the substrate having for driving the ITO of liquid crystal (tin indium oxide, Indium Tin Oxide) electrode etc..In addition, in reflection-type Liquid crystal indicates, if being only single sided substrate, the opaque substrate such as silicon wafer also to can be used, electrode at this time can also in element To 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 enumerate and utilize silk-screen printing, hectographic printing, flexible print Brush, ink-jet etc. are come the method that carries out；Dipping, roller coating, slot coated, spin coating etc..

The firing temperature of the film formed by coating of liquid crystalline alignment agent does not limit, such as can be with 100 DEG C~350 DEG C arbitrary temp carry out, preferably 120 DEG C~300 DEG C, further preferably 150 DEG C~250 DEG C.The firing can use Hot plate, recirculation furnace, infrared heating heating furnace etc. carry out.

It is preferably 5~300nm, more excellent in addition, the thickness of liquid crystal orientation film obtained from being burnt into is not particularly limited It is selected as 10~100nm.

Liquid crystal of the invention indicates that element is that the liquid crystal for having liquid crystal cells indicates that element, the liquid crystal cells have opposite Configuration 2 plate bases, the liquid crystal layer being arranged between the substrates and be arranged between substrate and liquid crystal layer by liquid crystal of the present invention The above-mentioned liquid crystal orientation film that alignment agent is formed.Specifically, being the liquid crystal expression for having the following liquid crystal cells for operating and making Element: by the way that aligning agent for liquid crystal of the invention to be coated on 2 plate bases and be burnt into, so that liquid crystal orientation film is formed, with the liquid The opposite mode of brilliant alignment films configures 2 plate bases, and the liquid crystal layer being made of liquid crystal is clamped between 2 plate base, is taken to liquid crystal Ultraviolet light is irradiated when applying voltage to film and liquid crystal layer, to make.Element is indicated as this liquid crystal of the invention, can be arranged Enumerate twisted nematic (TN:Twisted Nematic) mode, vertical orientation (VA:Vertical Alignment) mode, level The various modes such as (IPS:In-Plane Switching) mode of orientation.

In this way using the liquid crystal orientation film formed by aligning agent for liquid crystal of the invention, to liquid crystal orientation film and liquid crystal Layer irradiate ultraviolet light when applying voltage, make polymerism group possessed by the side chain of polyimide precursor, polyimides and Photo-induced dimerization group, that is, the polymerism group for being originated from diamine compound shown in above-mentioned formula [1] and photo-induced dimerization group occur Reaction, the orientation of liquid crystal is by being effectively fixed, so that becoming the obvious excellent liquid crystal of response speed indicates element.From not having to It says, aligning agent for liquid crystal of the invention can obtain the response speed more than same or same adding photopolymerizable compound Liquid crystal indicate element.

Substrate used in element is indicated as liquid crystal of the invention, is not limited especially as long as the high substrate of the transparency It is fixed, the substrate for driving the transparent electrode of liquid crystal is usually formed on substrate.As concrete example, can enumerate and above-mentioned liquid The identical substrate of the substrate recorded in brilliant alignment films.The substrate for being provided with previous electrode pattern, projection pattern can be used, but It is indicated in element in liquid crystal of the invention, the liquid of aforementioned present invention has been used as the aligning agent for liquid crystal for forming liquid crystal orientation film Brilliant alignment agent, therefore, even single sided substrate forms 1~10 μm of line/gap electrode pattern, opposite substrate is not formed narrow Seam pattern, projection pattern structure can also operate, liquid crystal with this configuration indicate technique when element can simplify manufacture, High-transmission rate can be obtained.

In addition, in high function element as TFT type element, can be used for drive liquid crystal electrode and substrate it Between be formed with the element of transistor etc.

In the case where transmission-type liquid crystal indicates element, as described above usually using substrate, member is indicated in reflective liquid crystal In part, the opaque substrate such as silicon wafer also can be used if only single sided substrate.At this point, the electrode for being formed in substrate can also To use the material of aluminium for reflected light etc.

Liquid crystal orientation film be by being coated with aligning agent for liquid crystal of the invention on the substrate after, be burnt into and formed, Details are as described above.

Liquid crystal of the invention indicates that the liquid crystal material of the composition liquid crystal layer of element is not particularly limited, and can be used previous Liquid crystal material used in vertical orientation mode is born such as MLC-6608, MLC-6609 that MERCK CORPORATION is manufactured Type liquid crystal；MLC-2041 etc..

As making the liquid crystal layer be held on the method between 2 plate bases, well known method can be enumerated.Such as it can enumerate Following method: preparing a pair of of the substrate for being formed with liquid crystal orientation film, on the liquid crystal orientation film of a substrate between distribution pearl etc. Another substrate is pasted on parting, the surface to be formed with liquid crystal orientation film side in a manner of becoming inside, decompression injection liquid crystal is simultaneously Sealing.In addition, even if benefit with the following method can make liquid crystal cells: prepare 1 pair of substrate for being formed with liquid crystal orientation film, Pearl is spread on the liquid crystal orientation film of one substrate at equal intervals after object, liquid crystal is added dropwise, thereafter to be formed with liquid crystal orientation film side Surface become the mode of inside and paste another substrate, and be sealed.The thickness of spacer at this time is preferably 1~30 μ M, 2~10 μm are more preferably.

The process example of liquid crystal cells is made by irradiating ultraviolet light when applying voltage to liquid crystal orientation film and liquid crystal layer It can such as enumerate: by applying voltage between the electrode being disposed on the substrate, to apply to liquid crystal orientation film and liquid crystal layer Electric field irradiates the method for ultraviolet light in the case where keeping the electric field.Herein, as the voltage applied between the electrodes, such as For 5~30Vp-p, preferably 5~20Vp-p.Ultraviolet irradiation amount is, for example, 1~60J/cm², preferably 40J/cm²Hereinafter, When ultraviolet irradiation amount is few, be able to suppress because constitute liquid crystal indicate element component breakage due to the reliability that generates reduces and Ultraviolet irradiation time is reduced, thus manufacture efficiency rises, so be suitble to.

Like this, when irradiating ultraviolet light when applying voltage to liquid crystal orientation film and liquid crystal layer, polyimide precursor, polyamides The reaction of polymerism group possessed by the side chain of imines and photo-induced dimerization group can promote, i.e., using from above-mentioned formula [1] The polymerism group of shown diamine compound carries out cross-linking reaction and carries out dimerization reaction using photo-induced dimerization group, as a result leads to Cross generated cross-linking part, dimerization position and remember the inclined direction of liquid crystal molecule, thus, it is possible to accelerate gained liquid crystal Indicate the response speed of element.

In addition, above-mentioned aligning agent for liquid crystal is served not only as making PSA type liquid crystal display, SC-PVA type liquid crystal display The liquid crystal of equal vertical orientation modes indicate the aligning agent for liquid crystal of element be it is useful, can also be suitably employed in handled using brushing, Light orientation processing and the purposes of liquid crystal orientation film made.

It is exemplified below embodiment and the present invention is described in more detail, but the present invention is not limited to them.

Embodiment

(tetracarboxylic dianhydride)

BODA: bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride

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

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

(diamines)

DBA:3,5- diaminobenzoic acid

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

Photoreactivity diamines shown in following formula DA-1~DA-5

Vertical orientation diamines shown in following formula DA-6~DA-9

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

BCS: butyl cellosolve

3AMP:3- aminomethyl-pyridine

Polymerizable compound shown in following formula RM1, RM2

The abbreviation of organic solvent used in embodiment etc. etc. is as follows.

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

BCS: butyl cellosolve

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

Device: セ Application シュー scientific company room temperature gel permeation chromatography (GPC) device (SSC-7200),

Column: the column (KD-803, KD-805) of Shodex company manufacture

Column temperature: 50 DEG C

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

Flow velocity: 1.0ml/ minutes

Standard curve making standard sample: (molecular weight is about TOSOH Co., Ltd TSK standard polyethylene oxide 9000,000,150,000,100,000,30,000) and Polymer Laboratories Ltd. polyethylene glycol (molecular weight About 12,000,4,000,1,000).

In addition, the acid imide rate of polyimides is operated as follows to measure.Polyimide powder 20mg is put into NMR sample In quality control (wasteland's science Co. Ltd. system NMR sample cell specification φ 5), deuterated dimethyl sulfoxide (DMSO-d is added₆, 0.05% TMS melange) 1.0ml, apply ultrasonic wave and makes it completely dissolved.The NMR analyzer manufactured using JEOL DATUM company (JNW-ECA500) to the proton NMR of solution measurement 500MHz.Acid imide rate will not become before and after being originated from imidizate The proton of the structure of change is determined as reference proton, is nearby gone out using the peak integrating value of the proton and from 9.5~10.0ppm The proton peak integrating value of the NH base of existing amic acid, is found out using following formula.It should be noted that x is from acyl in following formula When the proton peak integrating value of the NH base of amino acid, the peak integrating value that y is benchmark proton, α are polyamic acid (acid imide rate is 0%) Reference proton relative to amic acid NH base 1, proton number ratio.

Acid imide rate (%)=(1- α x/y) × 100

<¹The measurement of HNMR >

Device: Fourier transform type superconduction nuclear magnetic resonance device (FT-NMR) INOVA-400 (Varian corporation) 400MHz

Solvent: deuterated dimethyl sulfoxide (DMSO-d₆), deuterated chloroform (CDCl₃)

Standard substance: tetramethylsilane (TMS)

The synthesis of (synthesis example 1) DA-1

The synthesis of the precursor DA-1-1 of (synthesis example 1-1) DA-1

Into 2L four-neck flask add 4- bromine hydroxy benzenes (100g, 578mmol), tert-butyl acrylate (156g, 1.21mol), palladium acetate (II) (2.6g, 11.6mmol), three (o-tolyl) phosphines (7.0g, 23.1mmol), tri-butylamine (321g, 1.73mol), N, N '-dimethyl acetamide (hereinafter, being expressed as DMAc) (500g), with 100 DEG C of progress heating stirrings. Reaction solution is injected into 1M aqueous hydrochloric acid solution (2L) and is stirred a little while after the completion of reaction with HPLC following response.Xiang Qi Organic layer is cleaned 3 with saturated salt solution (500mL) after removing water layer by liquid separation operation by middle addition ethyl acetate (1L) It is secondary, organic layer is dried with magnesium sulfate, is filtered, distillation removal solvent obtains DA-1-1 (bronzing viscoid) 158g.It needs It is noted that gained compound is directly used in following process.

The synthesis of the precursor DA-1-2 of (synthesis example 1-2) DA-1

DA-1-1 22.0g, the chloro- 1- hexanol of N,N-dimethylformamide 250mL, 6- are added into 500mL four-neck flask 19.1g, potassium carbonate 41.5g, potassium iodide 1.7g, are stirred when being heated to 100 DEG C.After reaction, it is injected into 1L water Reaction system is neutralized, filtering precipitate with 1N- aqueous hydrochloric acid solution.The filtrate is cleaned and is made it dry with isopropanol, To obtain DA-1-2 (white solid) 13.2g (yield 43%).

The synthesis of the precursor DA-1-3 of (synthesis example 1-3) DA-1

DA-1-2 6.4g, tetrahydrofuran 60mL, 2,4- dinitrofluorobenzene 3.7g, three second are added into 300mL four-neck flask Amine 2.4g is stirred when being heated to 80 DEG C.After reaction, reaction system is injected into 500mL ethyl acetate, using full It is extracted with saline solution.Anhydrous magnesium sulfate is added into extracted organic layer to be dehydrated, and anhydrous magnesium sulfate is filtered. The solvent in removal gained filtrate is distilled using rotary evaporator, formic acid 50mL is added, is stirred when being heated to 50 DEG C.Instead After answering, reaction system, filtering precipitate are injected into 500mL water.The filtrate is cleaned and is made it dry with isopropanol, To obtain DA-1-3 (yellow solid) 7.4g (yield 81%).

The synthesis of the precursor DA-1-4 of (synthesis example 1-4) DA-1

DA-1-3 6.9g, tetrahydrofuran 70mL, 2-hydroxyethyl methacrylate are added into 300mL four-neck flask 2.5g, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride 5.3g, 4-dimethylaminopyridine 0.2g, at room temperature It is stirred.After reaction, reaction system, filtering precipitate are injected into 200mL water.The filtrate is carried out with isopropanol It cleans and makes it dry, to obtain DA-1-4 (white-yellowish solid) 8.6g (yield 96%).

The synthesis of (synthesis example 1-5) DA-1

DA-1-4 7.6g, ethyl acetate 70mL, pure water 70ml, reduced iron 7.8g, chlorine are added into 300mL four-neck flask Change ammonium 6.0g, is stirred when being heated to 60 DEG C.After reaction, reduced iron is filtered, organic layer is carried out with ethyl acetate It extracts.Anhydrous magnesium sulfate is added into organic layer and is dehydrated, and anhydrous magnesium sulfate is filtered.It is distilled using rotary evaporator Solvent in removal gained filtrate.Residue is cleaned and made it dry with isopropanol, (yellow-white is solid to obtain DA-1 Body) 5.3g (yield 78%).Utilization is shown as follows¹The result of H-NMR measurement obtained solid.From this result, it is confirmed that gained Solid is object DA-1.

¹H NMR(400MHz,[D₆]-DMSO):δ7.62-7.64(d,2H),7.56-7.68(d,1H),6.91-6.93(d, 2H),6.44-6.48(d,1H),6.42(s,1H),6.00(s,1H),5.91(s,1H),5.69-5.72(d,2H),5.66(s, 1H),4.36(s,2H),4.32(s,2H),3.96-4.00(t,2H),3.71-3.74(t,2H),1.84(s,3H),1.62- 1.72(m,4H),1.40-1.44(m,4H)

The synthesis of the precursor DA-2-1 of (synthesis example 2-1) DA-2

E-p-coumaric acid 102.0g, ethyl alcohol 500mL, sulfuric acid 5.8g are added into 1L three-neck flask, when being heated at reflux It is stirred.After reaction, it injects reaction system into 3L water, after filtering precipitate, keeps the filtrate dry, to obtain 90.0g object DA-2-1 (white solid) (yield 75%).

The synthesis of the precursor DA-2-2 of (synthesis example 2-2) DA-2

Into 500mL three-neck flask add DA-2-1 19.2g, the chloro- 1- hexanol 20.5g of dimethylformamide 250mL, 6-, Potassium carbonate 41.5g, potassium iodide 1.7g, are stirred with 60 DEG C.After reaction, reaction system is injected into 1.2L water, uses 1N- HCL aqueous solution is neutralized, filtering precipitate.The filtrate is dissolved in 300mL ethyl acetate, is carried out using saturated salt solution It extracts, after anhydrous magnesium sulfate is added into organic layer and dehydrated, filtered, the steaming of solvent is carried out using rotary evaporator It evaporates and removes, to obtain the object DA-2-2 (clear, viscous body) (yield 92%) of 26.99g.

The synthesis of the precursor DA-2-3 of (synthesis example 2-3) DA-2

DA-4-2 14.7g, ethyl alcohol 200mL, 10wt%KOH aqueous solution 30.0g are added into 500mL three-neck flask, side is returned Stream heating side is stirred.After reaction, reaction system is injected into 600mL water, is neutralized with 1N-HCl aqueous solution, mistake Filter sediment.The filtrate is cleaned and made it dry with ethyl acetate, to obtain the object DA-4-3 of 11.8g (white solid) (yield 89%).

The synthesis of the precursor DA-2-4 of (synthesis example 2-4) DA-2

DA-2-3 11.7g, triethylamine (Et are added into 300mL three-neck flask₃N) 4.9g and tetrahydrofuran 200mL.It will It is cooled to 0 DEG C in system, adds 3,5- dinitrobenzoyl chloride 15.2g, is stirred at room temperature.After reaction, it adds Pure water 50mL and after stirring, addition ethyl acetate simultaneously extracts organic layer, adds and anhydrous magnesium sulfate and is dehydrated into organic layer After dry, filtering, removed using the distillation that rotary evaporator carries out solvent.Residue is recrystallized with ethyl acetate, thus Obtain the object DA-2-4 (white-yellowish solid) (yield 35%) of 7.2g.

The synthesis of the precursor DA-2-5 of (synthesis example 2-5) DA-2

DA-2-4 6.9g, tetrahydrofuran 60mL, 2-hydroxyethyl methacrylate are added into 200mL three-neck flask (HEMA) 3.0g, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC) 4.4g, 4-dimethylaminopyridine (DMAP) 0.2g is stirred at room temperature.After reaction, organic layer is extracted with chloroform, is added into organic layer Anhydrous magnesium sulfate and after being dehydrated, being filtered, is removed using the distillation that rotary evaporator carries out solvent, by residue isopropyl Alcohol/hexane=1/5 is recrystallized, to obtain the object DA-2-5 (white-yellowish solid) (yield 69%) of 5.9g.

The synthesis of (synthesis example 2-6) DA-2

Add DA-2-5 5.9g, tetrahydrofuran 60mL and pure water 60mL into 300mL three-neck flask, in stirring system simultaneously Stannic chloride 13.3g is added, 70 DEG C will be heated in system and is stirred.After reaction, reaction is injected into 300mL ethyl acetate System using sodium bicarbonate and makes pH 7~8.White depositions are removed by filtering, organic layer is carried out with ethyl acetate It extracts, after anhydrous magnesium sulfate is added into organic layer and dehydrated, filtered, the steaming of solvent is carried out using rotary evaporator It evaporates and removes.Residue is recrystallized with ethyl acetate/hexane=1/5, so that the object DA-2 for obtaining 5.7g is (orange solid Body) (yield 99%).Use is shown as follows¹The result of H-NMR measurement obtained solid.From this result, it is confirmed that obtained solid is Object DA-4.

¹H NMR(400MHz,[D₆]-DMSO):δ7.54-7.67(d,2H),7.60(s,1H),6.94-6.97(d,2H), 6.48-6.52(d,1H),6.42-6.43(s,2H),6.01-6.05(m,2H),5.70(s,1H),4.99(s,4H),4.36- 4.40(m,4H),4.15-4.19(m,2H),4.00-4.03(m,2H),1.88(s,3H),1.66-1.75(m,4H),1.36- 1.46(m,4H)

The synthesis of (synthesis example 3) DA-3

(the use in above-mentioned reaction equation ● the cyclohexane ring of statement indicates that stereochemical structure is 1,4- trans cyclohexane ring.)

Into reaction vessel add compound DA-3-1 (74.43g, 261mmol), triethylamine (29.81g, 295mmol), THF (1,000g), after carrying out nitrogen displacement, no more than 10 DEG C sides dropwise addition methyl propionyl chlorides of marginal not meaning internal temperature (27.01g, THF (100g) solution 258mmol).After reaction with HPLC confirmation, reaction solution is injected into distilled water (3L), uses vinegar Acetoacetic ester (1.5L) extracts.After organic layer is cleaned 3 times with saturated salt solution (500g), it is dried with magnesium sulfate and mistake Filter, distillation removal solvent, to obtain the crude product of compound DA-3-2.Gained crude product with methanol (100g) is dispersed It cleans and filters, keep solid dry and obtain compound [12] (receipts amount 72.9g, yield 80%).Use described below¹H- The result of NMR measurement gained compound.

¹H-NMR(400MHz,DMSO-d₆,δppm):7.56(2H,d),7.47(1H,d),7.26(2H,d),6.42(1H, d),4.75-4.69(1H,m),2.59-4.47(1H,m),2.01-1.98(2H,m),1.85-1.78(5H,m),1.59-1.44 (4H,m).

Compound DA-3-2 (20.29g, 54.8mmol), DCM (100g) are put into reaction vessel, carry out nitrogen displacement Afterwards, trifluoracetic acid (31.2g, 274mol) is added dropwise.After reaction with HPLC confirmation, reaction solution is injected into distilled water (200mL) is extracted with ethyl acetate (1L).Thereafter, organic layer is cleaned 3 times with saturated salt solution (200g), it will be organic After layer magnesium sulfate drying, it is filtered and distills removal solvent with evaporator, to obtain the crude product of compound DA-3-3. Gained crude product with methanol (30g) is subjected to dispersion cleaning, filters simultaneously dry, (receipts amount is to obtain compound DA-3-3 10.9g, yield 64%).Use described below¹The result of H-NMR measurement gained compound.

¹H-NMR(400MHz,DMSO-d₆,δppm):12.32(1H,brs),7.58-7.50(3H,m),7.27(2H,d), 6.43(1H,d),5.99-5.98(1H,m),5.64-5.63(1H,m),4.78-4.70(1H,m),2.59-2.51(1H,m), 2.02-1.95(2H,m),1.82-1.79(5H,m),1.63-1.42(4H).

2- (dinitrophenyl group) ethyl alcohol (11.94g, 56.3mmol), compound DA-3-3 are added into reaction vessel (10.89g, 35.3mmol), EDC (11.62g, 61.0mmol), DMAP (0.57g, 4.7mmol), THF (130g), at room temperature It is stirred.After reaction using HPLC confirmation, reaction solution is injected into distilled water (600mL), filters out and has been precipitated Solid, obtain the crude product of compound DA-3-4 wash with distilled water.Gained crude product with methanol (100mL) is divided Cleaning is dissipated, after filtering and being dried under reduced pressure, to obtain compound DA-3-4 (receipts amount be 17.1g, yield 96%).It is described below With¹The result of H-NMR measurement gained compound.

¹H-NMR(400MHz,DMSO-d₆,δppm):8.70-8.69(1H,m),8.48-8.45(1H,m),7.87(1H, d),7.58-7.52(3H,m),7.27(2H,d),6.44(1H,d),5.99-5.98(1H,m),5.63-5.62(1H,m), 4.76-4.71(1H,m),4.41(2H,t),3.34(2H,t),2.57-2.54(1H,m),2.01-1.97(2H,m),1.84- 1.78(5H,m),1.60-1.45(4H,m).

Into reaction vessel add compound DA-3-4 (17.00g, 33.4mmol), ferrous components (11.2g, 201mmol), Ethyl acetate (150g), ammonium chloride (5.35g, 100mmol), distilled water (50g), with 70 DEG C of progress heating stirrings.It is true with HPLC Recognize after reaction, solid is filtered with Celite (セライト, Celite) and cleans removal with ethyl acetate (200mL).It will Filtrate is cleaned 3 times with saturated salt solution (200g), after organic layer magnesium sulfate drying, distills removal solvent with evaporator, from And obtain the crude product of compound DA-10.Gained crude product with methanol (100g) is dispersed to clean, filters and is dried under reduced pressure, from And obtain compound DA-3 (receipts amount be 10.3g, yield 69%).Use described below¹The knot of H-NMR measurement gained compound Fruit.

¹H-NMR(400MHz,DMSO-d₆,δppm):7.61-7.57(3H,m),7.27(2H,d),6.58-6.51(2H, m),5.99(1H,s),5.85(1H,d),5.75(1H,dd),5.65-5.63(1H,m),4.80-4.71(1H,m),4.63(2H, brs),4.57(2H,brs),4.12(2H,t),2.64(2H,t),2.59-2.53(1H,m),2.00-1.98(2H,m),1.85- 1.79(5H,m),1.64-1.44(4H,m).

The synthesis of the precursor DA-4-1 of (synthesis example 4-1) DA-4

2- methacrylic acid -6- [4- (2- hydroxycarbonyl group vinyl) phenyl]-own ester is added into 500mL four-neck flask 21.2g, tetrahydrofuran 300mL, 2- (dinitrophenyl group) ethyl alcohol 13.6g, 1- (3- dimethylamino-propyl) -3- ethyl carbon two Inferior amine salt hydrochlorate (EDC) 18.4g, 4-dimethylaminopyridine (DMAP) 0.8g, are stirred at room temperature.After reaction, will Organic layer is extracted with ethyl acetate, after anhydrous magnesium sulfate is added into organic layer and dehydrates, filter, uses rotary evaporator The distillation removal for carrying out solvent, residue is cleaned with isopropanol, is dry, to obtain the object DA-4-1 (yellow-white of 15.9g Solid) (yield 47%).

The synthesis of (synthesis example 4-2) DA-4

Into 500mL four-neck flask add DA-4-1 7.6g, ethyl acetate 150mL, pure water 150ml, reduced iron 8.4g, Ammonium chloride 6.5g is stirred when being heated to 60 DEG C.After reaction, reduced iron is filtered, extracts organic layer with ethyl acetate. Anhydrous magnesium sulfate is added into organic layer and is dehydrated, and anhydrous magnesium sulfate is filtered.It is distilled and is removed using rotary evaporator Solvent in gained filtrate.Residue is cleaned and made it dry with isopropanol, to obtain the object DA-4 of 13.4g (white-yellowish solid) (yield 95%).Use described below¹The result of H-NMR measurement obtained solid.From this result, it is confirmed that Obtained solid is object DA-4.

¹H NMR(400MHz,[D₆]-DMSO):δ7.64-7.66(d,2H),7.58-7.62(d,1H),6.95-6.97(d, 2H),6.60-6.62(d,1H),6.44-6.48(d,1H),6.02(s,1H),5.89(s,1H),5.78-5.81(d,1H), 5.66(s,1H),4.65(s,2H),4.59(s,2H),4.08-4.17(m,4H),4.00-4.03(t,2H),2.65-2.69(t, 2H),1.87(s,3H),1.62-1.74(m,4H),1.39-1.45(m,4H)

Herein, photoreactivity diamines shown in following formula is further synthesized.

The synthesis of (synthesis example 5) DA-10

The synthesis of the precursor DA-10-1 of (synthesis example 5-1) DA-10

At room temperature add 2- methacrylic acid -6- [4,4 '-(2- hydroxycarbonyl group vinyl) xenyl]-monooctyl ester (100g, 229mmol), 3,5- dinitrobenzyl chlorine (55g, 252mmol), n,N-Dimethylformamide (750g), investment potassium carbonate (47g, It after 344mmol), is heated to 80 DEG C and stirs, react it 3 hours.After cooled to room temperature (< 30 DEG C), water is added (1500g) and crystallization cures 30 minutes.

After filtering, filtrate is cleaned 3 times with water (100g).Filtrate is dried with 30 DEG C of vacuum.With four Hydrogen furans (2500g) makes it dissolve, and after carrying out short column (short column) with silica dioxide gel (50g), distillation removal is molten Agent and drying, to obtain DA-10-1 (brown solid) 142g (yield 100%).

The synthesis of (synthesis example 5-2) DA-10

It adds at room temperature 10% aqueous ammonium chloride solution (37g, 698mmol), after carrying out nitrogen displacement, adds reduced iron (78g, 1392mmol), the displacement of further progress nitrogen.The tetrahydrofuran (1435g) that DA-10-1 (72g, 116mmol) is added dropwise is molten After liquid, it is heated to 60 DEG C and stirs 17.5 hours.

After reaction solution cooled to room temperature (< 30 degree), it is filtered with filtration adjuvant (KCFLOCK).Into filtrate After adding ethyl acetate, water and liquid separation, organic layer is washed with water 3 times.Active carbon is added into organic layer and is stirred, and is used KCFLOCK is filtered.Filtrate water is cleaned 3 times, after being dried with magnesium sulfate, distillation removal solvent.Add into residue Add ethyl acetate (36g), hexane (288g) and is stirred at room temperature, crystallization.Leaching filtrate is simultaneously dried with 40 DEG C, To obtain DA-10 (yellow crystal) 107g (yield 83%).Use is shown as follows¹The result of H-NMR measurement gained compound.

1H NMR(400MHz,[D6]-DMSO):δ7.79-7.77(d,2H),7.72-7.65(m,4H),7.03-7.00 (d,2H),6.71-6.67(d,1H),6.02(s,1H),5.84-5.83(d,2H),5.79-5.78(d,2H),5.67-5.66 (d,1H),4.94(s,1H),4.80(s,4H),4.10-4.07(t,2H),4.01-3.98(t,2H),1.87(s,3H),1.74- 1.70(quint,2H),1.63-1.60(quint,2H),1.41-1.33(m,8H)

The synthesis of (synthesis example 6) DA-11

The synthesis of the precursor DA-11-1 of (synthesis example 6-1) DA-11

At room temperature add 2- methacrylic acid 6- [4- (2- hydroxycarbonyl group vinyl) phenyl]-own ester (100g, 301mmol), 3,5- dinitrobenzyl chlorine (58g, 331mmol), n,N-Dimethylformamide (750g), investment potassium carbonate (51g, After 452mmol), heating stirring is to 60 DEG C and reacts 1 hour.

After cooled to room temperature (< 30 DEG C), addition water (1500g) and crystallization are cured 30 minutes.After filtering, it will filter Object is cleaned 3 times with water (100g).Filtrate is carried out slurry with acetonitrile (200g) to wash and dry, so that it is (light to obtain DA-11-1 Tan crystals) 142g (yield 92%).

The synthesis of (synthesis example 6-2) DA-11

It adds at room temperature 10% aqueous ammonium chloride solution (77g, 1659mmol), after carrying out nitrogen displacement, adds reduced iron (161g, 3324mmol), the displacement of further progress nitrogen.The tetrahydrofuran (2126g) of DA-11-1 (142g, 277mmol) is added dropwise After solution, it is heated to 60 DEG C and stirs 18 hours.

After reaction solution cooled to room temperature (< 30 DEG C), it is filtered with KCFLOCK.Filtrate is concentrated and is distilled Except tetrahydrofuran, ethyl acetate, active carbon are added into residue and stirs, filter.Liquid separation is carried out to filtrate, by organic layer water Cleaning 2 times, is dried with sodium sulphate.After filtered filtrate is concentrated, the purification of silica dioxide gel column is carried out, to obtain DA-11 (reddish oil) 90g (yield 72%).Use is shown as follows¹The result of H-NMR measurement gained compound.

1H NMR(400MHz,[D6]-DMSO):δ7.68-7.65(d,2H),7.64-7.60(d,1H),6.70-6.94 (d,2H),6.52-6.48(d,1H),6.02-6.01(d,1H),5.81(s,2H),5.77-5.76(d,2H),5.67-5.65 (t,1H),4.90(s,2H),4.77(s,4H),4.11-4.08(t,2H),4.02-3.99(t,2H),1.87(s,3H),1.74- 1.70(quint,2H),1.66-1.62(quint,2H),1.46-1.38(m,4H)

The synthesis of (synthesis example 7) DA-13

The synthesis of the precursor DA-13-1 of (synthesis example 7-1) DA-13

Trimethylene chlorohydrin (56g, 591mmol) is dissolved in dehydration N,N-dimethylformamide (1000ml).2,4- is added dropwise Dinitrofluorobenzene (100g, 537mmol), triethylamine (109g, 1074mmol).After being warming up to 70 DEG C, stirs 19.5 hours and carry out Reaction.

After natural cooling, vacuum distillation removal n,N-Dimethylformamide, triethylamine.Add ethyl acetate (500g) and water (200g) and liquid separation, organic layer is washed with water 3 times.Organic layer is distilled to remove solvent, to obtain DA-13-1 (yellow Oil) 137g (yield 98%).

The synthesis of the precursor DA-13-2 of (synthesis example 7-2) DA-13

By DA-13-1 (73.9g, 360mmol), 2- methacrylic acid 6- [4- (2- hydroxycarbonyl group vinyl) phenyl]-oneself Ester (85.9g, 328mmol), potassium carbonate (107g, 984mmol), potassium iodide (3.2g, 36mmol) are dissolved in N, N- dimethyl methyl Amide (514g).It is heated to 100 DEG C and reacts 3.5 hours.

It dropwise reaction liquid and is stirred in Xiang Shui (2600g).Filtering precipitate simultaneously obtains yellow filtrate 192g.To gained mistake Acetonitrile (170g) is added in screening, after stirring 30 minutes, is filtered and obtains flaxen filtrate 162g.Filter gained Object is dissolved in ethyl acetate (200g) with 60 DEG C, is added hexane (180g) and is cooled to 0 DEG C.Filtering precipitate is simultaneously cleaned with hexane Afterwards, it is dried and obtains DA-13-2 (faint yellow solid) 117g (yield 81%).

The synthesis of (synthesis example 7-3) DA-13

It adds at room temperature 10% aqueous ammonium chloride solution (666g, 1242mmol), after carrying out nitrogen displacement, adds reduced iron (139g, 2484mmol), the displacement of further progress nitrogen.The tetrahydrofuran (1155g) of DA-13-2 (115g, 207mmol) is added dropwise After solution, it is heated to 60 DEG C and stirs 23 hours.

After reaction solution cooled to room temperature (< 30 DEG C), it is filtered with KCFLOCK.Concentration filtrate simultaneously distills removal Tetrahydrofuran adds ethyl acetate, active carbon into residue, stirs and filter.Liquid separation is carried out to filtrate, organic layer water is clear It washes 3 times, is dried with sodium sulphate.After filtered filtrate is concentrated, the purification of silica dioxide gel column is carried out, to obtain DA- 13 (loess color solid) 41g (yield 40%).Use is shown as follows¹The result of H-NMR measurement gained compound.

1H NMR(400MHz,[D6]-DMSO):δ7.67-7.64(d,2H),7.63-7.59(d,1H),6.96-6.94 (d,2H),6.51-6.47(m,2H),6.01(s,1H),5.94(d,1H),5.76-5.73(t,1H),5.66(s,1H),4.47 (s,2H),4.35-4.29(m,4H),4.11-4.08(t,2H),4.03-3.99(t,2H),3.89-3.86(t,2H),2.07- 2.00(quint,2H),1.87(s,2H),1.76-1.61(m,4H),1.48-1.35(m,4H)

<<Examples 1 to 4 and comparative example 1>>

(embodiment 1)

In the NMP (20.1g) dissolution BODA (1.25g, 5.0mmol), DA-1 (3.38g, 7.0mmol), DA-6 (1.14g, 3.0mmol), after reacting 5 hours with 60 DEG C, CBDA (0.92g, 4.7mmol) and NMP (6.7g) are added, it is small with 40 DEG C of reactions 10 When, to obtain polyamic acid solution.After being diluted to 6 mass % to addition NMP in the polyamic acid solution (30g), as Imidization catalyst adds acetic anhydride (2.2g) and pyridine (6.9g), is reacted 3 hours with 50 DEG C.The reaction solution is put into To methanol (440ml), leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure with 60 DEG C, to obtain Polyimide powder (A1).The acid imide rate of the polyimides is 50%, and number-average molecular weight 15,000, weight average molecular weight are 46,000。

NMP (22.0g) is added in gained polyimide powder (A) (3.0g), with 50 DEG C are stirred 3 hours and keep its molten Solution.3AMP (nmp solution of 1wt%) 3.0g, NMP (7.0g), BCS (15.0g) are added into the solution, it is small to be stirred at room temperature 5 When, to obtain aligning agent for liquid crystal (A1).

In addition, addition polymerizable compound RM1 0.06g is (relative to solid relative to above-mentioned aligning agent for liquid crystal (A1) 10.0g Body ingredient is 10 mass %), it is stirred at room temperature 3 hours and makes it dissolve, to prepare aligning agent for liquid crystal (A2).

(embodiment 2)

In the NMP (18.2g) dissolution BODA (1.25g, 5.0mmol), DA-2 (2.55g, 5.0mmol), DA-7 (0.87g, 2.0mmol), DBA (0.46g, 3.0mmol) after reacting 5 hours with 60 DEG C, adds CBDA (0.92g, 4.7mmol) and NMP (6.1g) is reacted 10 hours with 40 DEG C, to obtain polyamic acid solution.To addition NMP in the polyamic acid solution (29g) After being diluted to 6 mass %, as imidization catalyst, acetic anhydride (2.4g) and pyridine (7.6g) are added, it is small with 50 DEG C of reactions 3 When.The reaction solution is put into methanol (430ml), leaching gained sediment.The sediment is cleaned with methanol, with 60 DEG C into Row, which is dried under reduced pressure, obtains polyimide powder (B1).The acid imide rate of the polyimides is 51%, number-average molecular weight 14, 000, weight average molecular weight 39,000.

NMP (22.0g) is added in gained polyimide powder (B) (3.0g), with 50 DEG C are stirred 3 hours and keep its molten Solution.3AMP (nmp solution of 1wt%) 3.0g, NMP (7.0g), BCS (15.0g) are added into the solution, it is small to be stirred at room temperature 5 When, to obtain aligning agent for liquid crystal (B1).

In addition, addition polymerizable compound RM20.06g is (relative to solid relative to above-mentioned aligning agent for liquid crystal (B1) 10.0g Body ingredient is 10 mass %), it is stirred at room temperature 3 hours and makes it dissolve, to prepare aligning agent for liquid crystal (B2).

(embodiment 3)

In the NMP (12.2g) dissolution TCA (1.12g, 5.0mmol), DA-3 (2.24g, 5.0mmol), DA-8 (1.05g, 2.0mmol), 3AMPDA (0.73g, 3.0mmol) after reacting 5 hours with 80 DEG C, adds CBDA (0.94g, 4.8mmol) and NMP (6.1g) is reacted 10 hours with 40 DEG C, to obtain polyamic acid solution.To addition NMP in the polyamic acid solution (29g) After being diluted to 6 mass %, as imidization catalyst, acetic anhydride (2.4g) and pyridine (7.6g) are added, it is small with 50 DEG C of reactions 3 When.The reaction solution is put into methanol (430ml), leaching gained sediment.The sediment is cleaned with methanol, with 60 DEG C into Row is dried under reduced pressure, to obtain polyimide powder (C1).The acid imide rate of the polyimides is 51%, and number-average molecular weight is 11,000, weight average molecular weight 31,000.

NMP (22.0g) is added in gained polyimide powder (C) (3.0g), with 50 DEG C are stirred 3 hours and keep its molten Solution.3AMP (nmp solution of 1wt%) 3.0g, NMP (7.0g), BCS (15.0g) are added into the solution, are stirred at room temperature 5 Hour, to obtain aligning agent for liquid crystal (C1).

In addition, addition polymerizable compound RM20.06g is (relative to solid relative to above-mentioned aligning agent for liquid crystal (C1) 10.0g Body ingredient is 10 mass %), it is stirred at room temperature 3 hours and makes it dissolve, to prepare aligning agent for liquid crystal (C2).

(embodiment 4)

Make CBDA (1.92g, 10.0mmol), DA-4 (3.73g, 8.0mmol), DA-9 (0.80g, 2.0mmol) with room temperature In NMP (36.58g) after reaction 10 hours, NMP (32.3g), BCS (32.3g) are added, is stirred at room temperature 5 hours, thus Obtain aligning agent for liquid crystal (D1).The number-average molecular weight of the polyamic acid is 9,000, weight average molecular weight 32,000.

In addition, addition polymerizable compound RM1 0.06g is (relative to solid relative to above-mentioned aligning agent for liquid crystal (D1) 10.0g Body ingredient is 10 mass %), it is stirred at room temperature 3 hours and makes it dissolve, to prepare aligning agent for liquid crystal (D2).

(comparative example 1)

In the NMP (14.7g) dissolution BODA (1.25g, 5.0mmol), DA-5 (1.06g, 4.0mmol), DA-9 (1.20g, 3.0mmol), DBA (0.46g, 3.0mmol) after reacting 5 hours with 60 DEG C, adds CBDA (0.94g, 4.8mmol) and NMP (4.9g) is reacted 10 hours with 40 DEG C, to obtain polyamic acid solution.To addition NMP in the polyamic acid solution (23g) After being diluted to 6 mass %, as imidization catalyst, acetic anhydride (2.4g) and pyridine (7.4g) are added, it is small with 50 DEG C of reactions 3 When.The reaction solution is put into methanol (350ml), leaching gained sediment.The sediment is cleaned with methanol, with 60 DEG C into Row is dried under reduced pressure, to obtain polyimide powder (E).The acid imide rate of the polyimides is 50%, and number-average molecular weight is 17000, weight average molecular weight 48000.

NMP (22.0g) is added in gained polyimide powder (E) (3.0g), with 50 DEG C are stirred 3 hours and keep its molten Solution.3AMP (nmp solution of 1wt%) 3.0g, NMP (7.0g), BCS (15.0g) are added into the solution, are stirred at room temperature 5 Hour, to obtain aligning agent for liquid crystal (E1).

In addition, addition polymerizable compound RM1 0.06g is (relative to solid relative to above-mentioned aligning agent for liquid crystal (E1) 10.0g Body ingredient is 10 mass %), it is stirred at room temperature 3 hours and makes it dissolve, to prepare aligning agent for liquid crystal (E2).

<<embodiment 5~8 and comparative example 2~6>>

(embodiment 5)

Using aligning agent for liquid crystal obtained in embodiment 1 (A2), liquid crystal cells are carried out according to following shown such steps Production.Aligning agent for liquid crystal obtained in embodiment 1 (A2) is spun on be formed with Pixel Dimensions be 300 μm of 100 μ m and line/ Interval is respectively after press drying 90 seconds of 80 DEG C, to use on the ito surface of the ITO electrode substrate of 5 μm of ITO electrode pattern 200 DEG C of heated air circulation type baking oven carries out firing in 30 minutes, to form the liquid crystal orientation film that film thickness is 100nm.

In addition, aligning agent for liquid crystal (A2) to be spun on to the ito surface of not formed electrode pattern, made it dry with 80 DEG C of hot plate After 90 seconds, firing in 30 minutes is carried out with 200 DEG C of heated air circulation type baking oven, to form the liquid crystal aligning that film thickness is 100nm Film.

For 2 above-mentioned plate bases, after 4 μm of pearl spacer is spread on the liquid crystal orientation film of a substrate, from it Upper 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 surface of side is used as inside, after being pasted on previous substrate, makes sealant cures to make dummy cell.By depressurizing injection method Liquid crystal MLC-6608 (MERCK CORPORATION system, trade name) is injected into the dummy cell, to make liquid crystal cells.

The response speed of gained liquid crystal cells is measured using following methods.Thereafter, 40Vp- is being applied with to the liquid crystal cells In the state of p voltage, from the outside of the liquid crystal cells, irradiation has penetrated the UV 10J/cm of the bandpass filter of 365nm².Thereafter, Response speed is measured again, and compares the response speed of UV irradiation front and back.In addition, measuring pixel for the unit after UV irradiation Partial pre-tilt angle.Show the result in table 1.

" measuring method of response speed "

Firstly, by backlight, the measurement that one group of polarization plates, the sequence of light quantity detector of crossed nicols state are constituted be made filling In setting, liquid crystal cells are configured between one group of polarization plates.At this point, making the pattern to form the ITO electrode at wired/interval relative to friendship Pitch prism angle at 45 °.Also, the rectangular wave that above-mentioned liquid crystal cells are applied with voltage ± 6V, frequency 1kHz, is read with oscillograph The variation until reaching saturation using the brightness that light quantity detector observes is taken, brightness when by no applied voltage is set as 0%, and The brightness value that the voltage of application ± 4V is saturated is set as 100%, by brightness from 10% be changed to 90% needed for the time be denoted as Response speed.

" measurement of pre-tilt angle "

The LCD analyzer LCA-LUV42A for having used Meiryo Technica Corporation to manufacture.

(embodiment 6)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (B2), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

(embodiment 7)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (C2), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

(embodiment 8)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (D2), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

(comparative example 2)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (A1), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

(comparative example 3)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (B1), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

(comparative example 4)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (C1), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

(comparative example 5)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (D1), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

(comparative example 6)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (E2), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

<<embodiment 9~11>>

(embodiment 9)

BODA (3.50g, 14.0mmol), DA-10 (5.85g, 10.5mmol), DA-6 are dissolved in NMP (63.8g) (5.33g, 14.0mmol), 3AMPDA (2.54g, 10.5mmol), after being reacted 3 hours with 60 DEG C, addition CBDA (4.05g, 20.7mmol) with NMP (21.3g), reacted 10 hours with 40 DEG C, to obtain polyamic acid solution.To the polyamic acid solution Addition NMP in (95g) and after being diluted to 6.5 mass %, as imidization catalyst, add acetic anhydride (8.0g) and pyridine (24.7g) is reacted 3 hours with 50 DEG C.The reaction solution is put into methanol (1,300ml), leaching gained sediment.This is sunk Starch is cleaned with methanol, is dried under reduced pressure with 60 DEG C, to obtain polyimide powder (F).The acid imide of the polyimides Rate is 60%, number-average molecular weight 13,000, weight average molecular weight 45,000.

NMP (44.0g) is added in gained polyimide powder (F) (6.0g), with 50 DEG C are stirred 3 hours and keep its molten Solution.3AMP (nmp solution of 1wt%) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, are stirred at room temperature 5 Hour, to obtain aligning agent for liquid crystal (F1).

In addition, addition polymerizable compound RM1 0.06g is (relative to solid relative to above-mentioned aligning agent for liquid crystal (F1) 10.0g Body ingredient is 10 mass %), it is stirred at room temperature 3 hours and makes it dissolve, to prepare aligning agent for liquid crystal (F2).

(embodiment 10)

BODA (3.50g, 14.0mmol), DA-11 (4.75g, 10.5mmol), DA-6 are dissolved in NMP (60.5g) (5.33g, 14.0mmol), 3AMPDA (2.54g, 10.5mmol), after being reacted 3 hours with 60 DEG C, addition CBDA (4.05g, 20.7mmol) with NMP (20.2g), reacted 10 hours with 40 DEG C, to obtain polyamic acid solution.To the polyamic acid solution Addition NMP in (95g) and after being diluted to 6.5 mass %, as imidization catalyst, add acetic anhydride (8.0g) and pyridine (24.7g) is reacted 3 hours with 50 DEG C.The reaction solution is put into methanol (1,300ml), leaching gained sediment.This is sunk Starch is cleaned with methanol, is dried under reduced pressure with 60 DEG C, to obtain polyimide powder (G).The acid imide of the polyimides Rate is 60%, number-average molecular weight 12,000, weight average molecular weight 39,000.

NMP (44.0g) is added in gained polyimide powder (G) (6.0g), with 50 DEG C are stirred 3 hours and keep its molten Solution.3AMP (nmp solution of 1wt%) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, are stirred at room temperature 5 Hour, to obtain aligning agent for liquid crystal (G1).

In addition, addition polymerizable compound RM1 0.06g is (relative to solid relative to above-mentioned aligning agent for liquid crystal (G1) 10.0g Body ingredient is 10 mass %), it is stirred at room temperature 3 hours and makes it dissolve, to prepare aligning agent for liquid crystal (G2).

(embodiment 11)

BODA (3.50g, 14.0mmol), DA-13 (5.21g, 10.5mmol), DA-6 are dissolved in NMP (61.9g) (5.33g, 14.0mmol), 3AMPDA (2.54g, 10.5mmol), after being reacted 3 hours with 60 DEG C, addition CBDA (4.05g, 20.7mmol) with NMP (20.6g), reacted 10 hours with 40 DEG C, to obtain polyamic acid solution.To the polyamic acid solution Addition NMP in (95g) and after being diluted to 6.5 mass %, as imidization catalyst, add acetic anhydride (8.0g) and pyridine (24.7g) is reacted 3 hours with 50 DEG C.The reaction solution is put into methanol (1,300ml), leaching gained sediment.This is sunk Starch is cleaned with methanol, is dried under reduced pressure with 60 DEG C, to obtain polyimide powder (H).The acid imide of the polyimides Rate is 60%, number-average molecular weight 10,000, weight average molecular weight 27,000.

NMP (44.0g) is added in gained polyimide powder (H) (6.0g), with 50 DEG C are stirred 3 hours and keep its molten Solution.3AMP (nmp solution of 1wt%) 6.0g, NMP (4.0g), BCS (40.0g) are added into the solution, are stirred at room temperature 5 Hour, to obtain aligning agent for liquid crystal (H1).

In addition, addition polymerizable compound RM1 0.06g is (relative to solid relative to above-mentioned aligning agent for liquid crystal (H1) 10.0g Body ingredient is 10 mass %), it is stirred at room temperature 3 hours and makes it dissolve, to prepare aligning agent for liquid crystal (H2).

<<embodiment 12~14>>

(embodiment 12)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (F2), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

(embodiment 13)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (G2), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

(embodiment 14)

Aligning agent for liquid crystal (A2) is replaced using aligning agent for liquid crystal (H2), in addition to this, carries out identical behaviour with embodiment 5 Make, the response speed of comparison UV irradiation front and back.In addition, carrying out the measurement of pre-tilt angle.

[table 1]

As shown in table 1 like that, can be confirmed that by by photonasty side chain position have methylacryloyl, cinnamoyl this The polymer and polymerizable compound of the two are combined use, even the long wavelength ultraviolet light of 365nm etc can also show Sufficient response speed, inclination angle out.This is considered because: by making side chain position that there are 2 photonasty groups, it is fixed on height The photoreactivity at the photonasty side chain position in molecule improves, and existing polymerizable compound reacts anti-with dissociating in system The tremendous raising of answering property.

On the other hand, when not importing polymerizable compound of comparative example 2~5, have the effect of improve response speed, but It is perhaps because the light reaction of polymerization reaction, cross-linking reaction will not be pushed away sufficiently under the weaker ultraviolet light irradiation of the energy such as 365nm Into so that sufficient response speed, inclination angle can not be obtained.

In addition, as shown in comparative example 6, even if photosensitive side chain position is only had methylacryloyl In the case that macromolecule and polymerizable compound are applied in combination, when irradiating the ultraviolet light of 365nm, sufficient raising can not be also obtained Response speed, inclination angle expressive ability.

As a result, as in this embodiment, by the way that photonasty side chain position is had the optical polymerisms such as methylacryloyl The polymer and polymerizable compound of both photocrosslinking reactions bases such as group and cinnamoyl are combined use, even if irradiation The ultraviolet light of the long wavelengths such as 365nm can also obtain sufficient response speed, inclination angle.

Claims

1. a kind of aligning agent for liquid crystal, which is characterized in that it contains polymer and polymerizable compound, and the polymer is selected from poly- Imide precursor and carried out at least one kind of in polyimides obtained from imidizate, the polyimide precursor is logical Cross the diamines comprising diamine compound shown in following formula [1] and the diamine compound with the side chain for making liquid crystal vertical-tropism at Point with obtained from the reacting of tetracarboxylic dianhydride's ingredient,

In formula, R³It indicates to be selected from-CH₂,-O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH-, the group in-CO-；R⁴For The carbocyclic ring or heterocycle of the alkylidene, divalent that are formed by 1~carbon number of carbon number 30, the alkylidene, the carbocyclic ring of divalent or 1 on heterocycle Or multiple hydrogen atoms are optionally replaced by fluorine atom or organic group, in addition, not adjacent to each other in any group being exemplified below In the case of, R⁴In-CH₂Optionally replaced by these groups, the group be-O- ,-NHCO- ,-CONH- ,-COO- ,-OCO- ,- NH-,-NHCONH-,-CO-；R⁵Expression-CH₂,-O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH- ,-CO-, in singly-bound Any one；R⁶Indicate cinnamoyl；R⁷For the carbocyclic ring of singly-bound or the alkylidene, divalent that are formed by 1~carbon number of carbon number 30 or miscellaneous Ring, the alkylidene, the carbocyclic ring of divalent or one or more hydrogen atoms on heterocycle are optionally replaced by fluorine atom or organic group, separately Outside, in the case where any group being exemplified below is not adjacent to each other, R⁷In-CH₂It is optionally replaced by these groups, the base Group is-O- ,-NHCO- ,-CONH- ,-COO- ,-OCO- ,-NH- ,-NHCONH- ,-CO-；R⁸It indicates to be selected from acryloyl group, methyl The polymerism group of any one in acryloyl group.

2. aligning agent for liquid crystal according to claim 1, which is characterized in that diamine compound shown in formula [1] be diamines at 10 moles of %~90 mole % in point.

3. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, which is characterized in that having makes liquid crystal vertical-tropism Side chain diamine compound be diamine component in 10 moles of %~70 mole %.

4. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, which is characterized in that polymerizable compound is following formula Shown in polymerizable compound,

V is singly-bound or use-R¹O- is indicated and R¹For straight chain or the alkylidene of the carbon number 1~10 of branch；W is singly-bound or use- OR²Expression and R²For straight chain or the alkylidene of the carbon number 1~10 of branch；R¹²For H or the alkyl of carbon number 1~4.

5. a kind of liquid crystal orientation film, which is characterized in that it is the liquid crystal as described in any one of 1~claim 4 of claim What alignment agent obtained.

6. a kind of liquid crystal indicates element, which is characterized in that it has liquid crystal orientation film described in claim 5.

7. a kind of diamine compound, which is characterized in that its with following formula [DA-4] indicate,

8. a kind of diamine compound, which is characterized in that its with following formula [DA-10] indicate,

9. a kind of diamine compound, which is characterized in that its with following formula [DA-11] indicate,

10. a kind of diamine compound, which is characterized in that its with following formula [DA-13] indicate,