CN104081268B

CN104081268B - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: CN104081268B
Application number: CN201280065416.0A
Authority: CN
Inventors: 片山雅章; 高山祐树; 川野勇太; 后藤耕平
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2011-11-01
Filing date: 2012-10-31
Publication date: 2017-05-24
Anticipated expiration: 2032-10-31
Also published as: JP2017226647A; WO2013065755A1; JP6183212B2; TWI567107B; TW201335232A; JPWO2013065755A1; KR20140084278A; JP6465159B2; CN104081268A; KR101938923B1

Abstract

A liquid crystal aligning agent which contains at least one polymer that is selected from the group consisting of polyimide precursors having a side chain represented by formula [1A] or formula [1B] and polyimides obtained by imidizing the polyimide precursors. (In formula [1A] or [1B], each of X1 and X5 represents a single bond, -O-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -N(R1)- (wherein R1 represents a linear or branched alkyl group having 1-5 carbon atoms) or -S-; each of X2 and X3 represents a divalent cyclic group selected from among a benzene ring, a cyclohexyl ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups may be substituted by an alkyl group having 1-3 carbon atoms or the like; X4 represents an alkyl group, fluorine-containing alkyl group, alkoxyl group or fluorine-containing alkoxyl group having 1-18 carbon atoms; X6 represents an organic group having a steroid skeleton and 12-25 carbon atoms; m represents a number of 2-15; n represents a number of 1-3 and p represents a number of 0-3, with n + p being a number of 1-6; and q represents a number of 2-15.)

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells

Technical field

The present invention relates to new diamine compound, by the compound be used as raw material a part reacted obtained by polyamides Imines precursor, polyimides obtained by imidizate, the liquid crystal aligning comprising these polymer are carried out to the polyimide precursor Inorganic agent, liquid crystal orientation film and the liquid crystal display cells with the liquid crystal orientation film.

Background technology

Liquid crystal display cells are widely used as realizing slim, light weight display device now.The liquid crystal display cells are usual The state of orientation of liquid crystal is determined using liquid crystal orientation film.

The liquid crystal orientation film in most cases uses polyimide film.The formation of the polyimide film, use will be made For the solution of the polyamic acid of the precursor of polyimides or the solution coating of solvent-soluble polyimide is in substrate and is burnt Into method.The polyamic acid or solvent-soluble polyimide are typically by tetracarboxylic acid derivatives and diamines such as tetracarboxylic dianhydrides The reaction of composition is formed.

As to one of characteristic required by liquid crystal orientation film, liquid crystal molecule is protected relative to the orientation inclination angle of real estate Hold and be arbitrarily worth, i.e., the control of the tilt angle with so-called liquid crystal.The big I of the known tilt angle is constituted by selecting The structure of the polyimides of liquid crystal orientation film changes.In controlling the technology of tilt angle by the structure of polyimides, polyamides A part for the raw material of imines can control tilt angle, institute using the method for the diamines with side chain according to the use ratio of the diamines To be easier to obtain target tilt angle, can be used as increasing the method (see, for example patent document 1) of tilt angle.

Additionally, the diamine component of the tilt angle for being used to increase liquid crystal like this, is also carried out for improving pre-dumping The structural research of the stability and process dependency at angle.Here, the side-chain structure used by, puts forward containing phenyl or cyclohexyl Deng the structure (see, for example patent document 2) of ring structure.

, it is necessary to be filled to (box spacing) between being formed with 2 pieces of substrates of liquid crystal orientation film in the making of liquid crystal display cells The operation of liquid crystal.So far, liquid crystal filling is usually the pressure differential using atmospheric pressure and vacuum to filling liquid crystal between 2 pieces of substrates Vacuum injection mode.However, in the case of which, liquid crystal injecting port is only located at the one side of substrate, therefore in order to between box The filling liquid crystal away between the substrate for 3~5 μm, it is necessary to the long period, so being difficult to simplify the manufacturing process of liquid crystal display cells.It is special Be not liquid crystal TV set and giant display practical in recent years manufacture in, this turn into big problem.

Then, in order in solving the problems, such as above-mentioned vacuum injection mode, develop liquid crystal drop add mode (also referred to as ODF Mode).Which is that liquid crystal is added dropwise on the substrate of liquid crystal orientation film to being formed with, and after another piece of substrate is bonded in a vacuum, is made Encapsulant UV solidifies, so that the mode of filling liquid crystal.

On the other hand, as the continuous High precision of liquid crystal display cells is, it is necessary to control to show deviation.For ODF modes, Vacuum when all the time by reducing the dripping quantity of liquid crystal or improving bonding etc. mitigates the system of the influence of absorption water and impurity Process optimization is made to solve.However, with the maximization of liquid crystal display cells manufacturing line, it is excellent by conventional manufacturing process Change cannot suppress to show deviation, it is necessary to can more reduce the liquid crystal orientation film of display deviation than ever.

Prior art literature

Patent document

Patent document 1:Japanese Patent Laid-Open 2-282726 publications

Patent document 2:Japanese Patent Laid-Open 9-278724 publications

The summary of invention

The technical problems to be solved by the invention

Liquid crystal orientation film also be used to carrying out the control of tilt angle of the liquid crystalline phase for the angle of substrate, i.e. liquid crystal, but Liquid crystal display cells high performance, in the case that its range of application expands year by year, is not only the tilt angle for obtaining regulation, tilt angle Stability also become more and more important.

It is sometimes laggard in inclosure liquid crystal in order to improve the orientation uniformity of liquid crystal in the manufacturing process of liquid crystal display cells Row heats to make the temporary transient isotropization of liquid crystal.However, in the case that the stability of tilt angle is low, there is the isotropism The tilt angle or tilt angle that target sizes cannot be obtained after change treatment produce the problem of deviation.Especially for acquisition high brightness The liquid crystal display cells of the backlight using caloric value is big, more than the exposure of light, such as onboard navigation system and large-scale tv machine In, used in the environment of high temperature and illumination or placed for a long time sometimes.Under such rigor condition, pre-dumping When contention gradually there occurs change, appearance cannot obtain the display characteristic at initial stage or produce the problems such as showing deviation.

In the ODF modes of liquid crystal filling work procedure during as making liquid crystal display cells, liquid crystal is directly added dropwise in orientation On film, therefore when liquid crystal drop added-time or base plate bonding, liquid crystal bears physical stress with liquid crystal orientation film, in order in whole panel area Domain filling liquid crystal is, it is necessary to increase the dropwise addition point of liquid crystal.Therefore, the drop of liquid crystal dropwise addition portion and liquid crystal connects with adjacent liquid crystal Part easily produces the so-called orientation inequality for being referred to as that trace or lattice deviation is added dropwise, and in the case of being made liquid crystal display cells, deposits Causing the problem of display deviation because being orientated inequality.The orientation is not regarded as the liquid crystal aligning due to being formed on substrate The absorption water and impurity of membrane interface attachment are gathered because of the liquid crystal being added dropwise in ODF modes, and the amount of absorption water and impurity is in liquid crystal drop Plus portion is different with the part that liquid crystal droplet connects and produces.

The invention that the present invention is in view of the foregoing and completes.That is, even if it is an object of the invention to provide sudden and violent for a long time Being exposed to high temperature and illumination will not also occur the liquid crystal orientation film of change of tilt angle, and provides and can mitigate what is produced in ODF modes The uneven liquid crystal orientation film of liquid crystal aligning.In addition, the present invention also aims to provide the liquid with above-mentioned liquid crystal orientation film Crystal display element, the aligning agent for liquid crystal that above-mentioned liquid crystal orientation film can be provided, for obtaining the aligning agent for liquid crystal Polymer and the diamine compound for obtaining the polymer.

Solve the technical scheme that technical problem is used

Present inventor has performed conscientiously studying, as a result find that the liquid crystal of the polymer comprising the side chain with ad hoc structure takes In terms of inorganic agent states purpose in realization especially effectively, so as to complete the present invention.

That is, the present invention includes following technology contents.

(1) aligning agent for liquid crystal, it is characterised in that comprising selected from the side represented with following formulas [1A] or [1B] The polyimide precursor of chain and at least a kind polymer of polyimides obtained by imidizate is carried out to the polyimide precursor；

[changing 1]

In formula [1A], X₁It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₁)-or-S-, R₁For The straight-chain alkyl of carbon number 1~5 or the branch-like alkyl of carbon number 1~5；X₂Represent the divalent ring selected from phenyl ring, hexamethylene ring or heterocycle Shape group, the arbitrary hydrogen atom on these cyclic groups can be by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1 ~3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom substitution；X₃Represent 2 selected from phenyl ring, hexamethylene ring or heterocycle Valency cyclic group, the arbitrary hydrogen atom on these cyclic groups can be by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon Number 1~3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom substitution；X₄For the alkyl of carbon number 1~18, carbon number 1~ 18 fluoroalkoxy containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1~18；M is 2~15 integer, and n is 1~3 Integer, p is 0~3 integer, and n+p is 1~6 integer；

[changing 2]

In formula [1B], X₅It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₂)-or-S-, R₂For The straight-chain alkyl of carbon number 1~5 or the branch-like alkyl of carbon number 1~5；X₆It is having for the carbon number 12~25 with steroid skeleton Machine group；Q is 2~15 integer.

(2) aligning agent for liquid crystal as described above described in (1), wherein, the polyimide precursor be make to include to have with The diamine component of the diamine compound of the side chain that formula [1A] or formula [1B] are represented reacts and obtains with tetrabasic carboxylic acid composition.

(3) aligning agent for liquid crystal as described above described in (2), wherein, described with the side chain represented with formula [1A] two Amines is represented with following formulas [2A]；

[changing 3]

In formula [2A], X₁It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₁)-or-S-, R₁For The straight-chain alkyl of carbon number 1~5 or the branch-like alkyl of carbon number 1~5；X₂Represent the divalent ring selected from phenyl ring, hexamethylene ring or heterocycle Shape group, the arbitrary hydrogen atom on these cyclic groups can be by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1 ~3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom substitution；X₃Represent 2 selected from phenyl ring, hexamethylene ring or heterocycle Valency cyclic group, the arbitrary hydrogen atom on these cyclic groups can be by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon Number 1~3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom substitution；X₄For the alkyl of carbon number 1~18, carbon number 1~ 18 fluoroalkoxy containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1~18；M is 2~15 integer, and n is 1~3 Integer, p is 0~3 integer, and n+p is 1~6 integer.

(4) aligning agent for liquid crystal as described above described in (3), wherein, the diamine compound represented with formula [2A] with Following formulas [2a]~formula [2d] is represented；

[changing 4]

In formula [2a], R₁For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or The fluoroalkoxy of carbon number 1~18, m1 is 2~15 integer, and p1 is 0~3 integer；

In formula [2b], R₂For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or The fluoroalkoxy of carbon number 1~18, m2 is 2~15 integer, and p2 is 0~3 integer；

In formula [2c], R₃For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or The fluoroalkoxy of carbon number 1~18, m3 is 2~15 integer, and n1 is 1~3 integer, and p3 is 0~3 integer, and n1+p3 is 1 ~6 integer；

In formula [2d], R₄For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or The fluoroalkoxy of carbon number 1~18, m4 is 2~15 integer, and n2 is 1~3 integer, and p4 is 0~3 integer, and n2+p4 is 1 ~6 integer.

(5) aligning agent for liquid crystal as described above described in (2), wherein, described with the side chain represented with formula [1B] two Amines is represented with following formulas [2B]；

[changing 5]

In formula [2B], X₅It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₂)-or-S-, R₂For The straight-chain alkyl of carbon number 1~5 or the branch-like alkyl of carbon number 1~5；X₆It is having for the carbon number 12~25 with steroid skeleton Machine group；Q is 2~15 integer.

(6) the described aligning agent for liquid crystal in any one of (3)~(5) as described above, wherein, it is described with formula [2A] or formula 5~80 moles of % that the diamine compound that [2B] is represented is accounted in diamine component.

(7) aligning agent for liquid crystal as described above described in (4), wherein, the diamines represented with formula [2a]~formula [2d] 5~80 moles of % that compound is accounted in diamine component.

(8) the described aligning agent for liquid crystal in any one of (2)~(7) as described above, wherein, the tetrabasic carboxylic acid composition is With the tetracarboxylic dianhydride that following formulas [3] is represented；

[changing 6]

In formula [3], Z₁It is 4 valency organic groups of carbon number 4~13, and the non-aromatic cyclic hydrocarbon base comprising carbon number 4~10.

(9) aligning agent for liquid crystal as described above described in (8), wherein, the Z₁It is with following formulas [3a]~formula [3j] The structure of expression；

[changing 7]

In formula [3a], Z₂~Z₅It is hydrogen atom, methyl, chlorine atom or phenyl ring, may be the same or different respectively；In formula [3g], Z₆、Z₇It is hydrogen atom or methyl, may be the same or different respectively.

(10) the described aligning agent for liquid crystal in any one of (1)~(9) as described above, wherein, aligning agent for liquid crystal In comprising 80~99 mass % organic solvent.

(11) aligning agent for liquid crystal as described above described in (10), wherein, organic solvent includes that 5~60 mass %'s is bad Solvent.

(12) liquid crystal orientation film, is obtained by any one of above-mentioned (1)~(11) described aligning agent for liquid crystal.

(13) liquid crystal orientation film, using any one of above-mentioned (1)~(11) described aligning agent for liquid crystal by spray Black coating method is obtained.

(14) liquid crystal display cells, with the liquid crystal orientation film described in above-mentioned (12) or (13).

(15) liquid crystal orientation film as described above described in (12) or (13), for having between a pair of substrates for possessing electrode Liquid crystal layer and the liquid crystal display cells being made by following operations：Configuration is comprising by active-energy between the pair of substrate In ray and heat at least one party polymerization polymerizable compound liquid-crystal composition, between the electrode applied voltage it is same When the polymerizable compound is polymerized.

(16) liquid crystal display cells, with the liquid crystal orientation film described in above-mentioned (15).

(17) liquid crystal display cells as described above described in (16), are made by following operations：Possessing electrode and the liquid There is liquid crystal layer between a pair of substrates of brilliant alignment films, between the pair of substrate configuration comprising by active energy beam and The liquid-crystal composition of the polymerizable compound of at least one party's polymerization in heat, to making institute between the electrode while applied voltage State polymerizable compound polymerization.

(18) liquid crystal orientation film as described above described in (12) or (13), for having between a pair of substrates for possessing electrode Liquid crystal layer and the liquid crystal display cells being made by following operations：Configuration is comprising by active-energy between the pair of substrate The liquid crystal orientation film of the polymerizable group of at least one party's polymerization in ray and heat, between the electrode while applied voltage The polymerizable group is set to be polymerized.

(19) liquid crystal display cells, it is characterised in that with the liquid crystal orientation film described in above-mentioned (18).

(20) liquid crystal display cells as described above described in (19), are made by following operations：In a pair of bases for possessing electrode There is liquid crystal layer, configuration is comprising by least one party in active energy beam and heat between the pair of substrate between plate The liquid crystal orientation film of the polymerizable group of polymerization, is polymerized to the polymerizable group is made between the electrode while applied voltage.

(21) diamine compound represented with the formula [2A].

(22) diamine compound represented with the formula [2a]~formula [2d].

(23) make to include the diamine component and tetrabasic carboxylic acid composition of the diamine compound represented with formula [2A] or formula [2B] Polyamic acid obtained by reaction, or make the polyimides obtained by polyamic acid dehydration closed-loop.

(24) make to include the diamine component and tetrabasic carboxylic acid composition of the diamine compound represented with formula [2a]~formula [2d] Polyamic acid obtained by reaction, or make the polyimides obtained by polyamic acid dehydration closed-loop.

The effect of invention

By using the aligning agent for liquid crystal of the polymer comprising the side chain with ad hoc structure of the invention, it is possible to provide Even if the change of tilt angle will not also occur exposed to high temperature and illumination for a long time, and the liquid crystal produced in ODF modes can be mitigated It is orientated uneven liquid crystal orientation film.Thus, by using the liquid crystal orientation film, it is possible to provide display characteristic good reliability is high Liquid crystal display cells.

The mode for carrying out an invention

Hereinafter, the present invention is described in detail.

The present invention is comprising selected from the side chain represented with following formulas [1A] or [1B], (also referred to as particular side is chained Structure) polyimide precursor and at least a kind polymer of polyimides obtained by imidizate is carried out to the polyimide precursor The aligning agent for liquid crystal of (also referred to as particular polymers).

[changing 8]

In formula [1A], X₁It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₁)-or-S-, R₁For The straight-chain alkyl of carbon number 1~5 or the branch-like alkyl of carbon number 1~5.X₂Represent the divalent ring selected from phenyl ring, hexamethylene ring or heterocycle Shape group, the arbitrary hydrogen atom on these cyclic groups can be by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1 ~3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom substitution.X₃Represent 2 selected from phenyl ring, hexamethylene ring or heterocycle Valency cyclic group, the arbitrary hydrogen atom on these cyclic groups can be by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon Number 1~3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom substitution.X₄For the alkyl of carbon number 1~18, carbon number 1~ 18 fluoroalkoxy containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1~18.M is 2~15 integer, and n is 1~3 Integer, p is 0~3 integer, and n+p is 1~6 integer.

[changing 9]

In formula [1B], X₅It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₂)-or-S-, R₂For The straight-chain alkyl of carbon number 1~5 or the branch-like alkyl of carbon number 1~5.X₆It is having for the carbon number 12~25 with steroid skeleton Machine group.Q is 2~15 integer.

Specific side-chain structure of the invention is the structure represented with the formula [1A] or formula [1B].

The structure represented with formula [1A] is as phenyl ring, hexamethylene ring or heterocycle.Thus, side chain position is to hot and ultraviolet Stability is improved.Therefore, tilt angle can be obtained for liquid crystal orientation film that light and heat are also stablized.

Additionally, the structure represented with formula [1B] has the cyclic group formed by steroid skeleton.Therefore, can obtain The effect same with formula [1A], i.e. side chain position is improved to the stability of heat and ultraviolet, can obtain tilt angle for light and heat Also the liquid crystal orientation film stablized.

The structure represented with formula [1A] is as phenyl ring, hexamethylene ring or heterocycle.Additionally, the structure represented with formula [1B] With the cyclic group formed by steroid skeleton.In phenyl ring, hexamethylene ring or heterocycle and formula [1B] in these formulas [1A] by The cyclic group that steroid skeleton is formed is the liquid crystal aligning with the liquid crystal being added dropwise in structure as liquid crystal type, therefore ODF modes Infiltration spread on film is improved.Thus, produced when can mitigate base plate bonding to liquid crystal and the physical stress of liquid crystal orientation film. Based on these aspects, the liquid crystal aligning of the structure of the formula [1A] or formula [1B] with as specific side-chain structure of the invention It is uneven that film can mitigate the liquid crystal aligning produced in ODF modes.

The structure represented with formula [1A] in main polymer chain and formula [1A]-(CH₂)_m-X₁-(X₂)_n-(X₃)_p-X₄ Part between have alkyl.That is, hydrophobicity it is high-(CH₂)_m-X₁-(X₂)_n-(X₃)_p-X₄Part be present in and the owner that is polymerized The position that chain is separated by a certain distance.Therefore, when being made liquid crystal orientation film, should-(CH₂)_m-X₁-(X₂)_n-(X₃)_p-X₄Part it is efficient Come across orientation membrane interface, thus the hydrophobicity of liquid crystal orientation film can be improved.Thus, the water of liquid crystal aligning membrane interface can be suppressed With the absorption of impurity.Additionally ,-(CH₂)_m-X₁-(X₂)_n-(X₃)_p-X₄Part be present in and be separated by a certain distance with main polymer chain Position, therefore can efficiently come across orientation membrane interface with phenyl ring, hexamethylene ring or heterocycle as liquid crystal type.Therefore, it is above-mentioned Infiltration spread of the liquid crystal being added dropwise in ODF modes on liquid crystal orientation film is improved.

Similarly, the specific side-chain structure in the formula [1B] shows and make with the specific side-chain structure identical of formula [1A] With.

According to above-mentioned aspect, by using the liquid crystal aligning of the polymer comprising the side chain with ad hoc structure of the invention Inorganic agent, it is possible to provide even if the change of tilt angle will not also occur exposed to high temperature and illumination for a long time, in can mitigating ODF modes The uneven liquid crystal orientation film of the liquid crystal aligning of generation.Additionally, by using the liquid crystal orientation film, it is possible to provide display characteristic is good Reliability liquid crystal display cells high.

As particular polymers of the invention acid imide is carried out selected from polyimide precursor and to the polyimide precursor At least a kind of polyimides obtained by change has the specific side-chain structure represented with following formulas [1A].

[changing 10]

In formula [1A], X₁It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₁)-or-S-, R₁For The straight-chain alkyl of carbon number 1~5 or the branch-like alkyl of carbon number 1~5.Wherein, preferably singly-bound ,-O- ,-COO- ,-OCO- ,- CONH- ,-NHCO- ,-NH- or-N (R₁)-, R₁It is the straight-chain alkyl or the branch-like alkyl of carbon number 1~5 of carbon number 1~5.More preferably It is-O- ,-CONH- ,-NHCO- or-NH-.Further more preferably-O- ,-CONH- or-NHCO-.

In formula [1A], X₂The divalent cyclic group selected from phenyl ring, hexamethylene ring or heterocycle is represented, appointing on these cyclic groups The hydrogen atom of meaning can be contained containing fluoroalkyl, carbon number 1~3 by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 Fluoroalkyloxy or fluorine atom replace.At this moment, X₂Can be identical, also can be different.Wherein, X₂Preferably phenyl ring or hexamethylene ring.

In formula [1A], X₃The divalent cyclic group selected from phenyl ring, hexamethylene ring or heterocycle is represented, appointing on these cyclic groups The hydrogen atom of meaning can be contained containing fluoroalkyl, carbon number 1~3 by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 Fluoroalkyloxy or fluorine atom replace.At this moment, X₃Can be identical, also can be different.Wherein, X₃Preferably phenyl ring or hexamethylene ring.

In formula [1A], X₄For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or The fluoroalkoxy of carbon number 1~18.Wherein, preferably the alkyl of carbon number 1~18, carbon number 1~10 containing fluoroalkyl, carbon number 1~ 18 alkoxy or the fluoroalkoxy of carbon number 1~10.The more preferably alkoxy of the alkyl of carbon number 1~12 or carbon number 1~12.Enter The alkoxy of one the step more preferably alkyl of carbon number 1~10 or carbon number 1~10.

In formula [1A], m is 2~15 integer.Wherein, preferably 2~10 integer.More preferably 2~7 integer.

In formula [1A], n is 1~3 integer.Wherein, preferably 1 or 2 integer.

In formula [1A], p is 0~3 integer.Wherein, preferably 0~2 integer.

In formula [1A], n+p is 1~6 integer.Wherein, preferably 1~4 integer.

X in formula [1A]₁、X₂、X₃、X₄, m, n and p preferred compositions as shown in 1~table of table 36.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

[table 8]

[table 9]

[table 10]

[table 11]

[table 12]

[table 13]

[table 14]

[table 15]

[table 16]

[table 17]

[table 18]

[table 19]

[table 20]

[table 21]

[table 22]

[table 23]

[table 24]

[table 25]

[table 26]

[table 27]

[table 28]

[table 29]

[table 30]

[table 31]

[table 32]

[table 33]

[table 34]

[table 35]

[table 36]

Additionally, carrying out acyl selected from polyimide precursor and to the polyimide precursor as particular polymers of the invention At least a kind of polyimides obtained by imidization has the specific side-chain structure represented with following formulas [1B].

[changing 11]

In formula [1B], X₅It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₂)-or-S-, R₂For The straight-chain alkyl of carbon number 1~5 or the branch-like alkyl of carbon number 1~5.Wherein, preferably singly-bound ,-O- ,-COO- ,-OCO- ,- CONH- ,-NHCO- ,-NH- or-N (R₂)-, R₂It is the straight-chain alkyl or the branch-like alkyl of carbon number 1~5 of carbon number 1~5.More preferably It is-O- ,-CONH- ,-NHCO- or-NH-.Further more preferably-O- ,-CONH- or-NHCO-.

In formula [1B], X₆It is the organic group of the carbon number 12~25 with steroid skeleton, preferably with steroids bone The organic group of the carbon number 15~25 of frame.

In formula [1B], q is 2~15 integer.Wherein, preferably 2~10 integer.More preferably 2~7 integer.

As to particular polymers of the invention, i.e. selected from gathering that the reaction by diamine component and tetrabasic carboxylic acid composition is obtained Imide precursor and specific side-chain structure is introduced in making at least a kind of the polyimides obtained by polyimide precursor dehydration closed-loop Method, the diamine compound that will preferably be represented with following formulas [2A] (also referred to as specific side chain type diamine compound) is used as A part for raw material.

[changing 12]

In formula [2A], X₁It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₁)-or-S-, R₁For The straight-chain alkyl of carbon number 1~5 or the branch-like alkyl of carbon number 1~5.Wherein, preferably singly-bound ,-O- ,-COO- ,-OCO- ,- CONH- ,-NHCO- ,-NH- or-N (R₁)-, R₁It is the straight-chain alkyl or the branch-like alkyl of carbon number 1~5 of carbon number 1~5.More preferably It is-O- ,-CONH- ,-NHCO- or-NH-.Further more preferably-O- ,-CONH- or-NHCO-.

In formula [2A], X₂The divalent cyclic group selected from phenyl ring, hexamethylene ring or heterocycle is represented, appointing on these cyclic groups The hydrogen atom of meaning can be contained containing fluoroalkyl, carbon number 1~3 by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 Fluoroalkyloxy or fluorine atom replace.At this moment, X₂Can be identical, also can be different.Wherein, X₂Preferably phenyl ring or hexamethylene ring.

In formula [2A], X₃For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or The fluoroalkoxy of carbon number 1~18.Wherein, preferably the alkyl of carbon number 1~18, carbon number 1~10 containing fluoroalkyl, carbon number 1~ 18 alkoxy or the fluoroalkoxy of carbon number 1~10.The more preferably alkoxy of the alkyl of carbon number 1~12 or carbon number 1~12.Enter The alkoxy of one the step more preferably alkyl of carbon number 1~10 or carbon number 1~10.

In formula [2A], m is 2~15 integer.Wherein, preferably 2~10 integer.More preferably 2~7 integer.

In formula [2A], n is 1~3 integer.Wherein, preferably 1 or 2 integer.

In formula [2A], p is 0~3 integer.Wherein, preferably 0~2 integer.

In formula [2A], n+p is 1~6 integer.Wherein, preferably 1~4 integer.

2 amino (- NH in formula [2A]₂) binding site be not limited.Specifically, relative to the conjugated group of side chain (-(CH₂)_m-), 2 on phenyl ring, 3,2,4,2,5,2,6,3,4 or 3,5 can be enumerated.Wherein, from synthesis polyamides From the viewpoint of reactivity during imines precursor, preferably 2,4,2,5 or 3,5.Further consider two amine compounds of synthesis Difficulty during thing, more preferably 2,4 or 3,5.

X in formula [2A]₁、X₂、X₃, m, n and p preferred compositions it is same with formula [1A] as shown in 1~table of table 30.

The preferred structure of specific side chain type diamine compound of the invention is with following formulas [2a]~formula [2d] table The structure shown.

[changing 13]

In formula [2a], R₁For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or The fluoroalkoxy of carbon number 1~18.Wherein, preferably the alkyl of carbon number 1~18, carbon number 1~10 containing fluoroalkyl, carbon number 1~ 18 alkoxy or the fluoroalkoxy of carbon number 1~10.The more preferably alkoxy of the alkyl of carbon number 1~12 or carbon number 1~12.Enter The alkoxy of one the step more preferably alkyl of carbon number 1~9 or carbon number 1~9.

In formula [2a], m1 is 2~15 integer.Wherein, preferably 2~10 integer.More preferably 2~7 integer.

In formula [2a], p1 is 0~3 integer.Wherein, preferably 0~2 integer.

In formula [2b], R₂For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or The fluoroalkoxy of carbon number 1~18.Wherein, preferably the alkyl of carbon number 1~18, carbon number 1~10 containing fluoroalkyl, carbon number 1~ 18 alkoxy or the fluoroalkoxy of carbon number 1~10.The more preferably alkoxy of the alkyl of carbon number 1~12 or carbon number 1~12.Enter The alkoxy of one the step more preferably alkyl of carbon number 1~10 or carbon number 1~10.

In formula [2b], m2 is 2~15 integer.Wherein, preferably 2~10 integer.More preferably 2~7 integer.

In formula [2b], p2 is 0~3 integer.Wherein, preferably 0~2 integer.

In formula [2c], R₃For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or The fluoroalkoxy of carbon number 1~18.Wherein, preferably the alkyl of carbon number 1~18, carbon number 1~10 containing fluoroalkyl, carbon number 1~ 18 alkoxy or the fluoroalkoxy of carbon number 1~10.The more preferably alkoxy of the alkyl of carbon number 1~12 or carbon number 1~12.Enter The alkoxy of one the step more preferably alkyl of carbon number 1~10 or carbon number 1~10.

In formula [2c], m3 is 2~15 integer.Wherein, preferably 2~10 integer.More preferably 2~7 integer.

In formula [2c], n1 is 1~3 integer.Wherein, preferably 1 or 2 integer.

In formula [2c], p3 is 0~3 integer.Wherein, preferably 0~2 integer.

In formula [2c], n1+p3 is 1~6 integer.Wherein, preferably 1~4 integer.

In formula [2d], R₄For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or The fluoroalkoxy of carbon number 1~18.Wherein, preferably the alkyl of carbon number 1~18, carbon number 1~10 containing fluoroalkyl, carbon number 1~ 18 alkoxy or the fluoroalkoxy of carbon number 1~10.The more preferably alkoxy of the alkyl of carbon number 1~12 or carbon number 1~12.Enter The alkoxy of one the step more preferably alkyl of carbon number 1~10 or carbon number 1~10.

In formula [2d], m4 is 2~15 integer.Wherein, preferably 2~10 integer.More preferably 2~7 integer.

In formula [2d], n2 is 1~3 integer.Wherein, preferably 1 or 2 integer.

In formula [2d], p4 is 0~3 integer.Wherein, preferably 0~2 integer.

In formula [2d], n2+p4 is 1~6 integer.Wherein, preferably 1~4 integer.

2 amino (- NH in formula [2a]~formula [2d]₂) binding site be not limited.Specifically, relative to side chain Conjugated group (- (CH₂)_M1~m4-), 2 on phenyl ring, 3,2,4,2,5,2,6,3,4 or 3,5 can be enumerated.Wherein, From synthesis of polyimides precursor when reactivity from the viewpoint of, preferably 2,4,2,5 or 3,5.Further consider to close Into difficulty during diamine compound, more preferably 2,4 or 3,5.

The structure for more specifically for example being represented with following formulas [2-1]~formula [2-40].

[changing 14]

[changing 15]

[changing 16]

[changing 17]

[changing 18]

[changing 19]

[changing 20]

[changing 21]

[changing 22]

[changing 23]

[changing 24]

In formula [2-1]~formula [2-40], R₅It is each independently the alkyl of carbon number 1~10 or the alkoxy of carbon number 1~10, m₅ It is each independently 2~7 integer.

In above-mentioned specific example, preferably [2-1]~[2-5], [2-8], [2-11], [2-12], formula [2-14], [2- 15], [2-17]~[2-20], [2-25], [2-26], [2-29], [2-30], more preferably [2-1]~[2-5], [2-8], [2- 11], [2-12], [2-14], [2-15], [2-17]~[2-20].

For particular polymers of the invention, the diamine compound that will can be also represented with following formulas [2B] (with it is above-mentioned with The diamine compound that formula [2A] is represented is same, also referred to as specific side chain type diamine compound) it is used as a part for raw material.

[changing 25]

In formula [2B], X₅It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₂)-or-S-, R₂For The straight-chain alkyl of carbon number 1~5 or the branch-like alkyl of carbon number 1~5.Wherein, preferably singly-bound ,-O- ,-COO- ,-OCO- ,- CONH- ,-NHCO- ,-NH- or-N (R₂)-, R₂It is the straight-chain alkyl or the branch-like alkyl of carbon number 1~5 of carbon number 1~5.More preferably It is-O- ,-CONH- ,-NHCO- or-NH-.Further more preferably-O- ,-CONH- or-NHCO-.

In formula [2B], X₆It is the organic group of the carbon number 12~25 with steroid skeleton, preferably with steroids bone The organic group of the carbon number 15~25 of frame.

In formula [2B], q is 2~15 integer.Wherein, preferably 2~10 integer.More preferably 2~7 integer.

The method of the manufacture specific side chain type diamine compound represented with formula [2A] or formula [2B] of the invention is without especially limit It is fixed, can for example be manufactured by following methods.

For example, the specific diamine compound represented with formula [2A] of the invention can be by synthesizing represented with formula [2- I] two Nitro is reduced after nitro-body and be converted into amino and obtain.The method that dinitro compound is reduced is not particularly limited, is generally had Using palladium carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminum oxide, vulcanization platinum carbon etc. as catalyst in ethyl acetate, toluene, four Hydrogen furans, twoThe method carried out by hydrogen, hydrazine, hydrogen chloride etc. in alkane, alcohols equal solvent.X in formula [2- I]₁、X₂、X₃、 X₄, m, n and p definition it is identical with the definition of formula [2A].

[changing 26]

The dinitro matrix of formula [2- I] can by make dinitro matrix-(CH₂)_m- part is situated between with coupling part X₁With-(X₂)_n- (X₃)_p-X₄With reference to method etc. obtain.

X₁Be selected from singly-bound ,-O- (ehter bond) ,-COO- (ester bond) ,-OCO- (anti-ester bond) ,-CONH- (amido link) ,- NHCO- (anti-amido link) ,-NH- (amine key) ,-N (R₁)-(R₁It is the straight-chain alkyl or the branch-like of carbon number 1~5 of carbon number 1~5 The alkylation amine key of alkyl) or-S- (S keys) linking group, these linking groups can suitably select to use public in organic synthesis The method known is formed.

[changing 27]

For example, X₁In the case of for-O- (ehter bond), can enumerate makes the Xa in formula [2- II] be the halogen containing dinitro of halogen The method that Xb in plain derivative and formula [2- III] reacts in the presence of base for the hydroxy derivatives of hydroxyl (OH yls).It is described to contain The halogen of the halogen derivatives of dinitro is preferably Cl (chlorine) or Br (bromine).Additionally, the halogen derivatives containing dinitro can pass through The halogenation of corresponding dinitro benzylalcohol is obtained.As halogenating agent at this moment used, BBr can be enumerated₃、BCl₃、PBr₃、PCl₃、PPh₃/ CBr₄、PPh₃/CCl₄、SOBr₂、SOCl₂Deng.

X₁In the case of for-COO- (ester bond), can enumerate makes the Xa in formula [2- II] be the acyl chlorides containing dinitro of acyl chlorides The method that Xb in derivative and formula [2- III] reacts in the presence of base for the hydroxy derivatives of hydroxyl (OH yls).

X₁In the case of for-OCO- (anti-ester bond), can enumerate makes Xa in formula [2- II] be hydroxyl (OH yls) containing dinitro The method that Xb in the hydroxy derivatives and formula [2- III] of base reacts in the presence of base for the chloride derivative of acyl chlorides.

X₁In the case of for-CONH- (amido link), can enumerate makes the Xa in formula [2- II] be the acyl containing dinitro of acyl chlorides Chlorine derivative is amino (NH with the Xb in formula [2- III]₂Base) the method reacted in the presence of base of aminoderivative.

X₁In the case of for-NHCO- (anti-amido link), can enumerate makes the Xa in formula [2- II] be amino (NH₂Base) containing two The method that Xb in the aminoderivative and formula [2- III] of nitro reacts in the presence of base for the chloride derivative of acyl chlorides.

X₁It is-NH- (amine key) or N (R₁)-(alkylation amine key) in the case of, can enumerate makes the Xa in formula [2- II] be halogen The halogen derivatives containing dinitro of element and the Xb in formula [2- III] are amino (NH₂Base) or alkylated amine (NH (R₁) base) The method that amino or alkylated amine derivative react in the presence of base.

In the above-mentioned specific side chain type diamine compound represented with formula [2A], also including new compound.

In the present invention, as long as not destroying effect of the invention, other beyond specific side chain type diamine compound can be used Diamine compound (also referred to as other diamine compounds) is used as diamine component.Its specific example is enumerated below：

P-phenylenediamine, 2,3,5,6- tetramethyl-para-phenylene diamines, 2,5- dimethyl-p-phenylenediamines, isophthalic two can specifically be enumerated Amine, 2,4- dimethyl-m-phenylenediamines, 2,5- diaminotoluenes, 2,6- diaminotoluenes, 2,5- diaminophenols, 2,4- diaminourea Phenol, 3,5- diaminophenols, 3,5- diaminourea benzylalcohol, 2,4- diaminourea benzylalcohol, 4,6- diamino resorcins, 4,4'- bis- Aminobphenyl, 3,3'- dimethyl -4,4'- benzidines, 3,3'- dimethoxy-4 's, 4'- benzidines, 3,3'- dihydroxies Base -4,4'- benzidines, 3,3'- dicarboxyl -4,4'- benzidines, the fluoro- 4,4'- benzidines of 3,3'- bis-, 3, 3'- trifluoromethyl -4,4'- benzidines, 3,4'- benzidines, 3,3'- benzidines, 2,2'- benzidines, 2,3'- benzidines, 4,4'- diaminodiphenyl-methanes, 3,3'- diaminodiphenyl-methanes, 3,4'- diamino-diphenyls Methane, 2,2'- diaminodiphenyl-methanes, 2,3'- diaminodiphenyl-methanes, 4,4'- diamino-diphenyls ether, 3,3'- bis- ADP base ether, 3,4'- diamino-diphenyls ether, 2,2'- diamino-diphenyls ether, 2,3'- diamino-diphenyls ether, 4, 4'- sulfonyldianilines, 3,3'- sulfonyldianilines, double (4- aminophenyls) silane, double (3- aminophenyls) silane, diformazan Base-bis- (4- aminophenyls) silane, dimethyl-bis- (3- aminophenyls) silane, 4,4'- diamino diphenyl sulfides, 3,3'- bis- ADP base thioether, 4,4'- diamino-diphenyls amine, 3,3'- diamino-diphenyls amine, 3,4'- diamino-diphenyls amine, 2, 2'- diamino-diphenyls amine, 2,3'- diamino-diphenyls amine, N- methyl (4,4'- diamino-diphenyls) amine, N- methyl (3, 3'- diamino-diphenyls) amine, N- methyl (3,4'- diamino-diphenyls) amine, N- methyl (2,2'- diamino-diphenyls) amine, N- Methyl (2,3'- diamino-diphenyls) amine, 4,4'- diaminourea benzophenone, 3,3'- diaminourea benzophenone, 3,4'- diaminourea hexichol Ketone, 1,4- diaminonaphthalenes, 2,2'- diaminourea benzophenone, 2,3'- diaminourea benzophenone, 1,5- diaminonaphthalenes, 1,6- diaminourea Naphthalene, 1,7- diaminonaphthalenes, 1,8- diaminonaphthalenes, 2,5- diaminonaphthalenes, 2,6- diaminonaphthalenes, 2,7- diaminonaphthalenes, 2,8- diaminos Double (4- aminophenyls) ethane of base naphthalene, 1,2-, double (3- aminophenyls) ethane of 1,2-, 1,3- double (4- aminophenyls) propane, 1, Double (3- aminophenyls) propane of 3-, double (4- aminophenyls) butane of 1,4-, 1,4- double (3- aminophenyls) butane, double (3,5- bis- Ethyl -4- aminophenyls) methane, double (4- amino-benzene oxygens) benzene of 1,4-, double (4- amino-benzene oxygens) benzene of 1,3-, the double (4- of 1,4- Aminophenyl) benzene, double (4- aminophenyls) benzene of 1,3-, double (4- aminobenzyls) benzene of 1,4-, double (4- amino-benzene oxygens) benzene of 1,3-, 4,4'- [1,4- phenylenes double (methylene)] diphenylamines, 4,4'- [1,3- phenylenes are double (methylene)] diphenylamines, 3,4'- [1, 4- phenylenes are double (methylene)] diphenylamines, 3,4'- [1,3- phenylenes are double (methylene)] diphenylamines, 3,3'- [1,4- phenylenes Double (methylene)] diphenylamines, 3,3'- [1,3- phenylenes double (methylene)] diphenylamines, 1,4- phenylenes be double [(4- aminophenyls) Ketone], 1,4- phenylenes double [(3- aminophenyls) ketone], 1,3- phenylenes double [(4- aminophenyls) ketones], 1,3- Asias benzene Base double [(3- aminophenyls) ketones], 1,4- phenylenes double (PABA esters), double (the 3- aminobenzoic acids of 1,4- phenylenes Ester), 1,3- phenylenes double (PABA ester), 1,3- phenylenes double (3- Aminobenzoates), double (4- aminophenyls) Phthalic acid ester, double (3- aminophenyls) phthalic acid esters, double (4- aminophenyls) isophthalic acid esters, double (3- amino Phenyl) isophthalic acid ester, N, N'- (1,4- phenylenes) double (4- aminobenzamides), N, N'- (1,3- phenylenes) double (4- Aminobenzamide), N, N'- (1,4- phenylenes) double (3-ABs), N, N'- (1,3- phenylenes) double (3- amino Benzamide), N, N'- double (4- aminophenyls) phthalic amide, N, N'- double (3- aminophenyls) phthalic amide, N, N'- double (4- aminophenyls) isophtalamide, N, double (3- aminophenyls) isophtalamides of N'-, double (the 4- amino of 9,10- Phenyl) anthracene, double (4- amino-benzene oxygens) diphenyl sulfones of 4,4'-, 2,2'- double [4- (4- amino-benzene oxygens) phenyl] propane, 2,2'- Double (4- aminophenyls) HFC-236fas of double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas, 2,2'-, double (the 3- aminobenzenes of 2,2'- Base) HFC-236fa, double (3- amino -4- aminomethyl phenyls) HFC-236fas of 2,2'-, 2,2'- double (4- aminophenyls) propane, 2,2'- Double (3- aminophenyls) propane, 2,2'- double (3- amino -4- aminomethyl phenyls) propane, 3,5- diaminobenzoic acids, 2,5- diaminourea Double (4- amino-benzene oxygens) propane of benzoic acid, 1,3-, double (3- amino-benzene oxygens) propane of 1,3-, 1,4- are double (4- amino-benzene oxygens) Double (3- amino-benzene oxygens) butane of butane, 1,4-, double (4- amino-benzene oxygens) pentanes of 1,5-, double (the 3- amino-benzene oxygens) penta of 1,5- Double (4- amino-benzene oxygens) hexanes of alkane, 1,6-, double (3- amino-benzene oxygens) hexanes of 1,6-, 1,7- pairs of (4- amino-benzene oxygens) heptan Double (3- amino-benzene oxygens) heptane of alkane, 1,7-, double (4- amino-benzene oxygens) octanes of 1,8-, 1,8- double (3- amino-benzene oxygens) are pungent Double (3- amino-benzene oxygens) nonanes of double (4- amino-benzene oxygens) nonanes of alkane, 1,9-, 1,9-, 1,10- (4- amino-benzene oxygens) decane, 1,10- (3- amino-benzene oxygens) decane, 1,11- (4- amino-benzene oxygens) hendecane, 1,11- (3- amino-benzene oxygens) hendecane, 1,12- (4- amino-benzene oxygens) dodecane, 1,12- (3- amino-benzene oxygens) dodecane, 4- (amino methyl) aniline, 3- (amino Methyl) aromatic diamine, double (4- aminocyclohexyls) such as aniline, 4- (2- amino-ethyls) aniline or 3- (2- amino-ethyls) aniline The alicyclic diamines such as methane, double (4- amino -3- methylcyclohexyls) methane, 1,3- diaminopropanes, 1,4-Diaminobutane, 1, 5- 1,5-DAPs, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diamino nonanes, 1, The aliphatic diamines such as 10- diamino decanes, 1,11- diamino undecanes, 1,12- diamino dodecanes.

Additionally, not destroying in the range of effect of the invention, can be used with following formulas [DA-1]~formula [DA-31] table The diamine compound for showing.

[changing 28]

In formula [DA-1]~formula [DA-3], R₁It is-O- ,-OCH₂-、-CH₂O-、-COOCH₂- or-CH₂OCO-, R₂It is carbon number 1 ~22 straight-chain or branch-like alkyl, the straight-chain of carbon number 1~22 or branch-like alkoxy, the straight-chain of carbon number 1~22 or Straight-chain or branch-like fluoroalkoxy of the branch-like containing fluoroalkyl or carbon number 1~22.

[changing 29]

In formula [DA-4]~formula [DA-6], R₃It is-COO- ,-OCO- ,-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂- or- CH₂-, R₄For the straight-chain or branch-like alkyl of carbon number 1~22, the straight-chain of carbon number 1~22 or branch-like alkoxy, carbon number 1~ Straight-chain or branch-like fluoroalkoxy of 22 straight-chain or branch-like containing fluoroalkyl or carbon number 1~22.

[changing 30]

In formula [DA-7] and formula [DA-8], R₅Represent-COO- ,-OCO- ,-COOCH₂-、-CH₂OCO-、-CH₂O-、- OCH₂-、-CH₂- or-O-, R₆Represent fluorine-based, cyano group, trifluoromethyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or Hydroxyl.

[changing 31]

In formula [DA-9] and formula [DA-10], R₇It is the straight-chain or branch-like alkyl of carbon number 3~12, for Isosorbide-5-Nitrae-Asia ring The cis-trans isomerization of hexyl, respectively transisomer.

[changing 32]

In formula [DA-11] and formula [DA-12], R₈It is the straight-chain or branch-like alkyl of carbon number 3~12, for Isosorbide-5-Nitrae-Asia ring The cis-trans isomerization of hexyl, respectively transisomer.

[changing 33]

In formula [DA-13], A₄It is the straight-chain or branch-like alkyl of carbon number 3~20 that can be replaced by fluorine atoms, A₃It is 1,4- Cyclohexylidene or Isosorbide-5-Nitrae-phenylene, A₂It is-O- or-COO-* (the wherein key and A of band " * "₃With reference to), A₁It is-O- or-COO-* (its The key of middle band " * " and (CH₂)a₂With reference to).Additionally, a₁It is 0 or 1 integer, a₂It is 2~10 integer, a₃It is 0 or 1 integer.

[changing 34]

[changing 35]

[changing 36]

[changing 37]

[changing 38]

In addition, not destroying in the range of effect of the invention, two aminations represented with following formulas [DA-32] can be used Compound.

[changing 39]

In formula [DA-32], A₁It is selected from-O- ,-NH- ,-N (CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCO-、-CON (CH₃)-or-N (CH₃) CO- divalent organic group, A₂It is singly-bound, the aliphatic alkyl of carbon number 1~20, non-aromatic ring type hydrocarbon Base or aromatic hydrocarbyl.A₃It is singly-bound ,-O- ,-NH- ,-N (CH₃)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON (CH₃)-、-N(CH₃) CO- or-O (CH₂)_m-, m is 1~5 integer, A₄It is nitrogenous heteroaromatic.N is 1~4 integer.

As long as additionally, not destroying effect of the invention, can be used has alkyl or the diamines containing fluoroalkyl on two amine side chains Compound.

Specifically can the diamines that is represented with following formulas [DA-33]~formula [DA-44] of example.

[changing 40]

In formula [DA-33]~formula [DA-37], A₁For carbon number 1~22 straight-chain or branch-like alkyl or carbon number 1~ 22 straight-chain or branch-like contains fluoroalkyl.

[changing 41]

In formula [DA-38]~formula [DA-43], A₂It is-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂- ,-O- ,-CO- or- NH-, A₃It is that the straight-chain or branch-like alkyl of carbon number 1~22 or the straight-chain or branch-like of carbon number 1~22 contain fluoroalkyl.

[changing 42]

In formula [DA-44], p is 1~10 integer.

In addition, not destroying in the range of effect of the invention, it is possible to use with following formula [DA-45]~formula [DA- 52] diamine compound for representing.

[changing 43]

In formula [DA-49], m is 0~3 integer.In formula [DA-52], n is 1~5 integer.

In addition, not destroying in the range of effect of the invention, it is possible to use with following formula [DA-53]~formula [DA- 57] intramolecular for representing has the diamine compound of carboxyl.

[changing 44]

In formula [DA-53], m₁It is 1~4 integer.In formula [DA-54], A₄It is singly-bound ,-CH₂-、-C₂H₄-、-C (CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、- COO-、-OCO-、-CON(CH₃)-or-N (CH₃) CO-, m₂And m₃Separately for 0~4 integer, and m₂+m₃It is 1~4 Integer.In formula [DA-55], m₂And m₃It is separately 1~5 integer.In formula [DA-56], A₄It is the straight-chain of carbon number 1~5 Or branch-like alkyl, m₆It is 1~5 integer.In formula [DA-57], A₆It is singly-bound ,-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C (CF₃)₂-、-O-、-CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON (CH₃)-or-N (CH₃) CO-, m₇It is 1~4 integer.

In addition, not destroying in the range of effect of the invention, it is possible to use with following formulas [DA-58] and formula [DA- 59] diamine compound for representing.

[changing 45]

Other above-mentioned diamine compounds can be according to liquid crystal aligning, voltage retention, the product when being made liquid crystal orientation film The characteristics such as poly- electric charge are using a kind or are mixed with two or more.

In order to obtain particular polymers of the invention, the tetracarboxylic dianhydride that will preferably be represented with following formulas [3] is (also referred to as It is specific tetracarboxylic dianhydride) it is used as a part for raw material.

[changing 46]

Z₁The 4 valency groups for specially for example being represented with following formula [3a]~[3j].

[changing 47]

In formula [3a], Z₂~Z₅It is the group selected from hydrogen atom, methyl, chlorine atom or phenyl ring, may be the same or different respectively.

In formula [3g], Z₆And Z₇It is hydrogen atom or methyl, may be the same or different respectively.

In formula [3], according to polymerisation reactivity and the difficulty of synthesis, Z₁Particularly preferred structure be formula [3a], formula [3c], formula [3d], formula [3e], formula [3f] or formula [3g].Wherein, preferably formula [3a], formula [3e], formula [3f] or formula [3g].

In the present invention, do not destroying in the range of effect of the invention, its in addition to specific tetracarboxylic dianhydride is can be used Its tetracarboxylic dianhydride (also referred to as other tetracarboxylic dianhydrides).As other tetracarboxylic dianhydrides, tetrabasic carboxylic acid as shown below can be enumerated Tetracarboxylic dianhydride：

PMA, 2,3,6,7- naphthalenetetracarbacidic acidics, 1,2,5,6- naphthalenetetracarbacidic acidics, 1,4,5,8 naphthalenetetracarboxylic acid, 2,3,6,7- Anthracene tetracarboxylic acid, 1,2,5,6- anthracenes tetracarboxylic acid, 3,3', 4,4'- bibenzene tetracarboxylics, 2,3,3', 4- bibenzene tetracarboxylics, double (3,4- bis- Carboxyl phenyl) ether, 3,3', 4,4'- benzophenone tetracarboxylics, double (3,4- dicarboxyphenyis) sulfones, double (3,4- dicarboxyphenyis) first It is double (3,4- dicarboxyphenyis) propane of double (3,4- dicarboxyphenyis) propane of alkane, 2,2-, 1,1,1,3,3,3- hexafluoros -2,2-, double (3,4- dicarboxyphenyis) dimethylsilane, double (3,4- dicarboxyphenyis) diphenyl silanes, 2,3,4,5- pyridines tetracarboxylic acid, 2, 6- double (3,4- dicarboxyphenyis) pyridine, 3,3', 4,4'- diphenyl sulfones tetracarboxylic acid, 3,4,9,10- perylenes tetracarboxylic acid, 1,3- hexichol Base -1,2,3,4- cyclobutanetetracarboxylics.

Above-mentioned specific tetracarboxylic dianhydride and other tetracarboxylic dianhydrides can be according to liquid crystal alignings when being made liquid crystal orientation film Characteristic is using a kind or is mixed with two or more for property, voltage retention and Accumulating charge etc..

Particular polymers of the invention be selected from make diamine component and tetrabasic carboxylic acid composition react obtained by polyamic acid and make At least a kind polymer of the polyimides obtained by polyamic acid dehydration closed-loop.

Polyimide precursor is the structure represented with following formulas [A].

[changing 48]

In formula [A], R₁It is 4 valency organic groups, R₂It is divalent organic group, A₁And A₂It is hydrogen atom or the alkane of carbon number 1~8 Base, can be identical or different respectively.N represents positive integer.

Because by by the diamine component represented with following formulas [B] and the tetracarboxylic dianhydride that is represented with following formulas [C] Can more easily be obtained as raw material, therefore particular polymers of the invention are preferably the repetition by being represented with following formulas [D] Polyamic acid or make the polyimides obtained by polyamic acid imidizate that the structural formula of unit is formed.

[changing 49]

In formula [B], formula [C] and formula [D], R₁And R₂It is identical with the definition in formula [A].

In formula [A] and formula [D], R₁And R₂Can be respectively a kind, or there is different R respectively₁And R₂, it is single as repeating Unit's combination is different various.

In the present invention, the method for synthesizing particular polymers is not particularly limited.Generally, make diamine component anti-with tetrabasic carboxylic acid composition Answer and obtain.Typically make at least one tetrabasic carboxylic acid composition selected from tetrabasic carboxylic acid and its derivative and include one or more two aminations The diamine component reaction of compound, obtains polyamic acid.Specifically, tetracarboxylic dianhydride is made to be obtained with diamine component polycondensation Obtain the method for polyamic acid, tetrabasic carboxylic acid and diamine component is carried out dehydrating polycondensation reaction and is obtained the method for polyamic acid or make The carboxylic acid halides of tetrabasic carboxylic acid two and diamine component polycondensation and the method that obtains polyamic acid.

In order to obtain polyamic acid Arrcostab, the tetrabasic carboxylic acid for being esterified carboxyl dialkyl group is set to be contracted with diamine component Poly- method, make the method for the carboxylic acid halides of tetrabasic carboxylic acid two for being esterified carboxyl dialkyl group and diamine component polycondensation or by polyamic acid Converting carboxylate groups for ester method.

In order to obtain polyimides, make above-mentioned polyamic acid or polyamic acid Arrcostab closed loop and form polyamides The method of imines.

It is described with formula [1A] in above-mentioned diamine component using in the liquid crystal orientation film that particular polymers of the invention are obtained Or the content ratio of the specific side-chain structure of formula [1B] expression is higher, then hydrophobicity and liquid crystal when can make to be made liquid crystal orientation film Tilt angle it is higher.At this moment, diamine component is preferably the specific side chain type diamine represented with formula [2A] or formula [2B] described in Compound.Particularly preferably use the specific side chain type diamine compound represented with formula [2A].In order to improve the characteristic, preferably two 5 moles of more than %, 80 moles of below % of amine component are specific side chain type diamine compound.Wherein, from aligning agent for liquid crystal Coating and as the electrical characteristics of liquid crystal orientation film from the viewpoint of, preferably 5 moles of more than %, 60 moles of % of diamine component It is below specific side chain type diamine compound.

In order to obtain particular polymers of the invention, preferably tetrabasic carboxylic acid composition using it is described with formula [3] represent it is specific Tetracarboxylic dianhydride.The use of the Z1 in formula [3] is particularly preferably the tetrabasic carboxylic acid two of the structure represented with formula [3a]~formula [3j] Acid anhydride.At this moment, 1 mole of more than % of preferably tetrabasic carboxylic acid composition is specific tetracarboxylic dianhydride, more preferably 5 moles more than %, enters one More preferably 10 moles more than % of step.Furthermore, it is possible to 100 moles of % for making tetrabasic carboxylic acid composition are specific tetracarboxylic dianhydride.

Diamine component is generally carried out in organic solvent with the reaction of tetrabasic carboxylic acid composition.It is organic molten as what is at this moment used Agent, as long as the polyimide precursor of generation can be dissolved, is not particularly limited.Its specific example is enumerated below：

For example, DMF, DMA, METHYLPYRROLIDONE, dimethyl sulfoxide, γ- Butyrolactone, 1,3- dimethyl-imidazolinones, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4- hydroxy-4-methyl-2-pentanones etc..

They can be used alone, it is also possible to be used in mixed way.Even in addition, the molten of polyimide precursor dissolving cannot be made Agent, in the range of the polyimide precursor of generation will not be separated out, can mix into above-mentioned solvent and use.Additionally, organic solvent In moisture hinder polymerisation, also result in generation polyimide precursor hydrolysis, so organic solvent be preferably using enter The solvent gone after dehydrating.

When diamine component and tetrabasic carboxylic acid composition is reacted in organic solvent, following method can be enumerated：Stirring make diamines into It is dispersed or dissolved in solution obtained by organic solvent, by tetrabasic carboxylic acid composition directly or to be dispersed or dissolved in organic solvent laggard The method of row addition；Conversely, adding diamine component to making tetrabasic carboxylic acid composition be dispersed or dissolved in solution obtained by organic solvent Method；Method that tetrabasic carboxylic acid composition and diamine component are alternately added etc..Any one method therein can be used.In addition, In the case that diamine component or tetrabasic carboxylic acid composition use various reaction respectively, its can be made anti-in the state of being pre-mixed Should, it is also possible to it is reacted successively respectively, can also make to react respectively obtained by low-molecular weight hybrid reaction and obtain specific Polymer.At this moment polymerization temperature can select -20~150 DEG C of arbitrary temp, preferably in the range of -5~100 DEG C. Additionally, reaction can be carried out under arbitrary concentration, but if concentration is too low, then it is difficult to obtain the particular polymers of HMW, If excessive concentration, reaction solution sticky too high and be difficult to stir.Therefore, preferably 1~50 mass %, more preferably 5 ~30 mass %.Can in higher concentrations be carried out with initial reaction stage, then add organic solvent.

In the polymerisation of polyimide precursor, the ratio of the total mole number of diamine component and the total mole number of tetrabasic carboxylic acid composition Value preferably 0.8~1.2.Identical with common polycondensation reaction, the mol ratio is closer to 1.0, the polyimide precursor of generation Molecular weight it is bigger.

Polyimides of the invention be make above-mentioned polyimide precursor closed loop obtained by polyimides, can be used as obtaining Obtain the polymer of liquid crystal orientation film.

In polyimides of the invention, the closed loop rate (acid imide rate) of acid amides acidic group is not necessary for 100%, can be with root Arbitrarily it is adjusted according to purposes or purpose.

Method as polyimide precursor imidizate is made, can enumerate the solution of polyimide precursor is direct-fired Hot-imide or the catalyst acid imide to addition catalyst in the solution of polyimide precursor.

Make polyimide precursor in the solution hot-imide when temperature for 100~400 DEG C, preferably 120~250 DEG C, preferably carried out while the water that will be generated by imidization reaction is expelled to outside system.

The catalysis imidizate of polyimide precursor can be by adding base catalysis in the solution of polyimide precursor Agent and acid anhydrides, at -20~250 DEG C, stir and carry out preferably at 0~180 DEG C.The amount of base catalyst is in mol acid amides 0.5~30 times of acidic group, preferably 2~20 times, the amount of acid anhydrides is in mol 1~50 times of acid amides acidic group, preferably 3~30 Times.As base catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated, wherein pyridine has makes reaction The appropriate alkalescence for carrying out, therefore preferably.As acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, its In, it is easy to carry out reacting the purifying after terminating during using acetic anhydride, therefore preferably.Using the acid imide rate of catalysis imidizate Can be controlled by adjusting catalytic amount and reaction temperature, reaction time.

The polyimide precursor or polyimides of generation are reclaimed from the reaction solution of polyimide precursor or polyimides When, precipitate it during reaction solution is put into solvent.As the solvent for precipitating, methyl alcohol, ethanol, isopropyl can be enumerated Alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, benzene, water etc..Put into solvent In and the polymer that precipitates can be dried in normal temperature or heating under normal or reduced pressure after being recovered by filtration.In addition, If the polymer for repeating to reclaim precipitation is redissolved in the operation 2~10 times that organic solvent and reprecipitation reclaim, can be with Reduce the impurity in polymer.As solvent now, such as alcohols, ketone, hydro carbons etc. can be enumerated, if using selected from these The solvent of more than 3 kinds of solvent, then purification efficiency is further improved, therefore ideal.

In view of the polymer obtained by it by film strength, form polymer envelope when operability, polymer envelope Uniformity in the case of, the molecular weight of particular polymers of the invention is with by GPC (gel permeation chromatography, Gel Permeation Chromatography) method determine weight average molecular weight meter be preferably 5000~1000000, more preferably 10000 ~150000.

Aligning agent for liquid crystal of the invention is the coating fluid for forming liquid crystal orientation film, is for being formed comprising specific The coating fluid of the resin coating of polymer and organic solvent.

It is specific poly- that all component of polymer in aligning agent for liquid crystal of the invention can be used in all present invention Compound, can also be mixed with other polymer in addition in particular polymers of the invention.At this moment, in addition other The content of polymer is 0.5~15 mass %, preferably 1~10 mass %.As other polymer in addition, can enumerate Polyimide precursor or polyimides without specific side-chain structure.In addition, can also enumerate except polyimide precursor and polyamides are sub- Polymer beyond amine, specially acrylate copolymer, methacrylate polymer, polystyrene, polyamide etc..

From from the viewpoint of uniform envelope is formed by coating, organic solvent in aligning agent for liquid crystal of the invention Content is preferably 70~99 mass %, more preferably 80~99 mass %.Its content can be according to the target film thickness of liquid crystal orientation film And suitably change.As organic solvent at this moment, as long as the organic solvent that particular polymers dissolve can be made, without especially limit It is fixed.Its specific example is enumerated below：

For example, DMF, DMA, METHYLPYRROLIDONE, dimethyl sulfoxide, γ- Butyrolactone, 1,3- dimethyl-imidazolinones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4- hydroxy-4-methyl-2-pentanones etc..

They can be used alone, it is also possible to be used in mixed way.

In aligning agent for liquid crystal of the invention, do not destroying in the range of effect of the invention, can also import with ring Epoxide, NCO, oxetanyl, the cross-linked compound of cyclic carbonate group, with selected from hydroxyl, hydroxyalkyl and At least a kind cross-linked compound of substitution base of low-grade alkoxy alkyl, the cross-linked compound with polymerism unsaturated bond Deng.These substitution bases and polymerism unsaturated bond must have more than 2 in cross-linked compound.

As the cross-linked compound with epoxy radicals, NCO etc., such as bisphenol acetone glycidol can be enumerated Base ether, phenol novolac epoxy resins, cresol novolac epoxy, triglycidyl group isocyanuric acid ester, four are shunk Glyceryl amino connection stretches double (amino-ethyl) hexamethylenes of benzene, four glycidyl group m-xylene diamine, four glycidyl group -1,3- Alkane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl group diglycidyl Double (1- (2,3- the glycidoxies) -1- trifluoromethyl -2,2,2- trifluoromethyls) benzene of ether, 1,3-, the double (oxygen of 2,3- epoxies third of 4,4- Base) octafluorobiphenyl, triglycidyl group para-aminophenol, four glycidyl group m-xylene diamine, 2- (4- (2,3- epoxies third Epoxide) phenyl) -2- (4- (1,1- double (4- (2,3- glycidoxies) phenyl) ethyls) phenyl) propane, the double (4- (1- (4- of 1,3- (2,3- glycidoxies) phenyl) -1- (4- (1- (4- (2,3- glycidoxies) phenyl) -1- Methylethyls) phenyl) ethyl) Phenoxy group) -2- propyl alcohol etc..

It is that there are at least 2 oxygen represented with following formulas [4] as the cross-linked compound with oxetanyl The cross-linked compound of azetidinyl.

[changing 50]

The cross-linked compound for specially being represented with following formulas [4-1]~formula [4-11].

[changing 51]

[changing 52]

[changing 53]

It is that there are at least 2 rings represented with following formulas [5] as the cross-linked compound with cyclic carbonate group The cross-linked compound of shape carbonate group.

[changing 54]

The cross-linked compound for specially being represented with following formulas [5-1]~formula [5-37].

[changing 55]

[changing 56]

[changing 57]

[changing 58]

[changing 59]

[changing 60]

[changing 61]

[changing 62]

In formula [5-24], n is 1~5 integer.In formula [5-25], n is 1~5 integer.In formula [5-36], n be 1~ 100 integer.In formula [5-37], n is 1~10 integer.

In addition, can also enumerate with least a kind poly- silica of structure represented with following formulas [5-38]~formula [5-40] Alkane.

[changing 63]

In formula [5-38]~formula [5-40], R₁、R₂、R₃、R₄And R₅It is separately structure, the hydrogen original represented with formula [5] Son, hydroxyl, the alkyl of carbon number 1~10, alkoxy, aliphatic ring or aromatic ring, at least one are the structure represented with formula [5].

More particularly, the compound of following formula [5-41] and formula [5-42] can be enumerated.

[changing 64]

In formula [5-42], n is 1~10 integer.

Used as with least a kind cross-linked compound of substitution base selected from hydroxyl and alkoxy, can enumerate for example has The amino resins of hydroxyl or alkoxy, such as melmac, urea resin, guanamine resin, glycolurilformaldehyde resins, amber Amide-formaldehyde resin, ethene urea-formaldehyde resins etc..Specifically, the hydrogen atom of amino can be used by methylol and/or alcoxyl Melamine derivative, benzoguanamine derivative, glycoluril of ylmethyl substitution etc..The melamine derivative or benzene generation three Paracyanogen amine derivative can also the form of dimer or tripolymer exist.These compounds are preferably that every 1 triazine ring averagely has There are the methylol or alkoxy methyl of less than more than 36.

As such melamine derivative or the example of benzoguanamine derivative, can enumerate as commercially available product Every 1 triazine ring averagely has the MX-750 of 3.7 methoxies substitution, every 1 triazine ring averagely to have 5.8 methoxies Substituted MW-30 (being above Sanwa Chemical Co., Ltd (three and ケミカ Le society) system), Cymel 300,301,303,350, 370th, the methoxymethylated melamines such as 771,325,327,703,712, Cymel 235,236,238,212,253,254 etc. Butoxymethyl melamine, the Cymel such as methoxymethylated butoxymethyl melamine, Cymel 506,508 The methoxymethylated ethoxies such as the carboxylic methoxymethylated isobutoxymethyl melamines such as 1141, Cymel1123 The methoxymethylated butoxymethyl benzoguanamine such as ylmethyl benzoguanamine, Cymel 1123-10, The carboxylic methoxymethylated ethoxy such as the butoxymethyl such as Cymel 1128 benzoguanamine, Cymel 1125-80 Ylmethyl benzoguanamine (above for three well cyanamide Co., Ltd. (three well サイア Na ミ De societies) make).Additionally, as sweet The example of urea, can enumerate the methylolation glycolurils such as the butoxymethyl such as Cymel 1170 glycoluril, Cymel 1172, Grade methoxyl group methylolation glycolurils of POWDERLINK 1174 etc..

As benzene or phenoloid with hydroxyl or alkoxy, can enumerate such as 1,3,5- tri- (methoxy) Benzene, 1,2,4- tri- (i-propoxymethyl) benzene, 1,4- double (sec-butoxymethyl) benzene, 2,6- bishydroxymethyl p-t-butyl phenols Deng.

The cross-linked compound for more specifically being represented with following formulas [6-1]~formula [6-48].

[changing 65]

[changing 66]

[changing 67]

[changing 68]

[changing 69]

[changing 70]

As the cross-linked compound with polymerism unsaturated bond, such as trimethylolpropane tris (methyl) third can be enumerated Olefin(e) acid ester, pentaerythrite three (methyl) acrylate, bipentaerythrite five (methyl) acrylate, three (methyl) acryloxies There are 3 polymerisms not in many (methyl) the acrylate equimoleculars of many glycidyl ethers of ethyoxyl trimethylolpropane, glycerine The cross-linked compound of saturated group, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetrem two Alcohol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxirane-bisphenol-A Type two (methyl) acrylate, expoxy propane-bisphenol type two (methyl) acrylate, 1,6-HD two (methyl) acrylic acid Ester, glycerine two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidyl base ether two (methyl) Acrylate, diethylene glycol diglycidyl glyceryl ether two (methyl) acrylate, (first of phthalic acid 2-glycidyl base ester two Base) acrylate, there are 2 polymerism insatiable hungers in (methyl) the acrylate equimolecular of hydroxyl trimethylace tonitric DOPCP two With the cross-linked compound of group, 2- hydroxyethyls (methyl) acrylate, 2- hydroxypropyls (methyl) acrylate, 2- hydroxyls Butyl (methyl) acrylate, 2- phenoxy group -2- hydroxypropyl (methyl) acrylate, 2- (methyl) acryloxy -2- hydroxyls Base propyl group phthalic acid ester, 3- chlorine-2-hydroxyls propyl group (methyl) acrylate, glycerine list (methyl) acrylate, 2- (first Base) acryloyl-oxyethyl phosphate, there is 1 polymerism unsaturated group in N- methylols (methyl) acrylamide equimolecular Cross-linked compound etc..

In addition, it is also possible to use the compound represented with following formulas [7].

[changing 71]

In formula [7], E₁Be selected from hexamethylene ring, bicyclic own ring, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, fluorenes ring, anthracene nucleus and The group of phenanthrene ring, E₂It is the group selected from following formula [7a] or formula [7b], n is 1~4 integer.

[changing 72]

Above-claimed cpd is one of cross-linked compound, is not limited in these compounds.Additionally, liquid crystal of the invention Cross-linked compound contained by aligning agent can be a kind, it is also possible to two or more combination.

The content of the cross-linked compound in aligning agent for liquid crystal of the invention is relative to the matter of whole component of polymer 100 Amount part is preferably 0.1~150 mass parts.In order that cross-linking reaction is carried out and plays target effect, and the orientation of liquid crystal is not made Property decline, relative to the mass parts of whole component of polymer 100 more preferably 0.1~100 mass parts, particularly preferably 1~50 mass parts.

In aligning agent for liquid crystal of the invention, do not destroying in the range of effect of the invention, taken as liquid crystal is promoted To in film electric charge movement and promote using the liquid crystal orientation film liquid crystal cell electric charge remove compound, preferably add with The nitrogen heterocyclic ring amines that following formulas [M1]~formula [M156] is represented.The amines can directly make an addition to particular polymers Solution in, preferably with appropriate solvent adjust to the mass % of concentration 0.1~10, preferably 1~7 mass % solution after add Plus.As the solvent, as long as the organic solvent for dissolving above-mentioned particular polymers, is not particularly limited.

[changing 73]

[changing 74]

[changing 75]

[changing 76]

[changing 77]

[changing 78]

Do not destroying in the range of effect of the invention, aligning agent for liquid crystal of the invention takes coating of liquid crystalline The organic solvent that the uniformity and surface smoothness of the thickness of polymer envelope during to inorganic agent are improved is (also referred to as bad molten Agent) or compound.In addition, it is also possible to use compound for making liquid crystal orientation film be improved with the adaptation of substrate etc..

As the specific example of the poor solvent for improving film thickness uniformity and surface smoothness, can enumerate as shown below Solvent：

For example, ethanol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohols, 2- amylalcohols, 3- amylalcohols, 2- Methyl-1-butanol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanols, 2- methyl-1-pentenes alcohol, 2- methyl -2- Amylalcohol, 2- ethyls-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanols, sec-n-octyl alcohol, 2- ethyl -1- hexanols, cyclohexanol, 1- Methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,2- fourths Glycol, 1,3 butylene glycol, 1,4- butanediols, 2,3- butanediols, 1,5- pentanediols, 2- methyl -2,4-PD, 2- ethyl -1, 3- hexylene glycols, dipropyl ether, butyl oxide, two hexyl ethers, twoAlkane, glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, the fourth of diethylene glycol two Ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, 3- ethoxybutyls acetic acid esters, 1- methyl amyls acetic acid esters, 2- Ethyl-butyl acetic acid esters, 2- ethylhexyl acetates, ethylene glycol acetate, ethylene acetate, propylene carbonate, carbon Sour ethyl, glycol monoethyl ether, ethylene glycol monoethyl ether, 2- (methoxymethoxy) ethanol, glycol isopropyl ether, ethylene glycol list Butyl ether, ethylene glycol list isoamyl ether, ethylene glycol monohexylether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propane diols, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, 1- (Butoxyethoxy) propyl alcohol, propylene glycol methyl ether acetate, DPG, dipropylene glycol monomethyl ether, DPG list second Ether, Tripropylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, second Diol monoacetate, ethylene acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, 2- (2- second Epoxide ethyoxyl) ethylhexoate, diethylene glycol acetic acid esters, triethylene glycol, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ether, methyl pyruvate, Ethyl pyruvate, 3- methoxy methyl propionates, 3- ethoxy-propionic acid Methylethyls ester, 3- methoxypropionates, 3- ethyoxyls Propionic acid, 3- methoxypropionic acids, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, methyl lactate, ethyl lactate, lactic acid are just The organic solvent with low surface tension such as propyl ester, n-butyl lactate, isoamyl lactate.

These poor solvents can be used a kind, it is also possible to be used in mixed way various.During using poor solvent as described above, compared with It is well 5~80 mass %, more preferably 20~60 mass % of the organic solvent total amount included in aligning agent for liquid crystal.

As the uniformity or the compound of surface smoothness that can improve thickness, fluorine class surfactant, silicon can be enumerated Oxygen alkanes surfactant, nonionic surfactant etc..

More particularly, such as eftop EF301, EF303, EF352 (Tuo Kaimu products Co., Ltd. (トーケ can be enumerated System プロダクツ societies) system), MEGAFACE F171, F173, R-30 ((big Japan of Dainippon Ink. ＆ Chemicals Inc イ Application キ societies) system), Fluorad FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo スリーエ system society) system), AashiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass strain formula Commercial firm (Asahi Glass society) makes) etc..The use ratio of these surfactants is gathered relative to the whole contained by aligning agent for liquid crystal The mass parts of polymer component 100 are preferably 0.01~2 mass parts, more preferably 0.01~1 mass parts.

As the specific example of the compound for making liquid crystal orientation film be improved with the adaptation of substrate, can enumerate as shown below Compound containing functional silanes or the compound containing epoxy radicals：

For example, 3- TSL 8330s, APTES, 2- aminopropyls three can be enumerated Methoxy silane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- TSL 8330s, N- (2- Amino-ethyl) -3- amino propyl methyls dimethoxysilane, 3- ureido-propyl trimethoxy silanes, the ethoxy of 3- ureido-propyls three Base silane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyl -3- aminopropyl triethoxysilicanes Alkane, N- tri-ethoxy silylpropyls diethylenetriamine, N- trimethoxysilylpropyls diethylenetriamine, 10- front threes The azepine decane of TMOS base -1,4,7- three, the azepine decane of 10- triethoxysilicane alkyl -1,4,7- three, 9- trimethoxy silanes Base -3,6- diaza nonyls acetic acid esters, 9- triethoxysilicane alkyl -3,6- diaza nonyls acetic acid esters, N- benzyl -3- aminopropans Base trimethoxy silane, N- benzyls-APTES, N- phenyl -3- TSL 8330s, N- Double (the oxyethylene group) -3- TSL 8330s of phenyl-APTES, N-, double (the oxygen ethene of N- Base)-APTES, ethylene glycol diglycidyl base ether, polyethylene glycol diglycidyl base ether, propane diols Diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol two shrink sweet Oleyl ether, 1,6-HD diglycidyl ether, glycerine diglycidyl ether, 2,2- dibromoneopentyl glycol 2-glycidyls Base ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycols, N, N, N ', N '-four glycidyl group m-xylene diamine, 1,3- Double (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N ', N '-four glycidyl group -4,4 '-diamino-diphenyl first Alkane etc..

In the case of using the compound for making to be improved with the adaptation of substrate, its usage amount is relative to aligning agent for liquid crystal The contained mass parts of whole component of polymer 100 are preferably 0.1~30 mass parts, more preferably 1~20 mass parts.If be less than 0.1 mass parts, then cannot expect the effect that adaptation is improved；If above 30 mass parts, then liquid crystal aligning may be deteriorated.

In liquid crystal aligning treatment of the invention, except above-mentioned cross-linked compound, poor solvent, make the uniformity of thickness Outside the compound that is improved with surface smoothness and the compound for making with the raising of the adaptation of substrate, as long as do not destroying this hair In the range of bright effect, the dielectric of the electrical characteristics such as dielectric constant and electric conductivity for changing liquid crystal orientation film can be added Or conductive materials.

Aligning agent for liquid crystal of the invention can be on substrate be coated and after burning till, by friction treatment or illumination etc. Orientation process is carried out, so as to be used as liquid crystal orientation film.

Additionally, in the case of vertical orientated purposes etc., also can be used as liquid crystal aligning in the case where orientation process is not carried out Film is used.

As the substrate for now using, as long as transparency substrate high, is not particularly limited, glass substrate can be used And the plastic base such as acrylic acid substrate and polycarbonate substrate etc..From from the viewpoint of technique simplification, preferably use and be formed with The substrate of the ITO electrode for liquid crystal drive etc..Additionally, in the liquid crystal display cells of reflection-type, substrate that can be only in side is adopted With the opaque substrate such as silicon wafer, electrode in this case also can be used the material of the reflected lights such as aluminium.

The coating method of aligning agent for liquid crystal is not particularly limited, it is industrial general using silk-screen printing, it is hectographic printing, soft Version printing, ink-jet method etc..As other coating methods, also dip coating, rolling method, slot coated, spin-coating method, spraying process etc., These methods can be used according to purpose.

After aligning agent for liquid crystal is coated on substrate, dried by heating plate, thermal cycle type baking oven, IR (infrared ray) type The heater meanses such as case evaporate solvent in 50~300 DEG C, preferably 80~250 DEG C, so as to can be made into polymer envelope.After burning till If polymer envelope thickness it is excessive, be unfavorable in terms of the power consumption of liquid crystal display cells, if too small, liquid The reliability of crystal display element may be reduced, so preferably 5~300nm, more preferably 10~100nm.Take liquid crystal level To or tilted alignment in the case of, to burning till after polymer envelope by friction, polarized UV rays irradiate etc. process.

Liquid crystal display cells of the invention are to obtain band liquid crystal by aligning agent for liquid crystal of the invention by the above method After the substrate of alignment films, liquid crystal cell is made by known method, so as to be made liquid crystal display cells.

As the preparation method of liquid crystal cell, can the following method of example：Preparation is formed with a pair of substrates of liquid crystal orientation film, Sept is spread on one piece of liquid crystal orientation film of substrate, another piece of base is bonded in the way of liquid crystal aligning face is located at inner side Plate, decompression injection liquid crystal and the method for sealing；After the liquid crystal aligning face dropping liquid of sept crystalline substance is scattered with, adhesive base plate is simultaneously Method for being sealed etc..

In addition, aligning agent for liquid crystal of the invention is also preferably used for having liquid crystal between a pair of substrates for possessing electrode Layer and the liquid crystal display cells being made by following operations：Configuration is comprising by active energy beam and heat between a pair of substrates The liquid-crystal composition of the polymerizable compound of at least one party's polymerization in amount, is lived while applied voltage between electrode by irradiation Property energy-ray and heating at least one method polymerizable compound is polymerized.Herein, as active energy beam, compared with It is well ultraviolet.Used as ultraviolet, wavelength is 300~400nm, preferably 310~360nm.Using the situation of the polymerization of heating Under, heating-up temperature is 40~120 DEG C, preferably 60~80 DEG C.Additionally, ultraviolet irradiation and heating can be carried out simultaneously.

Above-mentioned liquid crystal display cells are by PSA (Polymer Sustained Alignment, polymer stabilizing orientation) Mode controls the tilt angle of liquid crystal molecule.For PSA modes, to a small amount of optical polymerism chemical combination is mixed into liquid crystal material in advance Thing, such as photopolymerization monomer, after assembling liquid crystal cell, to optical polymerism chemical combination in the state of assigned voltage is applied to liquid crystal layer Thing irradiation ultraviolet radiation etc., the tilt angle of the polymer controls liquid crystal molecule by generating.Liquid crystal molecule during generation polymer State of orientation can also be remembered after removal of the voltage, so can be formed at electric field of liquid crystal layer etc. by control to adjust liquid crystal point The tilt angle of son.Additionally, PSA modes do not need friction treatment, so being suitable for being difficult to control tilt angle by friction treatment Vertical alignment-type liquid crystal layer formation.

That is, in liquid crystal display cells of the invention, can by above-mentioned method by aligning agent for liquid crystal of the invention Liquid crystal cell is made after obtaining the substrate with liquid crystal orientation film, will be poly- by least one method in ultraviolet irradiation and heating Conjunction property compound polymerization, so as to control the orientation of liquid crystal molecule.

If one that the liquid crystal cell for enumerating PSA modes makes, following methods can be enumerated：Preparation is formed with liquid crystal orientation film A pair of substrates, spread sept on one piece of liquid crystal orientation film of substrate, by liquid crystal aligning face be located at inner side in the way of glue Close another piece of substrate, decompression injection liquid crystal and the method for sealing；After the liquid crystal aligning face dropping liquid of sept crystalline substance is scattered with Adhesive base plate and the method that is sealed etc..

Mix the polymerizable compound for irradiating and being polymerized by heating or ultraviolet in liquid crystal.As polymerizable compound, Intramolecular can be enumerated with more than 1 acrylate-based or the compound of the polymerism unsaturated group such as methacrylic acid ester group. At this moment, polymerizable compound is preferably 0.01~10 mass parts relative to 100 mass parts liquid crystal compositions, more preferably 0.1~5 mass Part.If polymerizable compound is less than 0.01 mass parts, polymerizable compound is not polymerized and cannot carry out the orientation control of liquid crystal System；If being more than 10 mass parts, unreacted polymerizable compound is more, and the sintering adhesion characteristics of liquid crystal display cells decline.

After being made liquid crystal cell, the voltage of AC or DC is applied to liquid crystal cell, while heating or irradiation ultraviolet radiation make to gather The compound polymerization of conjunction property.Take this, can control the orientation of liquid crystal molecule.

In addition, aligning agent for liquid crystal of the invention is also preferably used for the liquid crystal display cells being made by following operations： There is liquid crystal layer between a pair of substrates for possessing electrode, configuration is comprising by active energy beam between the pair of substrate The liquid crystal orientation film of the polymerizable group being polymerized with least one party in heat, to applied voltage between electrode.Herein, as work Property energy-ray, preferably ultraviolet.Used as ultraviolet, wavelength is 300~400nm, preferably 310~360nm.Using heating Polymerization in the case of, heating-up temperature be 40~120 DEG C, preferably 60~80 DEG C.Additionally, can carry out simultaneously ultraviolet irradiation and Heating.

In order to obtain the liquid crystal comprising the polymerizable group being polymerized by least one party in active energy beam and heat Alignment films, can enumerate to the method that the compound comprising the polymerizable group is added in aligning agent for liquid crystal or using comprising poly- The method of the component of polymer of conjunction property group.Aligning agent for liquid crystal of the invention is comprising with by heat or ultraviolet irradiation And the specific compound at the double bond position reacted, therefore liquid crystal point can be controlled by least one party in ultraviolet irradiation and heating The orientation of son.

If enumerating of liquid crystal cell making, following methods can be enumerated：Preparation is formed with a pair of bases of liquid crystal orientation film Plate, sept is spread on one piece of liquid crystal orientation film of substrate, and another piece is bonded in the way of liquid crystal aligning face is located at inner side Substrate, decompression injection liquid crystal and the method for sealing；To be scattered with the liquid crystal aligning face dropping liquid of sept crystalline substance after adhesive base plate And the method for being sealed etc..

After being made liquid crystal cell, by liquid crystal cell apply AC or DC voltage while heat or irradiate ultraviolet Line, can control the orientation of liquid crystal molecule.

As described above, the reliability of the liquid crystal display cells being made using aligning agent for liquid crystal of the invention is good, can Perform well in LCD TV of big picture, fine etc..

Embodiment

Embodiment exemplified below carries out more specific description to the present invention, but the present invention is not limited in these implementations Example.

[synthesis of specific side chain type diamine compound]

The analytical equipment and analysis condition used in the identification of specific side chain type diamine compound of the invention are as described below.

(¹The measure of H-NMR)

Device:Varian NMR systems 400NB (400MHz) (Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A. (Varian societies) system)

Determine solvent:CDCl₃(deuterochloroform) and DMSO-d₆(deuterated dimethyl sulfoxide)

Standard substance:TMS (tetramethylsilane) (δ:0.0ppm,¹) and CDCl H₃(δ:77.0ppm,¹³C)

The synthesis of specific side chain type diamine compound (1)

[changing 79]

To addition K in DMF (dimethylformamide) solution (190ml) of amphyl (a) (30.0g, 109mmol)₂CO₃ (potassium carbonate) (18.1g, 131mmol) and KI (KI) (1.81g, 10.9mmol), is heated up to 60 DEG C.Alkynes third is added dropwise thereto Bromide (19.5g, 164mmol), reacts 24 hours.Then, reaction solution is injected in water (360ml).It is separated by filtration precipitation Solid, by the solid of gained stirring and washing in methyl alcohol, obtains rough thing (the receipts amount of propargyl ether body (b):32.5g, yield: 95%).The rough thing of gained is directly used in follow-up reaction.

Propargyl ether body (b)：

¹H-NMR(CDCl₃,δppm):7.14(d,2H),6.91(d,2H),4.67(d,2H),2.51(t,1H),2.46- 2.37)(m,1H),1.90-1.81(m,4H),1.46-1.18(m,15H),1.11-0.95(m,2H),0.89(t,3H).

[changing 80]

To addition in THF (tetrahydrofuran) solution (106ml) of 3,5- dinitros iodobenzene (c) (23.5g, 80.1mmol) PdCl₂(PPh₃)₂(0.562g, 0.801mmol), CuI (cupric iodide (I)) (0.305g, 1.60mmol) and Et₂NH (diethylamine) After (7.61g, 104mmol), cooled down with water-bath.To the THF that propargyl ether body (b) (32.5g, 104mmol) is added dropwise in the solution Solution (22.0ml).Stirring 1 hour, reaction solution is injected in water (560ml).The solid of precipitation is separated by filtration, by gained Solid is recrystallized with the mixed solvent of ethyl acetate and hexane, obtains dinitro matrix (d) (receipts amount:23.6g, yield: 62%).

Dinitro matrix (d)：

¹H-NMR(CDCl₃,δppm):8.98(t,1H),8.56(d,2H),7.18(d,2H),6.94(d,2H),4.93(s, 2H),2.48-2.38(m,1H),1.92-1.81(m,4H),1.47-1.18(m,15H),1.10-0.94(m,2H),0.89(t, 3H).

¹³C-NMR(CDCl₃,δppm):155.43,148.34,141.52,131.48,127.81,126.02,118.38, 114.57,90.31,82.46,56.14,43.71,37.38,37.26,34.49,33.56,31.89,29.93,29.36, 26.97,22.68,14.11.

[changing 81]

Add in the THF (131ml) of dinitro matrix (d) (23.3g, 48.7mmol) and the mixed solution of toluene (134ml) Enter Pd/C (palladium carbon) (2.33g), be stirred in room temperature in a hydrogen atmosphere.After reaction 96 hours, by filtering removal Pd/C. Concentration filtrate, by the solid Isosorbide-5-Nitrae-two of gainedThe mixed solvent of alkane and hexane is recrystallized, and obtains specific side chain type two Amines (1) (receipts amount:11.9g, yield:58%).

Specific side chain type diamine compound (1)：

¹H-NMR(CDCl₃,δppm):7.11(d,2H),6.82(d,2H),5.99(d,2H),5.89(t,1H),3.93(t, 2H),3.51(Broad,4H),2.60(t,2H),2.45-2.35(m,1H),2.07-1.98(m,2H),1.90-1.81(m, 4H),1.44-1.17(m,15H),1.08-0.93(m,2H),0.89(t,3H).

¹³C-NMR(CDCl₃,δppm):157.09,147.43,143.97,139.93,127.53,114.27,106.30, 99.71,66.98,43.67,37.40,37.26,34.54,33.61,32.09,31.88,30.54,29.93,29.35, 26.96,22.66,14.10.

The synthesis of specific side chain type diamine compound (2)

[changing 82]

To addition K in the DMF solution (64.0ml) of amphyl (a) (30.0g, 109mmol)₂CO₃(27.2g, 197mmol), the chloro- 1- pentynes (15.7g, 153mmol) of KI (0.907g, 5.47mmol) and 5-, are heated up to 100 DEG C, and reaction 48 is small When.It is then cooled to add DMF (95.0ml) after 25 DEG C, to water (30ml) is added dropwise in the reaction solution, stop reaction.Will The reactant mixture is injected in water (150ml), is separated by filtration the solid of precipitation.By the solid ethyl acetate of gained and methyl alcohol Mixed solvent is recrystallized, and obtains ether body (e) (receipts amount:33.7g, yield:91%).

Ether body (e)：

¹H-NMR(CDCl₃,δppm):7.11(d,2H),6.83(d,2H),4.04(t,2H),2.45-2.36(m,1H), 2.40(dt,2H),2.03-1.95(m,2H),1.96(t,1H),1.89-1.79(m,4H),1.44-1.17(m,15H),1.08- 0.94(m,2H),0.89(t,3H).

¹³C-NMR(CDCl₃,δppm):156.93,140.21,127.62,114.24,83.59,68.74,66.05, 43.72,37.44,37.31,34.57,33.65,31.92,29.96,29.39,28.26,27.00,22.70,15.19, 14.13.

[changing 83]

To addition PdCl in the THF solution (90ml) of 3,5- dinitros iodobenzene (c) (20.0g, 68.0mmol)₂(PPh₃)₂ (0.477g, 0.680mmol), CuI (0.259g, 1.36mmol) and Et₂After NH (6.47g, 88.4mmol), cooled down with water-bath. To the THF solution (45.0ml) that terminal acetylene body (e) (30.1g, 88.4mmol) is added dropwise in the solution.Stirring 20 hours, will be anti- Solution is answered to inject in water (600ml).The solid of precipitation is separated by filtration, the solid of gained is entered with the mixed solvent of THF and methyl alcohol Row recrystallization, obtains dinitro matrix (f) (receipts amount:30.0g, yield:87%).

Dinitro matrix (f)：

¹H-NMR(CDCl₃,δppm):8.92(t,1H),8.50(d,2H),7.14(d,2H),6.85(d,2H),4.10(t, 2H),2.71(t,2H),2.45-2.36(m,1H),2.15-2.05(m,2H),1.89-1.78(m,4H),1.44-1.16(m, 15H),1.09-0.94(m,2H),0.89(t,3H).

¹³C-NMR(CDCl₃,δppm):156.76,148.33,140.45,131.34,127.69,127.56,117.43, 114.19,96.23,77.35,65.93,43.71,37.41,37.29,34.55,33.61,31.91,29.94,29.38, 28.03,22.69,16.28,14.11.

[changing 84]

Add in the THF (167ml) of dinitro matrix (f) (29.7g, 58.6mmol) and the mixed solution of toluene (172ml) Enter Pd/C (2.97g), be stirred in room temperature in a hydrogen atmosphere.After reaction 72 hours, by filtering removal Pd/C.Concentration filter Liquid, the solid of gained is recrystallized with the mixed solvent of THF and hexane, obtains specific side chain type diamine compound (2) (22.1g, 84%).

Specific side chain type diamine compound (2)：

¹H-NMR(CDCl₃,δppm):7.11(d,2H),6.82(d,2H),5.97(d,2H),5.89(t,1H),3.92(t, 2H),3.51(Broad,4H),2.44(t,2H),2.48-2.34(m,1H),1.89-1.74(m,6H),1.66-1.57(m, 2H),1.52-1.18(m,17H),1.07-0.95(m,2H),0.89(t,3H).

¹³C-NMR(CDCl₃,δppm):157.12,147.34,144.98,139.89,127.54,114.17,106.27, 99.60,67.77,43.68,37.41,37.27,35.83,34.55,33.62,31.89,30.89,29.93,29.36, 29.20,26.97,25.76,22.67,14.11.

The synthesis of specific side chain type diamine compound (3)

[changing 85]

Catechol boron was added dropwise with 1 hour in the THF solution (96.0ml) of terminad acetylene body (e) (17.0g, 49.9mmol) The THF solution (80.0ml) of 1 equivalent (80.0mmol) of alkane, is refluxed 24 hours at 80 DEG C.Then, let cool to after 25 DEG C, To the aqueous hydrochloric acid solution (150ml) that 2 equivalents are added in reaction solution, stir 2 hours, in injection water (2000ml).It is separated by filtration The solid of precipitation, is cleaned with hexane and obtains boronic acid derivatives (h).The boronic acid derivatives of gained are directly used in follow-up operation.

[changing 86]

To boronic acid derivatives (h) (17.7g, 45.8mmol), DNFB (k) (8.84g, 43.6mmol) and Pd (PPh₃)₄The Isosorbide-5-Nitrae-two of (0.530g, 0.459mmol)The wet chemical of 2.0mol/L is added in alkane solution (55.7ml) (55.7ml), stirs 2 hours at 80 DEG C.Then, a point liquid is carried out with ethyl acetate and water, organic layer is dried with magnesium sulfate.Will Solid obtained by concentration of organic layers carries out pillar layer separation with ethyl acetate and hexane, obtain dinitro matrix (m) (13.1g, 59%).

Dinitro matrix (m)：

¹H-NMR(CDCl₃,δppm):8.76(d,1H),8.37(dd,1H),7.79(d,2H),7.12(d,2H),6.95 (d,1H),6.83(d,2H),6.53(dt,1H),4.02(t,2H),2.58-2.50(m,2H),2.46-2.37(m,1H), 2.05-1.97(m,2H),1.92-1.81(m,4H),1.46-1.17(m,15H),1,09-0.98(m,2H),0.89(t,3H).

[changing 87]

To Pd/C (1.30g) is added in the THF solution (130ml) of dinitro matrix (m) (13.0g, 25.6mmol), in hydrogen It is stirred in room temperature under atmosphere.After reaction 24 hours, by filtering removal Pd/C.To being added in filtrate, activated carbon stirring 2 is small When, activated carbon is removed by filtration.Then, filtrate is concentrated, specific side chain type diamine compound (3) (11.0g, 95%) is obtained.

Specific side chain type diamine compound (3)：

¹H-NMR(CDCl₃,δppm):7.10(d,2H),6.811(d,2H),6.805(d,1H),6.10(dd,1H),6.04 (d,1H),3.92(t,2H),3.49(Broad,4H),2.41(t,2H),2.44-2.34(m,1H),1.90-1.75(m,6H), 1.68-1.57(m,2H),1.57-1.47(m,2H),1.46-1.36(m,2H)1.35-1.16(m,13H),1.08-0.96(m, 2H),0.88(t,3H).

¹³C-NMR(CDCl₃,δppm):153.89,142.18,141.57,136.72,127.10,124.34,114.12, 110.97,102.89,99.32,64.59,40.47,34.21,34.06,31.34,30.41,28.69,27.29,26.73, 26.16,26.03,25.78,23.77,22.85,19.47,10.91.

[synthesis of polyimide precursor and polyimides]

The abbreviation of the compound used in embodiment and comparative example is as follows.

(tetracarboxylic dianhydride)

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

BODA:Two rings [3.3.0] octane -2,4,6,8- tetracarboxylic dianhydrides

TCA:Tetracarboxylic dianhydride shown in following formula

TDA:Tetracarboxylic dianhydride shown in following formula

[changing 88]

(specific side chain type diamine compound)

A-1:The specific side chain type diamine compound (1) obtained by the synthesis path of embodiment 1

A-2:The specific side chain type diamine compound (2) obtained by the synthesis path of embodiment 2

A-3:The specific side chain type diamine compound (3) obtained by the synthesis path of embodiment 3

[changing 89]

(other diamine compounds)

p-PDA:P-phenylenediamine

m-PDA:M-phenylene diamine (MPD)

DBA:3,5- diaminobenzoic acids

AP18:1,3- diaminourea -4- octadecyl epoxide benzene

[changing 90]

(organic solvent)

NMP:METHYLPYRROLIDONE

BCS:Butyl cellosolve

The measure of molecular weight, being determined as follows for acid imide rate are carried out.

(molecular weight determination)

The molecular weight of the polyimides in synthesis example uses normal temperature gel permeation chromatography (GPC) device (GPC-101) (Showa Electrician Co., Ltd. (Showa Electricity works society) make), post (KD-803, KD-805) (Xiao De Ces Co., Ltd (Shodex societies) system), it is as follows It is measured.

Column temperature:50℃

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

Flow velocity:1.0ml/ minutes

Calibration curve making standard sample:TSK standard PEO (molecular weight:About 900000,150000, 100000 and 30000) ((East ソー societies of TOSOH Co., Ltd) system) and polyethylene glycol (molecular weight about 12000,4000 and 1000) (Polymer Laboratory company (Port リマーラボラトリー societies) system).

(measure of acid imide rate)

20mg polyimide powders are added into NMR sample cells ((wasteland's science Co., Ltd. of NMR sampling pipe standard types φ 5 (wasteland's science society) makes)), (DMSO-d6,0.05 mass %TMS (tetramethylsilane) mix addition 0.53ml deuterated dimethyl sulfoxides Product), applying ultrasonic wave is completely dissolved it.By NMR analyzers (JNW-ECA500) (De Tamu Co., Ltd. of JEOL (Japanese Electricity データ system society) makes) to the proton NMR of solution measure 500MHz.For acid imide rate, with from acyl Proton on the basis of the proton of unchanged structure before and after imidization, using the peak of the proton integrated value and appear in 9.5~ The integrated value at the peak of the NH bases from amic acid near 10.0ppm, acid imide rate is tried to achieve by following formula.

Acid imide rate (%)=(1- α x/y) × 100

In above formula, x is the proton peak integrated value of the NH bases from amic acid, the peak integrated value of proton on the basis of y, and α is Relative to 1 number ratio of the reference proton of the proton of the NH values of amic acid during polyamic acid (acid imide rate is 0%).

By CBDA (4.50g, 22.9mmol), A-1 (1.94g, 4.6mmol) and p-PDA (1.99g, 18.4mmol) in NMP Mixing in (25.3g), after being reacted 5.5 hours at 40 DEG C, obtains the polyamic acid that resin solid content concentration is 25.0 mass % Solution (1).The number-average molecular weight of the polyamic acid is 25900, and weight average molecular weight is 78100.

By BODA (3.83g, 15.3mmol), A-1 (2.59g, 6.1mmol) and DBA (2.17g, 14.3mmol) in NMP Mixing in (15.8g), CBDA (1.00g, 5.1mmol) and NMP (12.9g) is added after being reacted 4 hours at 80 DEG C, in 40 DEG C of reactions 6 hours, obtain the polyamic acid solution that resin solid content concentration is 25.0 mass %.

To NMP is added in the polyimide solution (20.1g) for obtaining, after being diluted to 6 mass %, add as imidizate The acetic anhydride (2.45g) and pyridine (1.85g) of catalyst, react 4.5 hours at 80 DEG C.The reaction solution is put into methyl alcohol In (350ml), the sediment of gained is separated by filtration.The sediment is cleaned with methyl alcohol, in 100 DEG C of drying under reduced pressure, polyamides is obtained Imines powder (2).The acid imide rate of the polyimides is 55%, and number-average molecular weight is 22100, and weight average molecular weight is 60100.

By BODA (2.37g, 9.5mmol), A-2 (2.56g, 5.7mmol) and DBA (2.02g, 13.3mmol) in NMP Mixing in (14.6g), CBDA (1.86g, 9.5mmol) and NMP (11.9g) is added after being reacted 4 hours at 80 DEG C, in 40 DEG C of reactions 6 hours, obtain the polyamic acid solution (3) that resin solid content concentration is 25.0 mass %.The equal molecule of number of the polyamic acid It is 23500 to measure, and weight average molecular weight is 72600.

To NMP is added in the polyamic acid solution (3) (20.0g) obtained in embodiment 6, after being diluted to 6 mass %, add As the acetic anhydride (4.50g) and pyridine (3.25g) of imidization catalyst, reacted 3.5 hours at 90 DEG C.By the reaction solution In input methyl alcohol (450ml), the sediment of gained is separated by filtration.The sediment is cleaned with methyl alcohol, in 100 DEG C of drying under reduced pressure, Obtain polyimide powder (4).The acid imide rate of the polyimides is 80%, and number-average molecular weight is 19500, weight average molecular weight It is 50100.

By BODA (3.04g, 12.2mmol), A-3 (2.34g, 5.2mmol), m-PDA (0.56g, 5.2mmol) and DBA (1.06g, 7.0mmol) mixing in the NMP (13.2g), 80 DEG C of reactions add after 5 hours CBDA (1.02g, 5.2mmol) and NMP (10.8g), reacts 6.5 hours at 40 DEG C, obtains the polyamic acid solution that resin solid content concentration is 25.0 mass %.

To NMP is added in the polyimide solution (20.0g) for obtaining, after being diluted to 6 mass %, add as imidizate The acetic anhydride (4.51g) and pyridine (3.25g) of catalyst, react 3.5 hours at 90 DEG C.The reaction solution is put into methyl alcohol In (450ml), the sediment of gained is separated by filtration.The sediment is cleaned with methyl alcohol, in 100 DEG C of drying under reduced pressure, polyamides is obtained Imines powder (5).The acid imide rate of the polyimides is 81%, and number-average molecular weight is 18300, and weight average molecular weight is 47400.

By BODA (2.11g, 8.4mmol), A-3 (2.28g, 5.1mmol), p-PDA (0.36g, 3.3mmol) and DBA (1.28g, 8.4mmol) mixing in the NMP (12.7g), 80 DEG C of reactions add after 5 hours CBDA (1.65g, 8.4mmol) and NMP (10.5g), reacts 6.5 hours at 40 DEG C, obtains the polyamic acid solution that resin solid content concentration is 25.0 mass %.

To NMP is added in the polyimide solution (20.0g) for obtaining, after being diluted to 6 mass %, add as imidizate The acetic anhydride (4.50g) and pyridine (3.31g) of catalyst, react 3.5 hours at 90 DEG C.The reaction solution is put into methyl alcohol In (450ml), the sediment of gained is separated by filtration.The sediment is cleaned with methyl alcohol, in 100 DEG C of drying under reduced pressure, polyamides is obtained Imines powder (6).The acid imide rate of the polyimides is 68%, and number-average molecular weight is 19300, and weight average molecular weight is 50900.

By TCA (4.48g, 20.0mmol), A-1 (1.70g, 4.0mmol) and DBA (2.44g, 16.0mmol) in NMP Mixing in (25.8g), after being reacted 6 hours at 40 DEG C, obtains the polyamic acid that resin solid content concentration is 25.0 mass % molten Liquid (7).The number-average molecular weight of the polyamic acid is 24200, and weight average molecular weight is 75800.

To addition NMP in the polyamic acid solution (7) (20.5g) obtained in embodiment 11, after being diluted to 6 mass %, plus Enter as the acetic anhydride (1.91g) and pyridine (1.50g) of imidization catalyst, reacted 4 hours at 80 DEG C.By the reaction solution In input methyl alcohol (350ml), the sediment of gained is separated by filtration.The sediment is cleaned with methyl alcohol, in 100 DEG C of drying under reduced pressure, Obtain polyimide powder (8).The acid imide rate of the polyimides is 58%, and number-average molecular weight is 20700, weight average molecular weight It is 55100.

By TCA (4.48g, 20.0mmol), A-3 (2.72g, 6.0mmol), p-PDA (0.65g, 6.0mmol) and DBA (1.22g, 8.0mmol) mixing in NMP (27.2g), after being reacted 6 hours at 40 DEG C, obtaining resin solid content concentration is The polyamic acid solution of 25.0 mass %.

To NMP is added in the polyimide solution (20.0g) for obtaining, after being diluted to 6 mass %, add as imidizate The acetic anhydride (1.90g) and pyridine (1.45g) of catalyst, react 4 hours at 80 DEG C.The reaction solution is put into methyl alcohol In (350ml), the sediment of gained is separated by filtration.The sediment is cleaned with methyl alcohol, in 100 DEG C of drying under reduced pressure, polyamides is obtained Imines powder (9).The acid imide rate of the polyimides is 55%, and number-average molecular weight is 21400, and weight average molecular weight is 56900.

By TDA (1.77g, 5.9mmol), A-2 (2.66g, 5.9mmol) and DBA (2.09g, 13.7mmol) in NMP Mixing in (15.2g), adds CBDA (2.68g, 13.7mmol) and NMP (12.5g), at 40 DEG C after being reacted 5.5 hours at 80 DEG C Reaction 6 hours, obtains the polyamic acid solution that resin solid content concentration is 25.0 mass %.

To NMP is added in the polyimide solution (20.0g) for obtaining, after being diluted to 6 mass %, add as imidizate The acetic anhydride (4.50g) and pyridine (3.30g) of catalyst, react 3.5 hours at 90 DEG C.The reaction solution is put into methyl alcohol In (500ml), the sediment of gained is separated by filtration.The sediment is cleaned with methyl alcohol, in 100 DEG C of drying under reduced pressure, polyamides is obtained Imines powder (10).The acid imide rate of the polyimides is 82%, and number-average molecular weight is 19400, and weight average molecular weight is 48300。

By TDA (4.06g, 13.5mmol), A-3 (3.65g, 8.1mmol) and p-PDA (2.05g, 19.0mmol) in NMP Mixing in (20.5g), adds CBDA (2.65g, 13.5mmol) and NMP (16.8g), at 40 DEG C after being reacted 5.5 hours at 80 DEG C Reaction 6 hours, obtains the polyamic acid solution that resin solid content concentration is 25.0 mass %.

To NMP is added in the polyimide solution (20.5g) for obtaining, after being diluted to 6 mass %, add as imidizate The acetic anhydride (1.95g) and pyridine (1.50g) of catalyst, react 4 hours at 80 DEG C.The reaction solution is put into methyl alcohol In (350ml), the sediment of gained is separated by filtration.The sediment is cleaned with methyl alcohol, in 100 DEG C of drying under reduced pressure, polyamides is obtained Imines powder (11).The acid imide rate of the polyimides is 56%, and number-average molecular weight is 21100, and weight average molecular weight is 52500。

By BODA (2.36g, 9.4mmol), AP18 (2.13g, 5.7mmol) and DBA (2.01g, 13.2mmol) in NMP Mixing in (14.0g), CBDA (1.85g, 9.4mmol) and NMP (11.0g) is added after being reacted 4 hours at 80 DEG C, in 40 DEG C of reactions 6 hours, obtain the polyamic acid solution (12) that resin solid content concentration is 25.0 mass %.The equal molecule of number of the polyamic acid It is 24200 to measure, and weight average molecular weight is 74100.

To addition NMP in the polyamic acid solution (12) (20.0g) obtained in synthesis example 1, after being diluted to 6 mass %, plus Enter as the acetic anhydride (4.50g) and pyridine (3.20g) of imidization catalyst, reacted 3.5 hours at 90 DEG C.The reaction is molten Liquid is put into methyl alcohol (450ml), is separated by filtration the sediment of gained.The sediment is cleaned with methyl alcohol, it is dry in 100 DEG C of decompressions It is dry, obtain polyimide powder (13).The acid imide rate of the polyimides is 80%, and number-average molecular weight is 19900, is divided equally again Son amount is 51600.

For the polyamic acid and polyimides that are obtained in embodiment 4~14, comparative example 1 and 2, collect and be shown in table 37.

[table 37]

*1:Polyamic acid

[preparation of aligning agent for liquid crystal]

In embodiment 15~25, comparative example 3 and 4, the preparation example of aligning agent for liquid crystal is described.For the liquid crystal of gained Aligning agent, collects and is shown in table 38.

[table 38]

[making of liquid crystal orientation film], [the hydrophobicity evaluation of liquid crystal orientation film], [infiltration on the liquid crystal orientation film of liquid crystal Diffusivity evaluate], [making (conventional box) of liquid crystal cell], [making (PSA boxes) of liquid crystal cell] and [evaluation of tilt angle] it is as follows Carry out.

Additionally, the characteristic of each liquid crystal orientation film obtained in embodiment 15~25, comparative example 3 and 4 collect be shown in table 39~ 42。

The hydrophobic evaluation result of liquid crystal orientation film is represented in table 39, is represented in table 40 on the liquid crystal orientation film of liquid crystal The evaluation result of infiltration spread, represents the evaluation result of the tilt angle using conventional box in table 41, represented in table 42 and use PSA The evaluation result of the tilt angle of box.

[making of liquid crystal orientation film]

Aligning agent for liquid crystal is spun on the ito surface of the substrate with ITO electrode of 30mm × 40mm, on hot plate in 80 DEG C are heated 5 minutes, then are heated 30 minutes in 230 DEG C in thermal cycle type cleaning oven, obtain band thickness 100nm Polyimide liquid crystal direct action membrane substrate.

[the hydrophobicity evaluation of liquid crystal orientation film]

The substrate with liquid crystal orientation film obtained in [making of liquid crystal orientation film] is used, the contact angle with water is determined. At this moment, the contact angle with water is higher, then hydrophobicity is high, and the contact angle with water is lower, then hydrophobicity is lower.With the contact angle of water Determine and use automatic contact angle meter CA-Z types (consonance interface science Co., Ltd. (Association and interface science society) system).

[infiltration spread on the liquid crystal orientation film of liquid crystal is evaluated]

The substrate with liquid crystal orientation film obtained in [making of liquid crystal orientation film] is used, the contact angle of liquid crystal is determined. At this moment, the contact angle that liquid crystal of the liquid crystal after 10 seconds is added dropwise is determined, the lower liquid crystal orientation film of the contact angle of liquid crystal, the liquid crystal of liquid crystal Infiltration spread in alignment films is better, the contact angle of liquid crystal liquid crystal orientation film higher, the leaching on the liquid crystal orientation film of liquid crystal Profit diffusivity is poorer.Liquid crystal uses MLC-6608 (Merck Japanese firm (メ Le Network ジャパ Application society) system), the survey of contact angle Surely automatic contact angle meter CA-Z types (consonance interface science Co. Ltd. system) is used.

[making (conventional box) of liquid crystal cell]

Aligning agent for liquid crystal is spun on the ito surface of the substrate with ITO electrode of 30mm × 40mm, on hot plate in 80 DEG C are heated 5 minutes, then are heated 45 minutes in 230 DEG C in thermal cycle type cleaning oven, obtain band thickness 100nm Polyimide liquid crystal direct action membrane ito substrate.By the rubbing device rayon cloth of roll neck 120mm with roller rotating speed 1000rpm, roller gait of march 50mm/ seconds, the condition of pushing amount 0.1mm carry out friction treatment to the coated surface of the ito substrate.

Prepare 2 pieces of ito substrates with liquid crystal orientation film of gained, 6 μ are clipped in the way of liquid crystal aligning face is located at inner side The sept of m is combined, and will be around bonded with sealant, is made sylphon.MLC- is injected by the injection method that depressurizes to the sylphon 6608 (Merck Japanese firm systems), inlet is sealed, and obtains liquid crystal cell (conventional box).

For the liquid crystal cell obtained in embodiment and comparative example, the orientation uniformity to liquid crystal is observed by polarizing microscope Confirmed.These liquid crystal cells be not accompanied by friction treatment grinding and be orientated it is bad, liquid crystal is uniformly directed.

[making (PSA boxes) of liquid crystal cell]

Aligning agent for liquid crystal is spun on the substrate and 10mm with ITO electrode of 20 μm of the pattern spacing of 10mm × 10mm The ito surface of the substrate with ITO electrode of × 40mm, heats 5 minutes in 80 DEG C on hot plate, then clean in thermal cycle type Heat 30 minutes in 230 DEG C in baking oven, obtain the polyimide coating film of thickness 100nm.After coated surface being cleaned with pure water, Heat 15 minutes in 100 DEG C in thermal cycle type cleaning oven, obtain the substrate with liquid crystal orientation film.

For the substrate with liquid crystal orientation film, 6 μm of sept is clipped in the way of liquid crystal aligning face is located at inner side It is combined, will be around bonded with sealant, is made sylphon.It is 0.3 mass % with the MLC-6608 relative to 100 mass % The polymerizable compound (1) that ratio is represented to mixing in MLC-6608 (Merck Japanese firm system) with following formula, is injected by depressurizing Method is injected in the sylphon, then inlet is sealed, and obtains liquid crystal cell.

[changing 91]

For the liquid crystal cell of gained, while the voltage of exchange 5V is applied, using the metal halide lamp of illumination 60mW, The wavelength of below 350nm is shielded, carries out being scaled 20J/cm with 365nm²Ultraviolet irradiation, obtain liquid crystal differently- oriented directivity obtain To the liquid crystal cell (PSA boxes) of control.The temperature in irradiation unit during to liquid crystal cell irradiation ultraviolet radiation is 50 DEG C.

Response speed to the liquid crystal after ultraviolet pre-irradiation and the ultraviolet irradiation of the liquid crystal cell is determined.For Response speed, determines the T90 → T10 of transmissivity 90% to transmissivity 10%.The PSA boxes obtained in embodiment and comparative example In, compared with the liquid crystal cell of ultraviolet pre-irradiation, the fast response time of the liquid crystal cell after ultraviolet irradiation, so confirming liquid crystal Differently- oriented directivity is controlled.

Additionally, all liquid crystal cells are observed by polarizing microscope confirms that liquid crystal is uniformly directed.

[evaluation of tilt angle]

The liquid crystal cell for obtained in [making (conventional box) of liquid crystal cell] and [making (PSA boxes) of liquid crystal cell] it is pre- The measure at inclination angle.For tilt angle, heat 5 hours after liquid crystal injection is heated 5 minutes after 95 DEG C and in 120 DEG C After be determined.In addition, the liquid crystal cell irradiation after heating 5 minutes after 95 DEG C for liquid crystal injection is converted with 365nm It is 10J/cm²Ultraviolet after be also carried out determine.Tilt angle uses PAS-301 (Ai Erxi skies company (ELSICON societies) makes) It is measured at room temperature.In addition, ultraviolet irradiation is using desk-top UV solidification equipments (HCT3B28HEX-1), and (gloomy grace optics is public Department (セ Application ライト societies) system) carry out.

To the polyamic acid solution (1) (10.0g) that the resin solid content concentration obtained in embodiment 4 is 25.0 mass % Middle addition NMP (12.9g) and BCS (18.8g), stir 3 hours at 25 DEG C, obtain aligning agent for liquid crystal (1).The liquid crystal aligning There are not the abnormal conditions such as muddy or precipitation in inorganic agent, confirms as uniform solution.

Aligning agent for liquid crystal (1) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To addition NMP (18.8g) and BCS (23.0g) in the polyimide powder (2) (2.51g) obtained in embodiment 5, Stirred 8 hours at 25 DEG C, so as to obtain aligning agent for liquid crystal (2).There is not muddy or precipitation etc. in the aligning agent for liquid crystal Abnormal conditions, confirm as uniform solution.

Aligning agent for liquid crystal (2) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To the polyamic acid solution (3) (10.5g) that the resin solid content concentration obtained in embodiment 6 is 25.0 mass % Middle addition NMP (11.4g) and BCS (21.9g), stir 3 hours at 25 DEG C, obtain aligning agent for liquid crystal (3).The liquid crystal aligning There are not the abnormal conditions such as muddy or precipitation in inorganic agent, confirms as uniform solution.

Aligning agent for liquid crystal (3) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To addition NMP (22.9g) and BCS (18.8g) in the polyimide powder (4) (2.50g) obtained in embodiment 7, Stirred 8 hours at 25 DEG C, so as to obtain aligning agent for liquid crystal (4).There is not muddy or precipitation etc. in the aligning agent for liquid crystal Abnormal conditions, confirm as uniform solution.

Aligning agent for liquid crystal (4) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To addition NMP (21.0g) and BCS (21.0g) in the polyimide powder (5) (2.52g) obtained in embodiment 8, Stirred 8 hours at 25 DEG C, so as to obtain aligning agent for liquid crystal (5).There is not muddy or precipitation etc. in the aligning agent for liquid crystal Abnormal conditions, confirm as uniform solution.

Aligning agent for liquid crystal (5) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To addition NMP (25.0g) and BCS (16.7g) in the polyimide powder (6) (2.50g) obtained in embodiment 9, Stirred 8 hours at 25 DEG C, so as to obtain aligning agent for liquid crystal (6).There is not muddy or precipitation etc. in the aligning agent for liquid crystal Abnormal conditions, confirm as uniform solution.

Aligning agent for liquid crystal (6) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To the polyamic acid solution (7) that the resin solid content concentration obtained in embodiment 10 is 25.0 mass % NMP (15.0g) and BCS (16.7g) is added in (10.0g), is stirred 3 hours at 25 DEG C, obtain aligning agent for liquid crystal (7).Should There are not the abnormal conditions such as muddy or precipitation in aligning agent for liquid crystal, confirms as uniform solution.

Aligning agent for liquid crystal (7) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To addition NMP (27.1g) and BCS (14.6g) in the polyimide powder (8) (2.50g) obtained in embodiment 11, Stirred 8 hours at 25 DEG C, so as to obtain aligning agent for liquid crystal (8).There is not muddy or precipitation etc. in the aligning agent for liquid crystal Abnormal conditions, confirm as uniform solution.

Aligning agent for liquid crystal (8) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To addition NMP (22.9g) and BCS (18.8g) in the polyimide powder (9) (2.50g) obtained in embodiment 12, Stirred 8 hours at 25 DEG C, so as to obtain aligning agent for liquid crystal (9).There is not muddy or precipitation etc. in the aligning agent for liquid crystal Abnormal conditions, confirm as uniform solution.

Aligning agent for liquid crystal (9) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To addition NMP (25.0g) and BCS in the polyimide powder (10) (2.50g) obtained in embodiment 13 (16.7g), stirs 8 hours, at 25 DEG C so as to obtain aligning agent for liquid crystal (10).There is not muddiness in the aligning agent for liquid crystal Or separate out etc. abnormal conditions, confirm as uniform solution.

Aligning agent for liquid crystal (10) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To addition NMP (23.1g) and BCS in the polyimide powder (11) (2.52g) obtained in embodiment 14 (18.9g), stirs 8 hours, at 25 DEG C so as to obtain aligning agent for liquid crystal (11).There is not muddiness in the aligning agent for liquid crystal Or separate out etc. abnormal conditions, confirm as uniform solution.

Aligning agent for liquid crystal (11) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To the polyamic acid solution (12) that the resin solid content concentration obtained in comparative example 1 is 25.0 mass % NMP (10.9g) and BCS (21.0g) is added in (10.1g), is stirred 3 hours at 25 DEG C, obtain aligning agent for liquid crystal (12).Should There are not the abnormal conditions such as muddy or precipitation in aligning agent for liquid crystal, confirms as uniform solution.

Aligning agent for liquid crystal (12) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

To addition NMP (23.1g) and BCS (18.9g) in the polyimide powder (13) (2.52g) obtained in comparative example 2, Stirred 8 hours at 25 DEG C, so as to obtain aligning agent for liquid crystal (13).There is not muddy or precipitation etc. in the aligning agent for liquid crystal Abnormal conditions, confirm as uniform solution.

Aligning agent for liquid crystal (13) obtained by use has carried out the making and various evaluations of box with above-mentioned condition.

[table 39]

[table 40]

[table 41]

[table 42]

From above-mentioned result, the liquid crystal orientation film obtained by the aligning agent for liquid crystal of embodiments of the invention with by comparing The liquid crystal orientation film that the aligning agent for liquid crystal of example is obtained is compared, even if for a long time exposed to high temperature and the photograph of light (ultraviolet) Penetrate, the change of tilt angle is also small.This is obtained for same result in conventional box and PSA boxes.Particularly be free of specific side chain The comparative example 3 and comparative example 4 of type diamine compound, for a long time change of the tilt angle after high temperature are big, (purple exposed to light Outside line) irradiation after tilt angle change it is especially big.

Additionally, in the case of using identical polyimide precursor and polyimides is constituted, comprising specific side chain type diamine In the embodiment of compound, even if in long-time after high temperature and light (ultraviolet), the change of tilt angle is also small.Specially The comparing of the conventional box of embodiment 17 and comparative example 3 and embodiment 18 and comparative example 4 shown in table 41.Additionally, also table 42 The comparing of the PSA boxes of shown embodiment 17 and comparative example 3 and embodiment 18 and comparative example 4.

In addition, the liquid crystal orientation film obtained by the aligning agent for liquid crystal of embodiments of the invention and the liquid crystal aligning by comparative example The liquid crystal orientation film that inorganic agent is obtained is compared, and liquid crystal orientation film is big with the contact angle of water.That is, the hydrophobicity of liquid crystal orientation film is high. The comparative example 3 and comparative example 4 of specific side chain type diamine compound are particularly free of, the water contact angle of liquid crystal orientation film is small, and liquid Infiltration spread on brilliant liquid crystal orientation film is poor (contact angle of liquid crystal is big).

Additionally, in the case of using identical polyimide precursor and polyimides is constituted, comprising specific side chain type diamine In the embodiment of compound, liquid crystal orientation film is big with the contact angle of water, and the hydrophobicity of liquid crystal orientation film is high.Additionally, comprising specific In the embodiment of side chain type diamine compound, the infiltration spread on the liquid crystal orientation film of liquid crystal is good.Specially shown in table 39 Embodiment 17 and comparative example 3 and embodiment 18 and the evaluation of the water contact angle of the liquid crystal orientation film of comparative example 4 comparing.This Outward, on liquid crystal orientation film of the embodiment 17 also shown in table 42 with comparative example 3 and embodiment 18 with the liquid crystal of comparative example 4 The comparing of the evaluation of infiltration spread.

The possibility utilized in industry

By using the aligning agent for liquid crystal of the polymer comprising the side chain with ad hoc structure of the invention, Neng Gouti Even if changing and can mitigating the liquid crystal produced in ODF modes for tilt angle will not also occur exposed to high temperature and illumination for long-time Uneven liquid crystal orientation film is orientated, by using the liquid crystal orientation film, it is possible to provide display characteristic good reliability liquid crystal high Display element, can be used for big picture, the liquid crystal TV set of fine, TN elements, STN elements, TFT liquid crystal cells etc..

In addition, can also be used to make liquid crystal display unit by the liquid crystal orientation film that aligning agent for liquid crystal of the invention is obtained The manufacture of the liquid crystal display cells of irradiation ultraviolet radiation is needed during part.

Specification, the power of the Japanese patent application 2011-240340 that on November 1st, 2011 files an application are quoted herein The full content of sharp claim and specification digest as specification of the invention announcement.

Claims

1. a kind of aligning agent for liquid crystal, it is characterised in that comprising entering selected from polyimide precursor and to the polyimide precursor At least a kind polymer of polyimides obtained by row imidizate；

The polyimide precursor is to make to include the diamine compound represented with following formulas [2a]~formula [2d] or formula [2B] Diamine component reacts and obtains with tetrabasic carboxylic acid composition；

[changing 1]

In formula [2a], R₁For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1 ~18 fluoroalkoxy, m1 is 2~15 integer, and p1 is 0~3 integer；

In formula [2b], R₂For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1 ~18 fluoroalkoxy, m2 is 2~15 integer, and p2 is 0~3 integer；

In formula [2c], R₃For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1 ~18 fluoroalkoxy, m3 is 2~15 integer, and n1 is 1~3 integer, and p3 is 0~3 integer, and n1+p3 is 1~6 Integer；

In formula [2d], R₄For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1 ~18 fluoroalkoxy, m4 is 2~15 integer, and n2 is 1~3 integer, and p4 is 0~3 integer, and n2+p4 is 1~6 Integer；

[changing 2]

In formula [2B], X₅It is singly-bound ,-O- ,-COO- ,-OCO- ,-CONH- ,-NHCO- ,-NH- ,-N (R₂)-or-S-, R₂It is carbon number 1~5 straight-chain alkyl or the branch-like alkyl of carbon number 1~5；X₆It is the organic group of the carbon number 12~25 with steroid skeleton Group；Q is 2~15 integer.

2. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that the diamine compound represented with formula [2B] 5~80 moles of % accounted in diamine component.

3. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that it is described represented with formula [2a]~formula [2d] two 5~80 moles of % that amines is accounted in diamine component.

4. the aligning agent for liquid crystal as described in any one of claims 1 to 3, it is characterised in that the tetrabasic carboxylic acid composition It is the tetracarboxylic dianhydride represented with following formulas [3]；

[changing 3]

5. aligning agent for liquid crystal as claimed in claim 4, it is characterised in that the Z₁It is with following formula [3a]~formulas The structure that [3j] is represented；

[changing 4]

In formula [3a], Z₂~Z₅It is hydrogen atom, methyl, chlorine atom or phenyl ring, may be the same or different respectively；In formula [3g], Z₆、Z₇For Hydrogen atom or methyl, may be the same or different respectively.

6. the aligning agent for liquid crystal as described in any one of claims 1 to 3, it is characterised in that aligning agent for liquid crystal In comprising 80~99 mass % organic solvent.

7. aligning agent for liquid crystal as claimed in claim 6, it is characterised in that organic solvent includes 5~60 mass % not Good solvent.

8. a kind of liquid crystal orientation film, it is characterised in that by the described aligning agent for liquid crystal of any one of claim 1~7 Obtain.

9. a kind of liquid crystal orientation film, it is characterised in that the described liquid crystal aligning treatment of usage right requirement any one of 1~7 Agent is obtained by ink-jet application method.

10. a kind of liquid crystal display cells, it is characterised in that with the liquid crystal orientation film described in claim 8 or 9.

11. liquid crystal orientation films as claimed in claim 8 or 9, it is characterised in that between a pair of substrates for possessing electrode The liquid crystal display cells being made with liquid crystal layer and by following operations：Configuration is comprising by activity between the pair of substrate The liquid-crystal composition of the polymerizable compound of at least one party's polymerization in energy-ray and heat, to applied voltage between the electrode While the polymerizable compound is polymerized.

12. a kind of liquid crystal display cells, it is characterised in that with the liquid crystal orientation film described in claim 11.

13. liquid crystal display cells as claimed in claim 12, it is characterised in that be made by following operations：Possessing electrode There is liquid crystal layer and a pair of substrates of the liquid crystal orientation film between, configuration is comprising by active energy between the pair of substrate The liquid-crystal composition of the polymerizable compound of at least one party's polymerization in amount ray and heat, to applied voltage between the electrode The polymerizable compound is set to be polymerized simultaneously.

14. liquid crystal orientation films as claimed in claim 8 or 9, it is characterised in that between a pair of substrates for possessing electrode The liquid crystal display cells being made with liquid crystal layer and by following operations：Configuration is comprising by activity between the pair of substrate The liquid crystal orientation film of the polymerizable group of at least one party's polymerization in energy-ray and heat, to applied voltage between the electrode The polymerizable group is set to be polymerized simultaneously.

15. a kind of liquid crystal display cells, it is characterised in that with the liquid crystal orientation film described in claim 14.

16. liquid crystal display cells as claimed in claim 15, it is characterised in that be made by following operations：Possessing electrode A pair of substrates between there is liquid crystal layer, configuration is comprising by active energy beam and heat between the pair of substrate The liquid crystal orientation film of the polymerizable group of at least one party's polymerization, to making the polymerism base between the electrode while applied voltage Reunite and close.

17. a kind of diamine compounds, it is characterised in that represented with following formula [2a]~formula [2d]；

[changing 5]

In formula [2d], R₄For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1 ~18 fluoroalkoxy, m4 is 2~15 integer, and n2 is 1~3 integer, and p4 is 0~3 integer, and n2+p4 is 1~6 Integer.

A kind of 18. polyamic acids, it is characterised in that make to include the diamine component of the diamine compound represented with following formula [2B] with Tetrabasic carboxylic acid composition reacts and obtains；

[changing 6]

19. a kind of polyimides, it is characterised in that make the polyamic acid dehydration closed-loop described in claim 18 and obtain.

20. a kind of polyamic acids, it is characterised in that make to include the two of the diamine compound represented with following formula [2a]~formula [2d] Amine component reacts and obtains with tetrabasic carboxylic acid composition；

[changing 7]

21. a kind of polyimides, it is characterised in that make the polyamic acid dehydration closed-loop described in claim 20 and obtain.