CN104081268A

CN104081268A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: CN104081268A
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: 2014-10-01
Anticipated expiration: 2032-10-31
Also published as: JP2017226647A; JP6183212B2; TWI567107B; JP6465159B2; JPWO2013065755A1; CN104081268B; KR101938923B1; TW201335232A; KR20140084278A; WO2013065755A1

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, this compound is reacted as the part of raw material and polyimide precursor, to this polyimide precursor carry out imidizate and polyimide, the aligning agent for liquid crystal that comprises these polymkeric substance, liquid crystal orientation film and there is the liquid crystal display cells of this liquid crystal orientation film.

Background technology

Liquid crystal display cells is widely used as realizing display device slim, light weight now.This liquid crystal display cells adopts liquid crystal orientation film to determine the state of orientation of liquid crystal conventionally.

This liquid crystal orientation film in most of the cases adopts polyimide film.The formation of this polyimide film, adopts as the solution of polyamic acid of the precursor of polyimide or the solution coat of solvent-soluble polyimide in substrate and the method for burning till.This polyamic acid or solvent-soluble polyimide generally wait the formation of reacting of tetracarboxylic acid derivatives and two amine components by tetracarboxylic dianhydride.

As to one of desired characteristic of liquid crystal orientation film, liquid crystal molecule is remained on to value arbitrarily with respect to the orientation pitch angle of real estate, there is the control of the tilt angle of so-called liquid crystal.The structure that the large I of known this tilt angle forms the polyimide of liquid crystal orientation film by selection changes.Control by the structure of polyimide in the technology of tilt angle, the part of the raw material of polyimide adopts the method for the diamines with side chain can be according to the usage ratio control tilt angle of this diamines, so be easier to obtain target tilt angle, can be used as increasing the method (reference example is as patent documentation 1) of tilt angle.

In addition, for increasing two amine components of tilt angle of liquid crystal, also carrying out stability for improving tilt angle and the structural research of process dependency for like this.At this, as side-chain structure used, put forward the structure (reference example is as patent documentation 2) containing ring structures such as phenyl or cyclohexyl.

In the making of liquid crystal display cells, need to be to the operation that is formed with (box spacing) filling liquid crystal between 2 substrates of liquid crystal orientation film.So far, liquid crystal filling is generally to utilize the vacuum injection mode of the pressure differential of atmospheric pressure and vacuum to filling liquid crystal between 2 substrates.But in the situation of which, liquid crystal injecting port is only located at the one-sided of substrate, therefore, in order to be filling liquid crystal between the substrate of 3～5 μ m to box spacing, need the long period, so be difficult to simplify the manufacturing process of liquid crystal display cells.Particularly, in the manufacture of practical in recent years liquid crystal TV set and giant display, this becomes large problem.

So, in order to solve the problem in above-mentioned vacuum injection mode, developed liquid crystal drop add mode (also referred to as ODF mode).Which is to drip liquid crystal to being formed with on the substrate of liquid crystal orientation film, after bonding another piece substrate, encapsulant UV is solidified in a vacuum, thus the mode of filling liquid crystal.

On the other hand, along with the continuous high-precision refinement of liquid crystal display cells, need to control demonstration deviation.For ODF mode, all the time by reducing the dripping quantity of liquid crystal or improving manufacturing process that vacuum tightness when bonding etc. alleviates the impact of planar water and impurity and optimize and solve.But, follow the maximization of liquid crystal display cells manufacturing line, optimize and cannot suppress to show deviation by manufacturing process in the past, need to be than more can reduce the liquid crystal orientation film that shows deviation in the past.

Prior art document

Patent documentation

Patent documentation 1: Japanese patent laid-open 2-282726 communique

Patent documentation 2: Japanese patent laid-open 9-278724 communique

The summary of invention

Invent technical matters to be solved

Liquid crystal orientation film is also used to carry out liquid crystal phase for the angle of substrate, the i.e. control of the tilt angle of liquid crystal, but at liquid crystal display cells high performance, in the situation that its range of application expands year by year, be not only the tilt angle that obtains regulation, it is more and more important that the stability of tilt angle also becomes.

In the manufacturing process of liquid crystal display cells, in order to improve the orientation homogeneity of liquid crystal, sometimes after inclosure liquid crystal, carry out heat treated and make the temporary transient isotropization of liquid crystal.But, in the low situation of the stability of tilt angle, there is cannot to obtain after this isotropization is processed the tilt angle of target sizes or tilt angle and produce the problem of deviation.Particularly use the liquid crystal display cells of the backlight that thermal value is large, the exposure of light is many in order to obtain high brightness, such as, in onboard navigation system and large-scale tv machine etc., long-time use under the environment that is exposed to high temperature and illumination or placement sometimes.Under such rigor condition, when tilt angle gradually variation has occurred, appearance cannot obtain the display characteristic at initial stage or produce problems such as showing deviation.

In the ODF mode of the liquid crystal filling work procedure during as making liquid crystal display cells, liquid crystal is directly dripped in alignment films, and therefore when liquid crystal drop added-time or base plate bonding, liquid crystal and liquid crystal orientation film bear physical stress, for at whole panel zone filling liquid crystal, need to increase the dropping point of liquid crystal.Therefore, the part that the drop of liquid crystal dropping portion and liquid crystal and the liquid crystal of adjacency join easily produces and is called as the so-called orientation inequality that drips trace or lattice deviation, makes in the situation of liquid crystal display cells, has the problem that causes showing deviation because being orientated inequality.Planar water and impurity that this orientation inequality is considered to adhere to due to the liquid crystal aligning membrane interface being formed on substrate are gathered because of the liquid crystal dripping in ODF mode, and part that the amount of planar water and impurity is joined with liquid crystal droplet in liquid crystal dropping portion is different and produce.

The present invention is the invention In view of the foregoing completing., be exposed to for a long time high temperature and the liquid crystal orientation film of the variation of tilt angle also can not occur in illumination even if the object of the present invention is to provide, and the liquid crystal orientation film that can alleviate the liquid crystal aligning inequality producing in ODF mode is provided.In addition, the present invention also aims to provide have above-mentioned liquid crystal orientation film liquid crystal display cells, the aligning agent for liquid crystal of above-mentioned liquid crystal orientation film can be provided, for obtaining the polymkeric substance of this aligning agent for liquid crystal and for obtaining the diamine compound of this polymkeric substance.

The technical scheme that technical solution problem adopts

The inventor has carried out conscientiously research, and it is effective especially that the aligning agent for liquid crystal that found that the polymkeric substance that comprises the side chain with ad hoc structure is stated object aspect in realization, thereby completed the present invention.

, the present invention includes following technology contents.

(1) aligning agent for liquid crystal, is characterized in that, comprise be selected from have the polyimide precursor of the side chain representing with following formula [1A] or [1B] and to this polyimide precursor carry out imidizate and at least a kind of polymkeric substance of polyimide;

[changing 1]

In formula [1A], X ₁for singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-,-N (R ₁)-or-S-, R ₁for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5; X ₂represent to be selected from the divalent cyclic group of phenyl ring, hexamethylene ring or heterocycle, the hydrogen atom arbitrarily on these cyclic groups can be replaced by fluoroalkoxy or the fluorine atom containing fluoroalkyl, carbon number 1～3 of the alkoxy of the alkyl of carbon number 1～3, carbon number 1～3, carbon number 1～3; X ₃represent to be selected from the divalent cyclic group of phenyl ring, hexamethylene ring or heterocycle, the hydrogen atom arbitrarily on these cyclic groups can be replaced by fluoroalkoxy or the fluorine atom containing fluoroalkyl, carbon number 1～3 of the alkoxy of the alkyl of carbon number 1～3, carbon number 1～3, carbon number 1～3; X ₄for 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; M is 2～15 integer, the integer that n is 1～3, the integer that p is 0～3, the integer that n+p is 1～6;

[changing 2]

In formula [1B], X ₅for singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-,-N (R ₂)-or-S-, R ₂for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5; X ₆for thering is the organic group of carbon number 12～25 of steroid skeleton; Q is 2～15 integer.

(2) aligning agent for liquid crystal as described in above-mentioned (1), wherein, described polyimide precursor is to make to comprise that two amine components of the diamine compound with the side chain representing with formula [1A] or formula [1B] react and obtain with tetrabasic carboxylic acid composition.

(3) aligning agent for liquid crystal as described in above-mentioned (2), wherein, described in there is the side chain representing with formula [1A] diamine compound represent with following formula [2A];

[changing 3]

In formula [2A], X ₁for singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-,-N (R ₁)-or-S-, R ₁for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5; X ₂represent to be selected from the divalent cyclic group of phenyl ring, hexamethylene ring or heterocycle, the hydrogen atom arbitrarily on these cyclic groups can be replaced by fluoroalkoxy or the fluorine atom containing fluoroalkyl, carbon number 1～3 of the alkoxy of the alkyl of carbon number 1～3, carbon number 1～3, carbon number 1～3; X ₃represent to be selected from the divalent cyclic group of phenyl ring, hexamethylene ring or heterocycle, the hydrogen atom arbitrarily on these cyclic groups can be replaced by fluoroalkoxy or the fluorine atom containing fluoroalkyl, carbon number 1～3 of the alkoxy of the alkyl of carbon number 1～3, carbon number 1～3, carbon number 1～3; X ₄for 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; M is 2～15 integer, the integer that n is 1～3, the integer that p is 0～3, the integer that n+p is 1～6.

(4) aligning agent for liquid crystal as described in above-mentioned (3), wherein, the described diamine compound representing with formula [2A] represents with following formula [2a]～formula [2d];

[changing 4]

In formula [2a], R ₁for 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, the integer that m1 is 2～15, the integer that p1 is 0～3;

In formula [2b], R ₂for 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, the integer that m2 is 2～15, the integer that p2 is 0～3;

In formula [2c], R ₃for 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, the integer that m3 is 2～15, the integer that n1 is 1～3, the integer that p3 is 0～3, the integer that n1+p3 is 1～6;

In formula [2d], R ₄for 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, the integer that m4 is 2～15, the integer that n2 is 1～3, the integer that p4 is 0～3, the integer that n2+p4 is 1～6.

(5) aligning agent for liquid crystal as described in above-mentioned (2), wherein, described in there is the side chain representing with formula [1B] diamine compound represent with following formula [2B];

[changing 5]

In formula [2B], X ₅for singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-,-N (R ₂)-or-S-, R ₂for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5; X ₆for thering is the organic group of carbon number 12～25 of steroid skeleton; Q is 2～15 integer.

(6) aligning agent for liquid crystal as described in any one in above-mentioned (3)～(5), wherein, the described diamine compound representing with formula [2A] or formula [2B] accounts for 5～80 % by mole in two amine components.

(7) aligning agent for liquid crystal as described in above-mentioned (4), wherein, the described diamine compound representing with formula [2a]～formula [2d] accounts for 5～80 % by mole in two amine components.

(8) aligning agent for liquid crystal as described in any one in above-mentioned (2)～(7), wherein, described tetrabasic carboxylic acid composition is the tetracarboxylic dianhydride who represents with following formula [3];

[changing 6]

In formula [3], Z ₁for 4 valency organic groups of carbon number 4～13, and the non-aromatic cyclic hydrocarbon group that comprises carbon number 4～10.

(9) aligning agent for liquid crystal as described in above-mentioned (8), wherein, described Z ₁the structure representing for the formula with following [3a]～formula [3j];

[changing 7]

In formula [3a], Z ₂～Z ₅for hydrogen atom, methyl, chlorine atom or phenyl ring, respectively can be identical or different; In formula [3g], Z ₆, Z ₇for hydrogen atom or methyl, respectively can be identical or different.

(10) aligning agent for liquid crystal as described in any one in above-mentioned (1)～(9), wherein, comprises the organic solvent of 80～99 quality % in aligning agent for liquid crystal.

(11) aligning agent for liquid crystal as described in above-mentioned (10), wherein, organic solvent comprises the poor solvent of 5～60 quality %.

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

(13) liquid crystal orientation film, uses the aligning agent for liquid crystal described in any one in above-mentioned (1)～(11) to obtain by ink-jet application method.

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

(15) liquid crystal orientation film as described in above-mentioned (12) or (13), liquid crystal display cells for thering is liquid crystal layer between a pair of substrate that possesses electrode and making through following operation: configuration packet is containing the liquid-crystal composition of the polymerizable compound of at least one party's polymerization by active energy beam and heat, to execute the alive described polymerizable compound polymerization that makes between described electrode simultaneously between described a pair of substrate.

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

(17) liquid crystal display cells as described in above-mentioned (16), make through following operation: between a pair of substrate that possesses electrode and described liquid crystal orientation film, there is liquid crystal layer, between described a pair of substrate, configuration packet is containing the liquid-crystal composition of the polymerizable compound by least one party's polymerization in active energy beam and heat, to execute the alive described polymerizable compound polymerization that makes between described electrode simultaneously.

(18) liquid crystal orientation film as described in above-mentioned (12) or (13), liquid crystal display cells for thering is liquid crystal layer between a pair of substrate that possesses electrode and making through following operation: configuration packet is containing the liquid crystal orientation film of the polymerizable group of at least one party's polymerization by active energy beam and heat, to execute the alive described polymerizable group polymerization that makes between described electrode simultaneously between described a pair of substrate.

(19) liquid crystal display cells, is characterized in that, has above-mentioned (18) described liquid crystal orientation film.

(20) liquid crystal display cells as described in above-mentioned (19), make through following operation: between a pair of substrate that possesses electrode, there is liquid crystal layer, between described a pair of substrate, configuration packet is containing the liquid crystal orientation film of the polymerizable group by least one party's polymerization in active energy beam and heat, to execute the alive described polymerizable group polymerization that makes between described electrode simultaneously.

(21) diamine compound representing with described formula [2A].

(22) diamine compound representing with described formula [2a]～formula [2d].

(23) two amine components that make to comprise the described diamine compound representing with formula [2A] or formula [2B] react with tetrabasic carboxylic acid composition and must polyamic acid, or make this polyamic acid dehydration closed-loop and must polyimide.

(24) two amine components that make to comprise the described diamine compound representing with formula [2a]～formula [2d] react with tetrabasic carboxylic acid composition and must polyamic acid, or make this polyamic acid dehydration closed-loop and must polyimide.

The effect of invention

The aligning agent for liquid crystal of the polymkeric substance that comprises the side chain with ad hoc structure of the application of the invention, even if can provide to be exposed to for a long time high temperature and the variation of tilt angle also can not occur in illumination, and can alleviate the liquid crystal orientation film of the liquid crystal aligning inequality producing in ODF mode.Thereby, by using this liquid crystal orientation film, can provide the liquid crystal display cells that display characteristic good reliability is high.

The mode carrying out an invention

Below, the present invention is described in detail.

The present invention be comprise be selected from have the polyimide precursor of the side chain (also referred to as particular side chain structure) representing with following formula [1A] or [1B] and to this polyimide precursor carry out imidizate and the aligning agent for liquid crystal of at least a kind of polymkeric substance (also referred to as particular polymers) of polyimide.

[changing 8]

In formula [1A], X ₁for singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-,-N (R ₁)-or-S-, R ₁for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5.X ₂represent to be selected from the divalent cyclic group of phenyl ring, hexamethylene ring or heterocycle, the hydrogen atom arbitrarily on these cyclic groups can be replaced by fluoroalkoxy or the fluorine atom containing fluoroalkyl, carbon number 1～3 of the alkoxy of the alkyl of carbon number 1～3, carbon number 1～3, carbon number 1～3.X ₃represent to be selected from the divalent cyclic group of phenyl ring, hexamethylene ring or heterocycle, the hydrogen atom arbitrarily on these cyclic groups can be replaced by fluoroalkoxy or the fluorine atom containing fluoroalkyl, carbon number 1～3 of the alkoxy of the alkyl of carbon number 1～3, carbon number 1～3, carbon number 1～3.X ₄for 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.M is 2～15 integer, the integer that n is 1～3, the integer that p is 0～3, the integer that n+p is 1～6.

[changing 9]

In formula [1B], X ₅for singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-,-N (R ₂)-or-S-, R ₂for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5.X ₆for thering is the organic group of carbon number 12～25 of steroid skeleton.Q is 2～15 integer.

Particular side chain structure of the present invention is the structure representing with described formula [1A] or formula [1B].

The described structure representing taking formula [1A] is phenyl ring, hexamethylene ring or heterocycle.Thus, improve heat and ultraviolet stability at side chain position.Therefore, can obtain tilt angle for light and heat also stable liquid crystal orientation film.

In addition, the described structure representing with formula [1B] has the cyclic group being formed by steroid skeleton.Therefore, can obtain the effect same with formula [1A], that is, side chain position is to heat and the raising of ultraviolet stability, can obtain tilt angle for light and heat also stable liquid crystal orientation film.

The described structure representing taking formula [1A] is phenyl ring, hexamethylene ring or heterocycle.In addition, the described structure representing with formula [1B] has the cyclic group being formed by steroid skeleton.The cyclic group being formed by steroid skeleton in phenyl ring, hexamethylene ring or heterocycle and formula [1B] in these formulas [1A] is and structure like liquid crystal type that the invasion on the liquid crystal orientation film of the liquid crystal therefore dripping in ODF mode improves.Thus, the physical stress to liquid crystal and liquid crystal orientation film producing can alleviate base plate bonding time.Based on these aspects, of the present invention have as the liquid crystal orientation film of the described formula [1A] of particular side chain structure or the structure of formula [1B] can alleviate the liquid crystal aligning inequality producing in ODF mode.

The described structure representing with formula [1A] in main polymer chain and formula [1A]-(CH ₂) _m-X ₁-(X ₂) _n-(X ₃) _p-X ₄part between there is alkyl., hydrophobicity high-(CH ₂) _m-X ₁-(X ₂) _n-(X ₃) _p-X ₄part be present in and main polymer chain position in a distance.Therefore, while making liquid crystal orientation film, should-(CH ₂) _m-X ₁-(X ₂) _n-(X ₃) _p-X ₄part come across efficiently alignment films interface, thereby can improve the hydrophobicity of liquid crystal orientation film.Thus, can suppress the absorption of water and the impurity of liquid crystal aligning membrane interface.In addition ,-(CH ₂) _m-X ₁-(X ₂) _n-(X ₃) _p-X ₄part be present in and main polymer chain position in a distance, therefore can come across efficiently alignment films interface with phenyl ring, hexamethylene ring or heterocycle like liquid crystal type.Therefore the invasion of the liquid crystal, dripping in above-mentioned ODF mode on liquid crystal orientation film improves.

Similarly, the particular side chain structure in described formula [1B] shows the effect identical with the particular side chain structure of formula [1A].

According to above-mentioned aspect, the aligning agent for liquid crystal of the polymkeric substance that comprises the side chain with ad hoc structure of the application of the invention, even if the variation that is exposed to for a long time high temperature and illumination and also can not occurs tilt angle can be provided, can alleviate the liquid crystal orientation film of the liquid crystal aligning inequality producing in ODF mode.In addition,, by using this liquid crystal orientation film, can provide the liquid crystal display cells that display characteristic good reliability is high.

< particular side chain structure >

As particular polymers of the present invention be selected from polyimide precursor and to this polyimide precursor carry out imidizate and at least a kind of polyimide there is the particular side chain structure representing with following formula [1A].

[changing 10]

In formula [1A], X ₁for singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-,-N (R ₁)-or-S-, R ₁for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5.Wherein, be better singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-or-N (R ₁)-, R ₁for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5.Be more preferably-O-,-CONH-,-NHCO-or-NH-.Further be more preferably-O-,-CONH-or-NHCO-.

In formula [1A], X ₂represent to be selected from the divalent cyclic group of phenyl ring, hexamethylene ring or heterocycle, the hydrogen atom arbitrarily on these cyclic groups can be replaced by fluoroalkoxy or the fluorine atom containing fluoroalkyl, carbon number 1～3 of the alkoxy of the alkyl of carbon number 1～3, carbon number 1～3, carbon number 1～3.At this moment, X ₂can be identical, also can be different.Wherein, X ₂better phenyl ring or hexamethylene ring.

In formula [1A], X ₃represent to be selected from the divalent cyclic group of phenyl ring, hexamethylene ring or heterocycle, the hydrogen atom arbitrarily on these cyclic groups can be replaced by fluoroalkoxy or the fluorine atom containing fluoroalkyl, carbon number 1～3 of the alkoxy of the alkyl of carbon number 1～3, carbon number 1～3, carbon number 1～3.At this moment, X ₃can be identical, also can be different.Wherein, X ₃better phenyl ring or hexamethylene ring.

In formula [1A], X ₄for 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, be better carbon number 1～18 alkyl, carbon number 1～10 containing fluoroalkyl, the alkoxy of carbon number 1～18 or the fluoroalkoxy of carbon number 1～10.Be more preferably the alkyl of carbon number 1～12 or the alkoxy of carbon number 1～12.Further be more preferably the alkyl of carbon number 1～10 or the alkoxy of carbon number 1～10.

In formula [1A], the integer that m is 2～15.Wherein, be better 2～10 integer.Be more preferably 2～7 integer.

In formula [1A], the integer that n is 1～3.Wherein, be better 1 or 2 integer.

In formula [1A], the integer that p is 0～3.Wherein, be better 0～2 integer.

In formula [1A], the integer that n+p is 1～6.Wherein, be better 1～4 integer.

X in formula [1A] ₁, X ₂, X ₃, X ₄, m, n and p preferred compositions as shown in table 1～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]

In addition, as particular polymers of the present invention be selected from polyimide precursor and to this polyimide precursor carry out imidizate and at least a kind of polyimide there is the particular side chain structure representing with following formula [1B].

[changing 11]

In formula [1B], X ₅for singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-,-N (R ₂)-or-S-, R ₂for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5.Wherein, be better singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-or-N (R ₂)-, R ₂for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5.Be more preferably-O-,-CONH-,-NHCO-or-NH-.Further be more preferably-O-,-CONH-or-NHCO-.

In formula [1B], X ₆for thering is the organic group of carbon number 12～25 of steroid skeleton, it is better the organic group with the carbon number 15～25 of steroid skeleton.

In formula [1B], the integer that q is 2～15.Wherein, be better 2～10 integer.Be more preferably 2～7 integer.

< particular side chain diamine compound >

As to particular polymers of the present invention, be selected from the polyimide precursor obtaining with reacting of tetrabasic carboxylic acid composition by two amine components and make to introduce at least a kind of polyimide that this polyimide precursor dehydration closed-loop obtains the method for particular side chain structure, it is better diamine compound (also referred to as particular side chain diamine compound) that the formula with following [2A] the is represented part as raw material.

[changing 12]

In formula [2A], X ₁for singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-,-N (R ₁)-or-S-, R ₁for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5.Wherein, be better singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-or-N (R ₁)-, R ₁for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5.Be more preferably-O-,-CONH-,-NHCO-or-NH-.Further be more preferably-O-,-CONH-or-NHCO-.

In formula [2A], X ₂represent to be selected from the divalent cyclic group of phenyl ring, hexamethylene ring or heterocycle, the hydrogen atom arbitrarily on these cyclic groups can be replaced by fluoroalkoxy or the fluorine atom containing fluoroalkyl, carbon number 1～3 of the alkoxy of the alkyl of carbon number 1～3, carbon number 1～3, carbon number 1～3.At this moment, X ₂can be identical, also can be different.Wherein, X ₂better phenyl ring or hexamethylene ring.

In formula [2A], X ₃for 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, be better carbon number 1～18 alkyl, carbon number 1～10 containing fluoroalkyl, the alkoxy of carbon number 1～18 or the fluoroalkoxy of carbon number 1～10.Be more preferably the alkyl of carbon number 1～12 or the alkoxy of carbon number 1～12.Further be more preferably the alkyl of carbon number 1～10 or the alkoxy of carbon number 1～10.

In formula [2A], the integer that m is 2～15.Wherein, be better 2～10 integer.Be more preferably 2～7 integer.

In formula [2A], the integer that n is 1～3.Wherein, be better 1 or 2 integer.

In formula [2A], the integer that p is 0～3.Wherein, be better 0～2 integer.

In formula [2A], the integer that n+p is 1～6.Wherein, be better 1～4 integer.

2 amino (NH in formula [2A] ₂) binding site indefinite.Specifically, with respect to the conjugated group ((CH of side chain ₂) _m-), can exemplify 2,3,2,4,2,5,2,6,3,4 or 3,5 on phenyl ring.Wherein, the reactive viewpoint during from synthesis of polyimides precursor, is better 2,4,2,5 or 3,5.Difficulty while further considering synthetic diamine compound, is more preferably 2,4 or 3,5.

X in formula [2A] ₁, X ₂, X ₃, m, n and p preferred compositions same as shown in table 1～table 30 with formula [1A].

The preferred structure of particular side chain diamine compound of the present invention is the structure representing with following formula [2a]～formula [2d].

[changing 13]

In formula [2a], R ₁for 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, be better carbon number 1～18 alkyl, carbon number 1～10 containing fluoroalkyl, the alkoxy of carbon number 1～18 or the fluoroalkoxy of carbon number 1～10.Be more preferably the alkyl of carbon number 1～12 or the alkoxy of carbon number 1～12.Further be more preferably the alkyl of carbon number 1～9 or the alkoxy of carbon number 1～9.

In formula [2a], the integer that m1 is 2～15.Wherein, be better 2～10 integer.Be more preferably 2～7 integer.

In formula [2a], the integer that p1 is 0～3.Wherein, be better 0～2 integer.

In formula [2b], R ₂for 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, be better carbon number 1～18 alkyl, carbon number 1～10 containing fluoroalkyl, the alkoxy of carbon number 1～18 or the fluoroalkoxy of carbon number 1～10.Be more preferably the alkyl of carbon number 1～12 or the alkoxy of carbon number 1～12.Further be more preferably the alkyl of carbon number 1～10 or the alkoxy of carbon number 1～10.

In formula [2b], the integer that m2 is 2～15.Wherein, be better 2～10 integer.Be more preferably 2～7 integer.

In formula [2b], the integer that p2 is 0～3.Wherein, be better 0～2 integer.

In formula [2c], R ₃for 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, be better carbon number 1～18 alkyl, carbon number 1～10 containing fluoroalkyl, the alkoxy of carbon number 1～18 or the fluoroalkoxy of carbon number 1～10.Be more preferably the alkyl of carbon number 1～12 or the alkoxy of carbon number 1～12.Further be more preferably the alkyl of carbon number 1～10 or the alkoxy of carbon number 1～10.

In formula [2c], the integer that m3 is 2～15.Wherein, be better 2～10 integer.Be more preferably 2～7 integer.

In formula [2c], the integer that n1 is 1～3.Wherein, be better 1 or 2 integer.

In formula [2c], the integer that p3 is 0～3.Wherein, be better 0～2 integer.

In formula [2c], the integer that n1+p3 is 1～6.Wherein, be better 1～4 integer.

In formula [2d], R ₄for 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, be better carbon number 1～18 alkyl, carbon number 1～10 containing fluoroalkyl, the alkoxy of carbon number 1～18 or the fluoroalkoxy of carbon number 1～10.Be more preferably the alkyl of carbon number 1～12 or the alkoxy of carbon number 1～12.Further be more preferably the alkyl of carbon number 1～10 or the alkoxy of carbon number 1～10.

In formula [2d], the integer that m4 is 2～15.Wherein, be better 2～10 integer.Be more preferably 2～7 integer.

In formula [2d], the integer that n2 is 1～3.Wherein, be better 1 or 2 integer.

In formula [2d], the integer that p4 is 0～3.Wherein, be better 0～2 integer.

In formula [2d], the integer that n2+p4 is 1～6.Wherein, be better 1～4 integer.

2 amino (NH in formula [2a]～formula [2d] ₂) binding site indefinite.Specifically, with respect to the conjugated group ((CH of side chain ₂) _m1～m4-), can exemplify 2,3,2,4,2,5,2,6,3,4 or 3,5 on phenyl ring.Wherein, the reactive viewpoint during from synthesis of polyimides precursor, is better 2,4,2,5 or 3,5.Difficulty while further considering synthetic diamine compound, is more preferably 2,4 or 3,5.

It is more specifically the structure for example representing with following formula [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], R ₅independent is respectively the alkyl of carbon number 1～10 or the alkoxy of carbon number 1～10, m ₅it is independently respectively 2～7 integer.

In above-mentioned object lesson, better [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] to be 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 present invention, the diamine compound (same with the above-mentioned diamine compound representing with formula [2A], also referred to as particular side chain diamine compound) that also formula with following [2B] can be represented is as a part for raw material.

[changing 25]

In formula [2B], X ₅for singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-,-N (R ₂)-or-S-, R ₂for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5.Wherein, be better singly-bound ,-O-,-COO-,-OCO-,-CONH-,-NHCO-,-NH-or-N (R ₂)-, R ₂for the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5.Be more preferably-O-,-CONH-,-NHCO-or-NH-.Further be more preferably-O-,-CONH-or-NHCO-.

In formula [2B], X ₆for thering is the organic group of carbon number 12～25 of steroid skeleton, it is better the organic group with the carbon number 15～25 of steroid skeleton.

In formula [2B], the integer that q is 2～15.Wherein, be better 2～10 integer.Be more preferably 2～7 integer.

The synthetic method > of < particular side chain diamine compound

The method of manufacturing the particular side chain diamine compound representing with formula [2A] or formula [2B] of the present invention is not particularly limited, for example can be by following method manufacture.

For example, the specific diamine compound representing with formula [2A] of the present invention can be converted into amino and obtains by reducing nitro after the synthetic dinitro matrix representing with formula [2-I].The method of dinitro compound reduction is not particularly limited, conventionally have the palladium of use carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminium oxide, platinum sulfide carbon etc. as catalyzer at ethyl acetate, toluene, tetrahydrofuran, two the method of being undertaken by hydrogen, hydrazine, hydrogen chloride etc. in alkane, alcohols equal solvent.X in formula [2-I] ₁, X ₂, X ₃, X ₄, m, n and p definition identical with the definition of formula [2A].

[changing 26]

The dinitro matrix of formula [2-I] can by make dinitro matrix-(CH ₂) _m-part is situated between with coupling part X ₁with-(X ₂) _n-(X ₃) _p-X ₄in conjunction with method etc. obtain.

X ₁to be 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 (R ₁)-(R ₁for the alkylated amines key of the straight chain-like alkyl of carbon number 1～5 or the branch-like alkyl of carbon number 1～5) or-linking group of S-(S key), these linking groups suitably in choice for use organic synthesis known method form.

[changing 27]

For example, X ₁in situation for-O-(ehter bond), the method that the hydroxy derivatives that the halogen derivatives containing dinitro that can to exemplify the Xa that makes in formula [2-II] be halogen is hydroxyl (OH yl) with the Xb in formula [2-III] reacts under the existence of alkali.The halogen of the described halogen derivatives containing dinitro is better Cl (chlorine) or Br (bromine).In addition can obtain by the halogenation of corresponding dinitro benzylalcohol containing the halogen derivatives of dinitro.As halogenating agent at this moment used, can exemplify BBr ₃, BCl ₃, PBr ₃, PCl ₃, PPh ₃/ CBr ₄, PPh ₃/ CCl ₄, SOBr ₂, SOCl ₂deng.

X ₁in situation for-COO-(ester bond), the method that the hydroxy derivatives that the chloride derivative containing dinitro that can to exemplify the Xa that makes in formula [2-II] be acyl chlorides is hydroxyl (OH yl) with the Xb in formula [2-III] reacts under the existence of alkali.

X ₁in situation for-OCO-(anti-ester bond), the method that the chloride derivative that the hydroxy derivatives containing dinitro that can exemplify the Xa making in formula [2-II] and be hydroxyl (OH yl) is acyl chlorides with the Xb in formula [2-III] reacts under the existence of alkali.

X ₁in situation for-CONH-(amido link), what can to exemplify the Xa that makes in formula [2-II] be acyl chlorides is amino (NH containing the Xb in chloride derivative and the formula [2-III] of dinitro ₂base) the aminoderivative method of reacting under the existence of alkali.

X ₁in situation for-NHCO-(anti-amido link), can exemplify the Xa making in formula [2-II] is amino (NH ₂base) the chloride derivative that is acyl chlorides with the Xb in formula [2-III] containing the aminoderivative of the dinitro method of reacting under the existence of alkali.

X ₁for-NH-(amine key) or N (R ₁)-(alkylated amines key) situation under, what can to exemplify the Xa that makes in formula [2-II] be halogen is amino (NH containing the Xb in halogen derivatives and the formula [2-III] of dinitro ₂base) or alkylation amino (NH (R ₁) base) and amino or the alkylation aminoderivative method of reacting under the existence of alkali.

In the above-mentioned particular side chain diamine compound representing with formula [2A], also comprise new compound.

Other diamine compound of < >

In the present invention, only otherwise destroy effect of the present invention, can use other diamine compound (also referred to as other diamine compound) beyond particular side chain diamine compound as two amine components.Exemplify its object lesson below:

Specifically can exemplify p-phenylenediamine (PPD), 2,3,5,6-tetramethyl-para-phenylene diamine, 2,5-dimethyl-p-phenylenediamine, m-phenylene diamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamido benzylalcohol, 2,4-diamido benzylalcohol, 4,6-diaminoresorcinol, 4,4'-benzidine, 3,3'-dimethyl-4,4'-benzidine, 3,3'-dimethoxy-4 ', 4'-benzidine, 3,3'-dihydroxy-4,4'-benzidine, 3,3'-dicarboxyl-4,4'-benzidine, 3,3'-bis-is fluoro-4,4'-benzidine, 3,3'-trifluoromethyl-4,4'-benzidine, 3,4'-benzidine, 3,3'-benzidine, 2,2'-benzidine, 2,3'-benzidine, 4,4'-diaminodiphenyl-methane, 3,3'-diaminodiphenyl-methane, 3,4'-diaminodiphenyl-methane, 2,2'-diaminodiphenyl-methane, 2,3'-diaminodiphenyl-methane, 4,4'-diamino-diphenyl ether, 3,3'-diamino-diphenyl ether, 3,4'-diamino-diphenyl ether, 2,2'-diamino-diphenyl ether, 2,3'-diamino-diphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, two (4-aminophenyl) silane, two (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4'-diamino-diphenyl thioether, 3,3'-diamino-diphenyl thioether, 4,4'-diamino-diphenyl amine, 3,3'-diamino-diphenyl amine, 3,4'-diamino-diphenyl amine, 2,2'-diamino-diphenyl amine, 2,3'-diamino-diphenyl amine, N-methyl (4,4'-diamino-diphenyl) amine, N-methyl (3,3'-diamino-diphenyl) amine, N-methyl (3,4'-diamino-diphenyl) amine, N-methyl (2,2'-diamino-diphenyl) amine, N-methyl (2,3'-diamino-diphenyl) amine, 4,4'-diamido benzophenone, 3,3'-diamido benzophenone, 3,4'-diamido benzophenone, Isosorbide-5-Nitrae-diaminonaphthalene, 2,2'-diamido benzophenone, 2,3'-diamido benzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, two (4-aminophenyl) ethane of 1,2-, two (3-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, two (3-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, Isosorbide-5-Nitrae-bis-(3-aminophenyl) butane, two (3,5-diethyl-4-aminophenyl) methane, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) benzene, two (4-aminophenyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminobenzyl) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 4,4'-[1,4-phenylene two (methylene)] diphenylamine, 4,4'-[1,3-phenylene two (methylene)] diphenylamine, 3,4'-[1,4-phenylene two (methylene)] diphenylamine, 3,4'-[1,3-phenylene two (methylene)] diphenylamine, 3,3'-[1,4-phenylene two (methylene)] diphenylamine, 3,3'-[1,3-phenylene two (methylene)] diphenylamine, Isosorbide-5-Nitrae-phenylene two [(4-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two (PABA ester), Isosorbide-5-Nitrae-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), two (4-aminophenyl) phthalic ester, two (3-aminophenyl) phthalic ester, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, N, N'-(Isosorbide-5-Nitrae-phenylene) two (4-aminobenzamides), N, N'-(1,3-phenylene) two (4-aminobenzamides), N, N'-(Isosorbide-5-Nitrae-phenylene) two (3-ABs), N, N'-(1,3-phenylene) two (3-ABs), N, two (4-aminophenyl) phthalic amides of N'-, N, two (3-aminophenyl) phthalic amides of N'-, N, benzenedicarboxamide between N'-two (4-aminophenyl), N, benzenedicarboxamide between N'-two (3-aminophenyl), two (4-aminophenyl) anthracenes of 9,10-, two (4-amino-benzene oxygen) diphenyl sulfones of 4,4'-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2'-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2'-, two (4-aminophenyl) HFC-236fa of 2,2'-, two (3-aminophenyl) HFC-236fa of 2,2'-, two (3-amino-4-aminomethyl phenyl) HFC-236fa of 2,2'-, two (4-aminophenyl) propane of 2,2'-, two (3-aminophenyl) propane of 2,2'-, two (3-amino-4-aminomethyl phenyl) propane of 2,2'-, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, two (4-amino-benzene oxygen) propane of 1,3-, two (3-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentanes of 1,5-, two (3-amino-benzene oxygen) pentanes of 1,5-, two (4-amino-benzene oxygen) hexanes of 1,6-, two (3-amino-benzene oxygen) hexanes of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, two (3-amino-benzene oxygen) heptane of 1,7-, two (4-amino-benzene oxygen) octanes of 1,8-, two (3-amino-benzene oxygen) octanes of 1,8-, two (4-amino-benzene oxygen) nonanes of 1,9-, two (3-amino-benzene oxygen) nonanes of 1,9-, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-amino-benzene oxygen) undecane, 1,11-(3-amino-benzene oxygen) undecane, 1,12-(4-amino-benzene oxygen) dodecane, 1,12-(3-amino-benzene oxygen) dodecane, 4-(amino methyl) aniline, 3-(amino methyl) aniline, the aromatic diamines such as 4-(2-amino-ethyl) aniline or 3-(2-amino-ethyl) aniline, two (4-aminocyclohexyl) methane, the alicyclic diamines such as two (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropanes, 1,4-Diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diamido heptane, 1,8-diamino-octane, 1,9-diamido nonane, 1,10-diamino decane, 1,11-diamido undecane, the aliphatic diamines such as 1,12-diamido dodecane.

In addition,, not destroying in the scope of effect of the present invention, can use the diamine compound representing with following formula [DA-1]～formula [DA-31].

[changing 28]

In formula [DA-1]～formula [DA-3], R ₁for-O-,-OCH ₂-,-CH ₂o-,-COOCH ₂-or-CH ₂oCO-, R ₂for the straight chain shape of the straight chain shape of the straight chain shape of carbon number 1～22 or branch-like alkyl, carbon number 1～22 or branch-like alkoxy, carbon number 1～22 or branch-like are containing straight chain shape or the branch-like fluoroalkoxy of fluoroalkyl or carbon number 1～22.

[changing 29]

In formula [DA-4]～formula [DA-6], R ₃for-COO-,-OCO-,-COOCH ₂-,-CH ₂oCO-,-CH ₂o-,-OCH ₂-or-CH ₂-, R ₄for the straight chain shape of the straight chain shape of the straight chain shape of carbon number 1～22 or branch-like alkyl, carbon number 1～22 or branch-like alkoxy, carbon number 1～22 or branch-like are containing straight chain shape or the branch-like fluoroalkoxy of fluoroalkyl or carbon number 1～22.

[changing 30]

In formula [DA-7] and formula [DA-8], R ₅expression-COO-,-OCO-,-COOCH ₂-,-CH ₂oCO-,-CH ₂o-,-OCH ₂-,-CH ₂-or-O-, R ₆represent 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], R ₇for straight chain shape or the branch-like alkyl of carbon number 3～12, for the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene, be respectively trans-isomer.

[changing 32]

In formula [DA-11] and formula [DA-12], R ₈for straight chain shape or the branch-like alkyl of carbon number 3～12, for the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene, be respectively trans-isomer.

[changing 33]

In formula [DA-13], A ₄for straight chain shape or the branch-like alkyl of the carbon number 3～20 that can be replaced by fluorine atom, A ₃for Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, A ₂for-O-or-COO-* (wherein key and the A of band " * " ₃in conjunction with), A ₁for-O-or-COO-* (the wherein key of band " * " and (CH ₂) a ₂in conjunction with).In addition a, ₁be 0 or 1 integer, a ₂be 2～10 integer, a ₃it is 0 or 1 integer.

[changing 34]

[changing 35]

[changing 36]

[changing 37]

[changing 38]

In addition, not destroying in the scope of effect of the present invention, can use the diamine compound representing with following formula [DA-32].

[changing 39]

In formula [DA-32], A ₁for be selected from-O-,-NH-,-N (CH ₃)-,-CONH-,-NHCO-,-CH ₂o-,-OCO-,-CON (CH ₃)-or-N (CH ₃) the divalent organic group of CO-, A ₂for aliphatic alkyl, non-aromatic ring type alkyl or the aromatic hydrocarbyl of singly-bound, carbon number 1～20.A ₃for singly-bound ,-O-,-NH-,-N (CH ₃)-,-CONH-,-NHCO-,-COO-,-OCO-,-CON (CH ₃)-,-N (CH ₃) CO-or-O (CH ₂) _m-, the integer that m is 1～5, A ₄for nitrogenous heteroaromatic.N is 1～4 integer.

In addition, only otherwise destroy effect of the present invention, can use and on two amine side chains, there is alkyl or the diamine compound containing fluoroalkyl.

The diamines specifically can example representing with following formula [DA-33]～formula [DA-44].

[changing 40]

In formula [DA-33]～formula [DA-37], A ₁for the straight chain shape of carbon number 1～22 or the straight chain shape of branch-like alkyl or carbon number 1～22 or branch-like are containing fluoroalkyl.

[changing 41]

In formula [DA-38]～formula [DA-43], A ₂for-COO-,-OCO-,-CONH-,-NHCO-,-CH ₂-,-O-,-CO-or-NH-, A ₃for the straight chain shape of carbon number 1～22 or the straight chain shape of branch-like alkyl or carbon number 1～22 or branch-like are containing fluoroalkyl.

[changing 42]

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

In addition, not destroying in the scope of effect of the present invention, also can use the diamine compound representing with following formula [DA-45]～formula [DA-52].

[changing 43]

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

In addition, not destroying in the scope of effect of the present invention, also can use the diamine compound in the molecule representing with following formula [DA-53]～formula [DA-57] with carboxyl.

[changing 44]

In formula [DA-53], m ₁it is 1～4 integer.In formula [DA-54], A ₄for singly-bound ,-CH ₂-,-C ₂h ₄-,-C (CH ₃) ₂-,-CF ₂-,-C (CF ₃) ₂-,-O-,-CO-,-NH-,-N (CH ₃)-,-CONH-,-NHCO-,-CH ₂o-,-OCH ₂-,-COO-,-OCO-,-CON (CH ₃)-or-N (CH ₃) CO-, m ₂and m ₃be respectively 0～4 integer independently, and m ₂+ m ₃it is 1～4 integer.In formula [DA-55], m ₂and m ₃be respectively 1～5 integer independently.In formula [DA-56], A ₄for straight chain shape or the branch-like alkyl of carbon number 1～5, m ₆it is 1～5 integer.In formula [DA-57], A ₆for singly-bound ,-CH ₂-,-C ₂h ₄-,-C (CH ₃) ₂-,-CF ₂-,-C (CF ₃) ₂-,-O-,-CO-,-NH-,-N (CH ₃)-,-CONH-,-NHCO-,-CH ₂o-,-OCH ₂-,-COO-,-OCO-,-CON (CH ₃)-or-N (CH ₃) CO-, m ₇it is 1～4 integer.

In addition, not destroying in the scope of effect of the present invention, also can use the diamine compound representing with following formula [DA-58] and formula [DA-59].

[changing 45]

Other above-mentioned diamine compound can be when making liquid crystal orientation film liquid crystal aligning, voltage retention, gather the characteristics such as electric charge and use a kind or be mixed with two or more.

The specific tetracarboxylic dianhydride > of <

In order to obtain particular polymers of the present invention, it is better tetracarboxylic dianhydride (also referred to as specific tetracarboxylic dianhydride) that the formula with following [3] the is represented part as raw material.

[changing 46]

Z ₁be specially the 4 valency groups that for example represent with following formula [3a]～[3j].

[changing 47]

In formula [3a], Z ₂～Z ₅for being selected from the group of hydrogen atom, methyl, chlorine atom or phenyl ring, respectively can be identical or different.

In formula [3g], Z ₆and Z ₇for hydrogen atom or methyl, respectively can be identical or different.

In formula [3], according to polymerisation reactivity and synthetic difficulty, Z ₁particularly preferred structure be formula [3a], formula [3c], formula [3d], formula [3e], formula [3f] or formula [3g].Wherein, be better formula [3a], formula [3e], formula [3f] or formula [3g].

Other tetracarboxylic dianhydride > of <

In the present invention, not destroying in the scope of effect of the present invention, can use other tetracarboxylic dianhydride (also referred to as other tetracarboxylic dianhydride) except specific tetracarboxylic dianhydride.As other tetracarboxylic dianhydride, can exemplify the tetracarboxylic dianhydride of tetrabasic carboxylic acid shown below:

Pyromellitic acid, 2, 3, 6, 7-naphthalenetetracarbacidic acidic, 1, 2, 5, 6-naphthalenetetracarbacidic acidic, 1, 4, 5, 8-naphthalenetetracarbacidic acidic, 2, 3, 6, 7-anthracene tetracarboxylic acid, 1, 2, 5, 6-anthracene tetracarboxylic acid, 3, 3', 4, 4'-bibenzene tetracarboxylic, 2, 3, 3', 4-bibenzene tetracarboxylic, two (3, 4-dicarboxyl phenyl) ether, 3, 3', 4, 4'-benzophenone tetracarboxylic acid, two (3, 4-dicarboxyl phenyl) sulfone, two (3, 4-dicarboxyl phenyl) methane, 2, 2-two (3, 4-dicarboxyl phenyl) propane, 1, 1, 1, 3, 3, 3-hexafluoro-2, 2-two (3, 4-dicarboxyl phenyl) propane, two (3, 4-dicarboxyl phenyl) dimethylsilane, two (3, 4-dicarboxyl phenyl) diphenyl silane, 2, 3, 4, 5-pyridine tetracarboxylic acid, 2, 6-two (3, 4-dicarboxyl phenyl) pyridine, 3, 3', 4, 4'-diphenyl sulfone tetracarboxylic acid, 3, 4, 9, 10-perylene tetracarboxylic acid, 1, 3-diphenyl-1, 2, 3, 4-cyclo-butane tetracarboxylic acid.

Above-mentioned specific tetracarboxylic dianhydride and other tetracarboxylic dianhydride can be when making liquid crystal orientation film liquid crystal aligning, voltage retention and gather the characteristics such as electric charge and use a kind or be mixed with two or more.

< particular polymers >

Particular polymers of the present invention be selected from two amine components are reacted with tetrabasic carboxylic acid composition and polyamic acid and make this polyamic acid dehydration closed-loop and at least a kind of polymkeric substance of polyimide.

Polyimide precursor is the structure representing with following formula [A].

[changing 48]

In formula [A], R ₁be 4 valency organic groups, R ₂for divalent organic group, A ₁and A ₂for the alkyl of hydrogen atom or carbon number 1～8, can be identical or different respectively.N represents positive integer.

Because can obtain more easily as raw material with the tetracarboxylic dianhydride who represents using following formula [C] by two amine components that the formula with following [B] is represented, therefore particular polymers of the present invention be better the polyamic acid that forms of the structural formula of the repetitive that represented by the formula with following [D] or make this polyamic acid imidizate and must polyimide.

[changing 49]

In formula [B], formula [C] and formula [D], R ₁and R ₂identical with the definition in formula [A].

In formula [A] and formula [D], R ₁and R ₂can be respectively a kind, or there is respectively different R ₁and R ₂, combine different multiple as repetitive.

In the present invention, the method for synthetic particular polymers is not particularly limited.Conventionally, make two amine components react and obtain with tetrabasic carboxylic acid composition.Generally make at least one the tetrabasic carboxylic acid composition that is selected from tetrabasic carboxylic acid and derivant thereof react with two amine components that comprise one or more diamine compounds, obtain polyamic acid.Specifically, can use tetracarboxylic dianhydride and two amine component polycondensations and obtain polyamic acid method, make tetrabasic carboxylic acid and two amine components dewater polycondensation reaction and obtain the method for polyamic acid or make tetrabasic carboxylic acid two carboxylic acid halides and two amine component polycondensations and obtain the method for polyamic acid.

In order to obtain polyamic acid Arrcostab, the method for the tetrabasic carboxylic acid that can use the esterification of carboxyl dialkyl group and the method for two amine component polycondensations, tetrabasic carboxylic acid two carboxylic acid halides that made the esterification of carboxyl dialkyl group and two amine component polycondensations or the carboxyl of polyamic acid is converted into the method for ester.

In order to obtain polyimide, can use above-mentioned polyamic acid or polyamic acid Arrcostab closed loop and form the method for polyimide.

Use in the liquid crystal orientation film that particular polymers of the present invention obtains, containing of the described particular side chain structure representing with formula [1A] or formula [1B] in above-mentioned two amine components is proportional higher, and the hydrophobicity can make to make liquid crystal orientation film time and the tilt angle of liquid crystal are higher.At this moment, two amine components be better use described in the particular side chain diamine compound that represents with formula [2A] or formula [2B].Particularly preferably use the particular side chain diamine compound representing with formula [2A].In order to improve this characteristic, be better that 5 % by mole above 80 % by mole of two amine components are particular side chain diamine compound below.Wherein, from the coating of aligning agent for liquid crystal with as the viewpoint of the electrical characteristics of liquid crystal orientation film, be better 5 % by mole of two amine components above 60 % by mole following be particular side chain diamine compound.

In order to obtain particular polymers of the present invention, be better the specific tetracarboxylic dianhydride who represents with formula [3] described in tetrabasic carboxylic acid composition uses.Particularly preferably using the Z1 in formula [3] is the tetracarboxylic dianhydride of the described structure representing with formula [3a]～formula [3j].At this moment, be better 1 % by mole of above specific tetracarboxylic dianhydride of being of tetrabasic carboxylic acid composition, be more preferably more than 5 % by mole, be further more preferably more than 10 % by mole.In addition, can make 100 % by mole of tetrabasic carboxylic acid composition is specific tetracarboxylic dianhydride.

Two amine components carry out in organic solvent with reacting conventionally of tetrabasic carboxylic acid composition.As the organic solvent at this moment using, as long as can dissolve the polyimide precursor of generation, be not particularly limited.Exemplify its object lesson below:

For example, DMF, DMA, METHYLPYRROLIDONE, dimethyl sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone etc.

They can be used alone, and also can mix use.In addition, even the solvent that cannot make polyimide precursor dissolve, in the scope that can not separate out at the polyimide precursor generating, can be mixed in above-mentioned solvent and use.In addition, the moisture in organic solvent hinders polyreaction, also can cause the polyimide precursor generating to be hydrolyzed, so organic solvent is better the solvent using after dehydrating.

When two amine components and tetrabasic carboxylic acid composition are reacted in organic solvent, can exemplify following method: stir make two amine components be dispersed or dissolved in organic solvent and solution, by tetrabasic carboxylic acid composition directly or be dispersed or dissolved in the method for adding after organic solvent; Otherwise, the method for adding two amine components in the solution obtaining to making tetrabasic carboxylic acid composition be dispersed or dissolved in organic solvent; The method that tetrabasic carboxylic acid composition and two amine components are alternately added etc.Can use any method wherein.In addition, two amine components or tetrabasic carboxylic acid composition use respectively in multiple situation of reacting, can under the state being pre-mixed, make its reaction, also can make its respectively reaction successively, can also make to react respectively and low-molecular-weight body hybrid reaction and obtain particular polymers.At this moment polymerization temperature can be selected the arbitrary temp of-20～150 DEG C, is better in the scope of-5～100 DEG C.In addition, reaction can carried out under concentration arbitrarily, if but concentration is too low, be difficult to obtain the particular polymers of high molecular, if excessive concentration, the viscosity of reactant liquor is too high and be difficult to stir.Therefore, be better 1～50 quality %, be more preferably 5～30 quality %.Can initial reaction stage carry out under high concentration, then append organic solvent.

In the polyreaction of polyimide precursor, the ratio of the total mole number of the total mole number of two amine components and tetrabasic carboxylic acid composition is better 0.8～1.2.Identical with common polycondensation reaction, this mol ratio is more close to 1.0, and the molecular weight of the polyimide precursor of generation is larger.

Polyimide of the present invention be make above-mentioned polyimide precursor closed loop and polyimide, can be used as the polymkeric substance for obtaining liquid crystal orientation film.

In polyimide of the present invention, the closed loop rate of acid amides acidic group (acid imide rate) is not necessary for 100%, can at random adjust according to purposes or object.

As the method that makes polyimide precursor imidizate, can exemplify by direct-fired the solution of polyimide precursor hot-imide or to the catalyzer acid imide that adds catalyzer in the solution of polyimide precursor.

Making polyimide precursor temperature when hot-imide in solution is 100～400 DEG C, is better 120～250 DEG C, is better to carry out when the water being generated by imidization reaction is expelled to outside system.

The catalysis imidizate of polyimide precursor can be by add base catalyst and acid anhydrides in the solution of polyimide precursor, at-20～250 DEG C, preferably at 0～180 DEG C, stirs and carry out.The amount of base catalyst, mole to count 0.5～30 times of acid amides acidic group, is better 2～20 times, and the amount of acid anhydrides, mole to count 1～50 times of acid amides acidic group, is better 3～30 times.As base catalyst, can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc., wherein pyridine has the appropriate alkalescence that the reaction of making is carried out, therefore preferred.As acid anhydrides, can exemplify acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc., wherein, while using acetic anhydride, be easy to react the purifying after finishing, therefore preferred.Adopt the acid imide rate of catalysis imidizate to control by adjusting catalytic amount and temperature of reaction, reaction time.

When the polyimide precursor that recovery generates from the reaction solution of polyimide precursor or polyimide or polyimide, reaction solution is dropped in solvent it is precipitated.As the solvent for precipitating, can exemplify methyl alcohol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water etc.Put in solvent and the polymkeric substance of precipitation can, after filtered and recycled, be dried in normal temperature or heating under normal pressure or decompression.In addition, if the polymkeric substance that repeats precipitation is reclaimed is dissolved in the organic solvent operation that also precipitation reclaims again 2～10 times again, can reduce the impurity in polymkeric substance.As solvent now, can exemplify such as alcohols, ketone, hydro carbons etc., if use 3 kinds of above solvents that are selected from these solvents, purification efficiency further improves, therefore desirable.

Consider in the inhomogeneity situation of operability by film strength, while forming polymkeric substance tunicle of polymkeric substance by its acquisition, polymkeric substance tunicle, the molecular weight of particular polymers of the present invention is to pass through GPC (gel permeation chromatography, Gel Permeation Chromatography) to haggle over be 5000～1000000 to the weight-average molecular weight measured of method, is more preferably 10000～150000.

< aligning agent for liquid crystal >

Aligning agent for liquid crystal of the present invention is the coating fluid that is used to form liquid crystal orientation film, is the coating fluid that is used to form the resin coating that comprises particular polymers and organic solvent.

All component of polymer in aligning agent for liquid crystal of the present invention can be all the particular polymers using in the present invention, also can in particular polymers of the present invention, be mixed with other polymkeric substance in addition.At this moment, the content of other polymkeric substance is in addition 0.5～15 quality %, is better 1～10 quality %.As other polymkeric substance in addition, can exemplify not polyimide precursor or the polyimide containing particular side chain structure.In addition, also can exemplify the polymkeric substance except polyimide precursor and polyimide, be specially acrylate copolymer, methacrylate polymer, polystyrene, polyamide etc.

From form the viewpoint of even tunicle by coating, the content of the organic solvent in aligning agent for liquid crystal of the present invention is better 70～99 quality %, is more preferably 80～99 quality %.Its content can be according to the target film thickness of liquid crystal orientation film and appropriate change.As organic solvent at this moment, as long as the organic solvent that can make particular polymers dissolve, be not particularly limited.Exemplify its object lesson below:

For example, DMF, DMA, METHYLPYRROLIDONE, dimethyl sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone etc.

They can be used alone, and also can mix use.

In aligning agent for liquid crystal of the present invention, not destroying in the scope of effect of the present invention, also can import the cross-linked compound with epoxy radicals, isocyanate group, oxetanyl, cyclic carbonate group, there is at least a kind of substituent cross-linked compound that is selected from hydroxyl, hydroxyalkyl and low-grade alkoxy alkyl, there is the cross-linked compound of polymerism unsaturated link etc.These substituting groups and polymerism unsaturated link must have more than 2 in cross-linked compound.

As thering is epoxy radicals, the cross-linked compound of isocyanate group etc., can exemplify for example bisphenol acetone glycidyl ether, phenol phenolic resin varnish, cresols phenolic resin varnish, triglycidyl group isocyanuric acid ester, the amino connection of four glycidyl group is stretched benzene, four glycidyl group m-xylene diamine, four glycidyl group-1, two (amino-ethyl) cyclohexanes of 3-, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl group diglycidyl ether, two (1-(2,3-glycidoxy)-1-trifluoromethyl-2,2, the 2-trifluoromethyl) benzene of 1,3-, two (2,3-glycidoxy) the octafluoro biphenyl of 4,4-, triglycidyl group para-aminophenol, four glycidyl group m-xylene diamine, 2-(4-(2,3-glycidoxy) phenyl)-2-(4-(two (4-(2, the 3-glycidoxy) phenyl) ethyls of 1,1-) phenyl) propane, 1, two (4-(1-(the 4-(2 of 3-, 3-glycidoxy) phenyl)-1-(4-(1-(4-(2,3-glycidoxy) phenyl)-1-Methylethyl) phenyl) ethyl) phenoxy group)-2-propyl alcohol etc.

As the cross-linked compound with oxetanyl, it is the cross-linked compound with at least 2 oxetanyls that represent with following formula [4].

[changing 50]

Be specially the cross-linked compound representing with following formula [4-1]～formula [4-11].

[changing 51]

[changing 52]

[changing 53]

As the cross-linked compound with cyclic carbonate group, it is the cross-linked compound with at least 2 cyclic carbonate group that represent with following formula [5].

[changing 54]

Be specially the cross-linked compound representing with following formula [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], the integer that n is 1～5.In formula [5-25], the integer that n is 1～5.In formula [5-36], the integer that n is 1～100.In formula [5-37], the integer that n is 1～10.

In addition, also can exemplify the polysiloxane with at least a kind of structure representing with following formula [5-38]～formula [5-40].

[changing 63]

In formula [5-38]～formula [5-40], R ₁, R ₂, R ₃, R ₄and R ₅be respectively alkyl, alkoxy, aliphatics ring or the aromatic ring of the structure that represents with formula [5], hydrogen atom, hydroxyl, carbon number 1～10 independently, at least 1 is the structure representing with formula [5].

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

[changing 64]

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

As thering is at least a kind of substituent cross-linked compound that is selected from hydroxyl and alkoxy, can exemplify the amino resins for example with hydroxyl or alkoxy, such as melamine resin, urea resin, guanamine resin, sweet urea-formaldehyde resins, succinamide-formaldehyde resin, ethene urea-formaldehyde resins etc.Specifically, can use amino hydrogen atom by the melamine derivative of methylol and/or alkoxy methyl replacement, benzoguanamine derivant, glycoluril etc.This melamine derivative or benzoguanamine derivant also can dimer or the existence of trimerical form.These compounds are better that every 1 triazine ring on average has 3 above 6 following methylol or alkoxy methyls.

As the example of such melamine derivative or benzoguanamine derivant, can exemplify the MX-750 that on average has 3.7 methoxies to replace as every 1 triazine ring of commercially available product, every 1 triazine ring on average has the MW-30 that 5.8 methoxies replace (being Sanwa Chemical Co., Ltd (three and ケミカ Le society) system above), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 melamines such as methoxy such as grade, Cymel 235, 236, 238, 212, 253, 254 melamines such as butoxymethyl such as methoxy such as grade, Cymel 506, the butoxymethyl melamines such as 508, the carboxylic methoxy isobutoxy methylated melamine such as Cymel 1141, the methoxy ethoxyl methyl benzoguanamines such as Cymel1123, the methoxy butoxymethyl benzoguanamines such as Cymel 1123-10, the butoxymethyl benzoguanamines such as Cymel 1128, the carboxylic methoxy ethoxyl methyl benzoguanamines such as Cymel 1125-80 (being Mitsui cyanamide Co., Ltd. (Mitsui サイア Na ミ De society) system above).In addition,, as the example of glycoluril, can exemplify the methoxyl methylolation glycolurils such as the methylolation such as butoxymethyl glycoluril, Cymel 1172 glycoluril, POWDERLINK 1174 such as Cymel 1170 etc.

As benzene or the phenoloid with hydroxyl or alkoxy, for example can exemplify 1,3,5-tri-(methoxy) benzene, 1,2,4-tri-(isopropoxy methyl) benzene, 1, two (sec-butoxy methyl) benzene, 2 of 4-, 6-dihydroxy methyl p-t-butyl phenol etc.

It is more specifically the cross-linked compound representing with following formula [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 link, can exemplify for example trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, bipentaerythrite five (methyl) acrylate, three (methyl) acryloyl-oxy base oxethyl trimethylolpropane, in the many glycidyl ethers of glycerine many (methyl) acrylate equimolecular, there is the cross-linked compound of 3 polymerism unsaturated groups, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxirane-bisphenol A-type two (methyl) acrylate, epoxypropane-bisphenol type two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol bisthioglycolate glycidyl ether two (methyl) acrylate, diethylene glycol diglycidyl ether two (methyl) acrylate, phthalic acid diglycidyl ester two (methyl) acrylate, in hydroxyl trimethylace tonitric DOPCP two (methyl) acrylate equimolecular, there is the cross-linked compound of 2 polymerism unsaturated groups, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate, 2-phenoxy group-2-hydroxypropyl (methyl) acrylate, 2-(methyl) acryloxy-2-hydroxypropyl phthalic ester, 3-chlorine-2-hydroxyl propyl group (methyl) acrylate, glycerine list (methyl) acrylate, 2-(methyl) acryloxy ethyl phosphonic acid ester, in N-methylol (methyl) acrylamide equimolecular, there is the cross-linked compound of 1 polymerism unsaturated group etc.

In addition, also can use the compound representing with following formula [7].

[changing 71]

In formula [7], E ₁for being selected from the group of hexamethylene ring, the own ring of dicyclo, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, fluorenes ring, anthracene nucleus and phenanthrene ring, E ₂for being selected from the group of following formula [7a] or formula [7b], the integer that n is 1～4.

[changing 72]

Above-claimed cpd is an example of cross-linked compound, is not limited in these compounds.In addition, the contained cross-linked compound of aligning agent for liquid crystal of the present invention can be a kind, also can two or more combination.

The content of the cross-linked compound in aligning agent for liquid crystal of the present invention is better 0.1～150 mass parts with respect to whole component of polymer 100 mass parts.Bring into play target effect for cross-linking reaction is carried out, and do not make the orientation of liquid crystal decline, be more preferably 0.1～100 mass parts with respect to whole component of polymer 100 mass parts, particularly preferably 1～50 mass parts.

In aligning agent for liquid crystal of the present invention, not destroying in the scope of effect of the present invention, as promoting the electric charge in liquid crystal orientation film move and promote the compound that the electric charge of the liquid crystal cell that uses this liquid crystal orientation film is removed, be better to add the nitrogen heterocyclic ring amines representing with following formula [M1]～formula [M156].This amines can directly make an addition in the solution of particular polymers, is preferably adjusted to concentration 0.1～10 quality %, is better to add after the solution of 1～7 quality % with suitable solvent.As this solvent, as long as the organic solvent that above-mentioned particular polymers is dissolved, be not particularly limited.

[changing 73]

[changing 74]

[changing 75]

[changing 76]

[changing 77]

[changing 78]

Not destroying in the scope of effect of the present invention, organic solvent (also referred to as poor solvent) or compound that the homogeneity of the thickness of polymkeric substance tunicle when aligning agent for liquid crystal of the present invention can use coating of liquid crystalline aligning agent and surface smoothness improve.The compound etc. that in addition, also can use the adaptation of liquid crystal orientation film and substrate to improve.

As the object lesson of the poor solvent that film thickness uniformity and surface smoothness are improved, can exemplify solvent shown below:

For example, ethanol, isopropyl alcohol, n-butyl alcohol, 2-butanols, isobutyl alcohol, the tert-butyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, isoamylol, tert-pentyl alcohol, 3-methyl-2-butanols, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-ethyl-n-butyl alcohol, 1-heptanol, 2-enanthol, 3-enanthol, 1-octanol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, cyclohexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2-ethyl-1, 3-hexanediol, dipropyl ether, butyl oxide, two hexyl ethers, two alkane, 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, dibutyl ethylene glycol ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4-heptanone, 3-ethoxy butylacetic acid ester, 1-methyl amyl acetic acid esters, 2-ethyl-butyl acetic acid esters, 2-ethylhexyl acetic acid esters, ethylene glycol acetate, ethylene acetate, propylene carbonate, ethylene carbonate, glycol monoethyl ether, ethylene glycol monoethyl ether, 2-(methoxymethoxy) ethanol, glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol list isoamyl oxide, ethylene glycol ether, 2-(own oxygen base) ethanol, furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, 1-(butoxy ethoxy) propyl alcohol, propylene glycol methyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, DPE, Tripropylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol acetate, ethylene acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, 2-(2-ethoxy ethoxy) 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, acetic acid propylene glycol ester list ether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid Methylethyl ester, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the organic solvent of low surface tension.

These poor solvents can use a kind, also can mix use multiple.While using poor solvent as above, be better 5～80 quality % of the organic solvent total amount that comprises in aligning agent for liquid crystal, more preferably 20～60 quality %.

As the compound of homogeneity or surface smoothness that can improve thickness, can exemplify fluorine class surfactant, siloxane type surfactants, nonionic surfactant etc.

More particularly, can exemplify for example eftop EF301, EF303, EF352 (Tuo Kaimu goods Co., Ltd. (トーケ system プロダクツ society) system), MEGAFACE F171, F173, R-30 (Dainippon Ink. & Chemicals Inc's (large Japanese イ Application キ society) 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 Co., Ltd (Asahi Glass society) system) etc.The usage ratio of these surfactants whole component of polymer 100 mass parts contained with respect to aligning agent for liquid crystal are better 0.01～2 mass parts, are more preferably 0.01～1 mass parts.

As the object lesson of the compound that the adaptation of liquid crystal orientation film and substrate is improved, can exemplify the shown below compound that contains functional silanes or the compound containing epoxy radicals:

For example, can exemplify 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-tri-ethoxy silylpropyl diethylenetriamine, N-trimethoxy silane base propyl group diethylenetriamine, 10-trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilicane alkyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxy silane base-3,6-diaza nonyl acetic acid esters, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330s of N-, two (the oxyethylene group)-APTESs of N-, ethylene glycol bisthioglycolate glycidyl ether, polyglycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerine diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N '-four glycidyl group m-xylene diamine, two (N, the N-diglycidyl amino methyl) cyclohexanes of 1,3-, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.

Use makes in the situation of the compound improving with the adaptation of substrate, and its use amount whole component of polymer 100 mass parts contained with respect to aligning agent for liquid crystal are better 0.1～30 mass parts, are more preferably 1～20 mass parts.If lower than 0.1 mass parts, cannot expect the effect that adaptation improves; If higher than 30 mass parts, liquid crystal aligning may variation.

During liquid crystal aligning of the present invention is processed, the compound improving except above-mentioned cross-linked compound, poor solvent, the homogeneity that makes thickness and surface smoothness and the compound that makes to improve with the adaptation of substrate, as long as not destroying in the scope of effect of the present invention, can add dielectric or the conductive materials of the electrical specification such as specific inductive capacity and electric conductivity for changing liquid crystal orientation film.

< liquid crystal orientation film and liquid crystal display cells >

Aligning agent for liquid crystal of the present invention can, coating on substrate and after burning till, carry out orientation process by friction treatment or illumination etc., thereby use as liquid crystal orientation film.

In addition,, in the situation of vertical orientated purposes etc., in the situation that not carrying out orientation process, also can be used as liquid crystal orientation film and use.

As the substrate now using, as long as the high substrate of the transparency, be not particularly limited, can use the plastic base such as glass substrate and acrylic acid substrate and polycarbonate substrate etc.From the viewpoint of work simplification, preferably use the substrate being formed with for the ITO electrode of liquid crystal drive etc.In addition, in the liquid crystal display cells of reflection-type, can only adopt the opaque substrates such as silicon wafer at the substrate of a side, the electrode in this situation also can use the catoptrical materials such as aluminium.

The coating process of aligning agent for liquid crystal is not particularly limited, industrial general employing serigraphy, hectographic printing, flexographic printing, ink-jet method etc.As other coating process, also have dip coating, rolling method, slot coated, spin-coating method, spraying process etc., can use these methods according to object.

After aligning agent for liquid crystal is coated on substrate, by the heater meanses such as heating plate, thermal cycle type baking oven, IR (infrared ray) type baking oven 50～300 DEG C, be better 80～250 DEG C and make solvent evaporation, thereby can be made into polymkeric substance tunicle.If the thickness of the polymkeric substance tunicle after burning till is excessive, aspect the power consumption of liquid crystal display cells, be disadvantageous, if too small, the reliability of liquid crystal display cells may reduce, so be better 5～300nm, is more preferably 10～100nm.Make in the situation of liquid crystal horizontal alignment or tilted alignment, the polymkeric substance tunicle after burning till is processed by friction, polarized UV rays irradiation etc.

Liquid crystal display cells of the present invention is to be obtained after the substrate with liquid crystal orientation film by aligning agent for liquid crystal of the present invention by said method, makes liquid crystal cell, thereby make liquid crystal display cells by known method.

As the method for making of liquid crystal cell, can the following method of example: a pair of substrate of preparing to be formed with liquid crystal orientation film, on the liquid crystal orientation film of a substrate, scatter sept, be positioned at bonding another piece substrate of mode of inner side with liquid crystal aligning face, the method for liquid crystal sealing is injected in decompression; To being scattered with after the liquid crystal aligning face dropping liquid crystalline substance of sept, adhesive base plate method of sealing etc.

In addition, the liquid crystal display cells that aligning agent for liquid crystal of the present invention is also preferred for having liquid crystal layer between a pair of substrate that possesses electrode and makes through following operation: configuration packet, containing the liquid-crystal composition of the polymerizable compound by least one party's polymerization in active energy beam and heat, alively makes polymerizable compound polymerization by irradiating active energy beam and adding at least one method of hankering to executing between electrode simultaneously between a pair of substrate.Here, as active energy beam, be better ultraviolet ray.As ultraviolet ray, wavelength is 300～400nm, is better 310～360nm.Adopt in the situation of polymerization of heating, heating-up temperature is 40～120 DEG C, is better 60～80 DEG C.In addition, can carry out ultraviolet ray irradiates and heats simultaneously.

Above-mentioned liquid crystal display cells is by the tilt angle of PSA (Polymer Sustained Alignment, polymer stabilizing orientation) mode control liquid crystal molecule.For PSA mode, in liquid crystal material, sneak in advance a small amount of optical polymerism compound, for example photopolymerization monomer, after assembling liquid crystal cell, under the state that applies assigned voltage to liquid crystal layer to optical polymerism compound irradiation ultraviolet radiation etc., by the tilt angle of the polymer controls liquid crystal molecule that generates.The state of orientation that generates liquid crystal molecule when polymkeric substance also can be remembered removing after voltage, so the electric field etc. that can be formed at liquid crystal layer by control is adjusted the tilt angle of liquid crystal molecule.In addition, PSA mode does not need friction treatment, so be suitable for being difficult to control by friction treatment the formation of the vertical alignment-type liquid crystal layer of tilt angle.

; in liquid crystal display cells of the present invention; can after obtaining the substrate with liquid crystal orientation film by aligning agent for liquid crystal of the present invention, the method by above-mentioned make liquid crystal cell; by ultraviolet irradiation and add at least one method of hankering by polymerizable compound polymerization, thereby control the orientation of liquid crystal molecule.

If exemplify the example that the liquid crystal cell of PSA mode is made, can exemplify following method: a pair of substrate of preparing to be formed with liquid crystal orientation film, on the liquid crystal orientation film of a substrate, scatter sept, be positioned at bonding another piece substrate of mode of inner side with liquid crystal aligning face, the method for liquid crystal sealing is injected in decompression; To method that is scattered with adhesive base plate after the liquid crystal aligning face dropping liquid crystalline substance of sept and seal etc.

In liquid crystal, mix by heating or ultraviolet ray and irradiate and the polymerizable compound of polymerization.As polymerizable compound, can exemplify the compound in molecule with 1 above polymerism unsaturated group such as acrylate-based or methacrylate based.At this moment, polymerizable compound is better 0.01～10 mass parts with respect to 100 mass parts liquid crystal compositions, is more preferably 0.1～5 mass parts.If polymerizable compound is less than 0.01 mass parts, not polymerization of polymerizable compound and cannot carry out the orientation control of liquid crystal; If more than 10 mass parts, unreacted polymerizable compound is many, and the sintering adhesion characteristics of liquid crystal display cells declines.

Make after liquid crystal cell, liquid crystal cell is applied to the voltage of interchange or direct current, heating or irradiation ultraviolet radiation make polymerizable compound polymerization simultaneously.Take this, can control the orientation of liquid crystal molecule.

In addition, aligning agent for liquid crystal of the present invention is also preferred for the liquid crystal display cells of making through following operation: between a pair of substrate that possesses electrode, have liquid crystal layer, between described a pair of substrate, configuration packet, containing the liquid crystal orientation film of the polymerizable group by least one party's polymerization in active energy beam and heat, applies voltage between electrode.Here, as active energy beam, be better ultraviolet ray.As ultraviolet ray, wavelength is 300～400nm, is better 310～360nm.Adopt in the situation of polymerization of heating, heating-up temperature is 40～120 DEG C, is better 60～80 DEG C.In addition, can carry out ultraviolet ray irradiates and heats simultaneously.

In order to obtain the liquid crystal orientation film comprising by the polymerizable group of at least one party's polymerization in active energy beam and heat, can exemplify in aligning agent for liquid crystal and add the method for compound or the method for the component of polymer that use comprises polymerizable group that comprise this polymerizable group.Aligning agent for liquid crystal of the present invention comprises and has the specific compound that irradiates two keys position of reacting by heat or ultraviolet ray, therefore can be irradiated and be added at least one party who hankers and control by ultraviolet ray the orientation of liquid crystal molecule.

If exemplify the example that liquid crystal cell is made, can exemplify following method: preparation is formed with a pair of substrate of liquid crystal orientation film, on the liquid crystal orientation film of a substrate, scatter sept, be positioned at bonding another piece substrate of mode of inner side with liquid crystal aligning face, the method for liquid crystal sealing is injected in decompression; To method that is scattered with adhesive base plate after the liquid crystal aligning face dropping liquid crystalline substance of sept and seal etc.

Make after liquid crystal cell, by heating or irradiation ultraviolet radiation in the voltage that liquid crystal cell is applied to interchange or direct current, can control the orientation of liquid crystal molecule.

As mentioned above, use the reliability of the liquid crystal display cells that aligning agent for liquid crystal of the present invention makes good, can perform well in the LCD TV of large picture, fine etc.

Embodiment

Below exemplify embodiment the present invention is carried out to more specific description, but the present invention is not limited in these embodiment.

[synthesizing of particular side chain diamine compound]

The analytical equipment and the analysis condition that in the qualification of particular side chain diamine compound of the present invention, adopt are as described below.

( ¹the mensuration of H-NMR)

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

Measure solvent: CDCl ₃(deuterochloroform) and DMSO-d ₆(deuterated dimethyl sulfoxide)

Standard substance: TMS (tetramethylsilane) (δ: 0.0ppm, ¹and CDCl H) ₃(δ: 77.0ppm, ¹³c)

< embodiment 1>

Synthesizing of particular side chain diamine compound (1)

[changing 79]

(a) in the DMF of (30.0g, 109mmol) (dimethyl formamide) solution (190ml), add K to amphyl ₂cO ₃(sal tartari) (18.1g, 131mmol) and KI (potassium iodide) (1.81g, 10.9mmol), heat to 60 DEG C.Drip wherein propargyl bromide (19.5g, 164mmol), react 24 hours.Then, by reaction solution injected water (360ml).The solid that isolated by filtration is separated out, by the solid of gained stirring and washing in methyl alcohol, obtains rough thing (receipts amount: 32.5g, the yield: 95%) of propargyl ether body (b).The rough thing of gained is directly used in follow-up reaction.

Propargyl ether body (b):

¹H-NMR(CDCl ₃,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]

In THF (tetrahydrofuran) solution (106ml) of 3,5-dinitro iodobenzene (c) (23.5g, 80.1mmol), add PdCl ₂(PPh ₃) ₂(0.562g, 0.801mmol), CuI (cupric iodide (I)) (0.305g, 1.60mmol) and Et ₂after NH (diethylamine) (7.61g, 104mmol), cooling with water-bath.To the THF solution (22.0ml) that drips propargyl ether body (b) (32.5g, 104mmol) in this solution.Stir 1 hour, by reaction solution injected water (560ml).The solid that isolated by filtration is separated out, carries out recrystallization by the solid of gained with the mixed solvent of ethyl acetate and hexane, obtains dinitro matrix (d) (receipts amount: 23.6g, yield: 62%).

Dinitro matrix (d):

¹H-NMR(CDCl ₃,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(CDCl ₃,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]

To dinitro matrix (d) (23.3g, in THF (131ml) 48.7mmol) and the mixed solution of toluene (134ml), add Pd/C (palladium carbon) (2.33g), under hydrogen atmosphere, stir in room temperature.React after 96 hours, remove Pd/C by filtration.Concentrated filtrate, by Isosorbide-5-Nitrae-bis-for solid of gained the mixed solvent of alkane and hexane carries out recrystallization, obtains particular side chain diamine compound (1) (receipts amount: 11.9g, yield: 58%).

Particular side chain diamine compound (1):

¹H-NMR(CDCl ₃,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(CDCl ₃,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.

< embodiment 2>

Synthesizing of particular side chain diamine compound (2)

[changing 82]

(a) in the DMF solution (64.0ml) of (30.0g, 109mmol), add K to amphyl ₂cO ₃(27.2g, 197mmol), KI (0.907g, 5.47mmol) and the chloro-1-pentyne of 5-(15.7g, 153mmol), heat to 100 DEG C, reacts 48 hours.Then, add DMF (95.0ml) after being cooled to 25 DEG C, in this reaction solution, drip water (30ml), reaction is stopped.By in this reaction mixture injected water (150ml), the solid that isolated by filtration is separated out.The solid of gained is carried out to recrystallization with the mixed solvent of ethyl acetate and methyl alcohol, obtain ether body (e) (receipts amount: 33.7g, yield: 91%).

Ether body (e):

¹H-NMR(CDCl ₃,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(CDCl ₃,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]

In the THF solution (90ml) of 3,5-dinitro iodobenzene (c) (20.0g, 68.0mmol), add PdCl ₂(PPh ₃) ₂(0.477g, 0.680mmol), CuI (0.259g, 1.36mmol) and Et ₂after NH (6.47g, 88.4mmol), cooling with water-bath.To the THF solution (45.0ml) that drips end acetylene body (e) (30.1g, 88.4mmol) in this solution.Stir 20 hours, by reaction solution injected water (600ml).The solid that isolated by filtration is separated out, carries out recrystallization by the solid of gained with the mixed solvent of THF and methyl alcohol, obtains dinitro matrix (f) (receipts amount: 30.0g, yield: 87%).

Dinitro matrix (f):

¹H-NMR(CDCl ₃,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(CDCl ₃,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]

In the THF (167ml) of dinitro matrix (f) (29.7g, 58.6mmol) and the mixed solution of toluene (172ml), add Pd/C (2.97g), under hydrogen atmosphere, stir in room temperature.React after 72 hours, remove Pd/C by filtration.Concentrated filtrate, carries out recrystallization by the solid of gained with the mixed solvent of THF and hexane, obtains particular side chain diamine compound (2) (22.1g, 84%).

Particular side chain diamine compound (2):

¹H-NMR(CDCl ₃,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(CDCl ₃,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.

< embodiment 3>

Synthesizing of particular side chain diamine compound (3)

[changing 85]

Terminad acetylene body (e) (17.0g, in THF solution (96.0ml) 49.9mmol) with the THF solution (80.0ml) of 1 equivalent (80.0mmol) of 1 hour dropping catecholborane, 80 DEG C of return stirrings 24 hours.Then, let cool after 25 DEG C, to the aqueous hydrochloric acid solution (150ml) that adds 2 equivalents in reaction solution, stir 2 hours, in injected water (2000ml).The solid that isolated by filtration is separated out, obtains boronic acid derivatives (h) with hexane cleaning.The boronic acid derivatives of gained is 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 (PPh ₃) ₄isosorbide-5-Nitrae-bis-of (0.530g, 0.459mmol) in alkane solution (55.7ml), add the wet chemical (55.7ml) of 2.0mol/L, stir 2 hours at 80 DEG C.Then, carry out separatory with ethyl acetate and water, by organic layer dried over mgso.The solid that concentrated organic layer is obtained carries out column chromatography with ethyl acetate and hexane and separates, and obtains dinitro matrix (m) (13.1g, 59%).

Dinitro matrix (m):

¹H-NMR(CDCl ₃,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]

In the THF solution (130ml) of dinitro matrix (m) (13.0g, 25.6mmol), add Pd/C (1.30g), under hydrogen atmosphere, stir in room temperature.React after 24 hours, remove Pd/C by filtration.In filtrate, add activated charcoal to stir 2 hours, by removing by filter activated charcoal.Then, concentrated filtrate, obtains particular side chain diamine compound (3) (11.0g, 95%).

Particular side chain diamine compound (3):

¹H-NMR(CDCl ₃,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(CDCl ₃,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.

[synthesizing of polyimide precursor and polyimide]

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

(tetracarboxylic dianhydride)

CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride

BODA: two ring [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride

TCA: the tetracarboxylic dianhydride shown in following formula

TDA: the tetracarboxylic dianhydride shown in following formula

[changing 88]

(particular side chain diamine compound)

A-1: the particular side chain diamine compound (1) obtaining by the synthesis path of embodiment 1

A-2: the particular side chain diamine compound (2) obtaining by the synthesis path of embodiment 2

A-3: the particular side chain diamine compound (3) obtaining by the synthesis path of embodiment 3

[changing 89]

(other diamine compound)

P-PDA: p-phenylenediamine (PPD)

M-PDA: m-phenylene diamine

DBA:3,5-diaminobenzoic acid

AP18:1,3-diamido-4-octadecyl oxygen base benzene

[changing 90]

(organic solvent)

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

BCS: butyl cellosolve

Mensuration, being determined as follows of acid imide rate of molecular weight are carried out.

(molecular weight determination)

The molecular weight of the polyimide in synthesis example uses normal temperature gel permeation chromatography (GPC) device (GPC-101) (Showa Denko K. K (clear and Electricity work society) system), post (KD-803, KD-805) (Xiao De Ces Co.,Ltd (Shodex society) system), measures as follows.

Column temperature: 50 DEG C

Eluent: N, and N '-dimethyl formamide (as adjuvant, lithium bromide monohydrate (LiBrH ₂o) be 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) is 30mmol/L, and tetrahydrofuran (THF) is 10mL/L)

Flow velocity: 1.0ml/ minute

Calibration curve making standard model: TSK standard polyethylene oxide (molecular weight: approximately 900000,150000,100000 and 30000) ((East ソー society of TOSOH Co., Ltd) system) and polyglycol (molecular weight approximately 12000,4000 and 1000) (polymkeric substance laboratory company (Port リマーラボラトリー society) system).

(mensuration of acid imide rate)

20mg polyimide powder is added to NMR sample hose (NMR sampling pipe standard form φ 5 (wasteland's science Co., Ltd. (wasteland's science society) system)), add 0.53ml deuterated dimethyl sulfoxide (DMSO-d6,0.05 quality %TMS (tetramethylsilane) melange), apply ultrasound wave it is dissolved completely.By NMR analyzer (JNW-ECA500) (NEC De Tamu Co., Ltd. (Japanese Electricity データ system society) system) proton N MR to this measured in solution 500MHz.For acid imide rate, taking the proton that derives from unchanged structure before and after imidizate as benchmark proton, use this proton peak integrated value and appear near the integrated value at the peak of the NH base that derives from amic acid 9.5～10.0ppm, try to achieve acid imide rate by following formula.

Acid imide rate (%)=(1-α x/y) × 100

In above formula, x is the proton peak integrated value that derives from the NH base of amic acid, and y is the peak integrated value of benchmark proton, when α is polyamic acid (acid imide rate is 0%) with respect to the number ratio of the benchmark proton of the proton of the NH value of 1 amic acid.

< embodiment 4>

By CBDA (4.50g, 22.9mmol), A-1 (1.94g, 4.6mmol) and p-PDA (1.99g, 18.4mmol) in NMP (25.3g), mix, 40 DEG C of reactions, after 5.5 hours, obtaining resin solid constituent concentration is the polyamic acid solution (1) of 25.0 quality %.The number-average molecular weight of this polyamic acid is 25900, and weight-average molecular weight is 78100.

< embodiment 5>

By BODA (3.83g, 15.3mmol), A-1 (2.59g, 6.1mmol) and DBA (2.17g, 14.3mmol) in NMP (15.8g), mix, after 4 hours, add CBDA (1.00g 80 DEG C of reactions, 5.1mmol) and NMP (12.9g), 40 DEG C of reactions 6 hours, obtaining resin solid constituent concentration was the polyamic acid solution of 25.0 quality %.

In the polyimide solution obtaining (20.1g), add NMP, after dilution is 6 quality %, add acetic anhydride (2.45g) and pyridine (1.85g) as imidization catalyst, 80 DEG C of reactions 4.5 hours.This reaction solution is dropped in methyl alcohol (350ml) to the sediment of isolated by filtration gained.By this sediment washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (2).The acid imide rate of this polyimide is 55%, and number-average molecular weight is 22100, and weight-average molecular weight is 60100.

< embodiment 6>

By BODA (2.37g, 9.5mmol), A-2 (2.56g, 5.7mmol) and DBA (2.02g, 13.3mmol) in NMP (14.6g), mix, after 4 hours, add CBDA (1.86g 80 DEG C of reactions, 9.5mmol) and NMP (11.9g), 40 DEG C of reactions 6 hours, obtaining resin solid constituent concentration was the polyamic acid solution (3) of 25.0 quality %.The number-average molecular weight of this polyamic acid is 23500, and weight-average molecular weight is 72600.

< embodiment 7>

Add NMP to the polyamic acid solution (3) obtaining in embodiment 6 in (20.0g), after dilution is 6 quality %, add acetic anhydride (4.50g) and pyridine (3.25g) as imidization catalyst, 90 DEG C of reactions 3.5 hours.This reaction solution is dropped in methyl alcohol (450ml) to the sediment of isolated by filtration gained.By this sediment washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (4).The acid imide rate of this polyimide is 80%, and number-average molecular weight is 19500, and weight-average molecular weight is 50100.

< embodiment 8>

By BODA (3.04g, 12.2mmol), A-3 (2.34g, 5.2mmol), m-PDA (0.56g, 5.2mmol) and DBA (1.06g, 7.0mmol) in NMP (13.2g), mix, after 5 hours, add CBDA (1.02g, 5.2mmol) and NMP (10.8g) 80 DEG C of reactions, 40 DEG C of reactions 6.5 hours, obtaining resin solid constituent concentration was the polyamic acid solution of 25.0 quality %.

In the polyimide solution obtaining (20.0g), add NMP, after dilution is 6 quality %, add acetic anhydride (4.51g) and pyridine (3.25g) as imidization catalyst, 90 DEG C of reactions 3.5 hours.This reaction solution is dropped in methyl alcohol (450ml) to the sediment of isolated by filtration gained.By this sediment washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (5).The acid imide rate of this polyimide is 81%, and number-average molecular weight is 18300, and weight-average molecular weight is 47400.

< embodiment 9>

By BODA (2.11g, 8.4mmol), A-3 (2.28g, 5.1mmol), p-PDA (0.36g, 3.3mmol) and DBA (1.28g, 8.4mmol) in NMP (12.7g), mix, after 5 hours, add CBDA (1.65g, 8.4mmol) and NMP (10.5g) 80 DEG C of reactions, 40 DEG C of reactions 6.5 hours, obtaining resin solid constituent concentration was the polyamic acid solution of 25.0 quality %.

In the polyimide solution obtaining (20.0g), add NMP, after dilution is 6 quality %, add acetic anhydride (4.50g) and pyridine (3.31g) as imidization catalyst, 90 DEG C of reactions 3.5 hours.This reaction solution is dropped in methyl alcohol (450ml) to the sediment of isolated by filtration gained.By this sediment washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (6).The acid imide rate of this polyimide is 68%, and number-average molecular weight is 19300, and weight-average molecular weight is 50900.

< embodiment 10>

By TCA (4.48g, 20.0mmol), A-1 (1.70g, 4.0mmol) and DBA (2.44g, 16.0mmol) in NMP (25.8g), mix, 40 DEG C of reactions, after 6 hours, obtaining resin solid constituent concentration is the polyamic acid solution (7) of 25.0 quality %.The number-average molecular weight of this polyamic acid is 24200, and weight-average molecular weight is 75800.

< embodiment 11>

Add NMP to the polyamic acid solution (7) obtaining in embodiment 11 in (20.5g), after dilution is 6 quality %, add acetic anhydride (1.91g) and pyridine (1.50g) as imidization catalyst, 80 DEG C of reactions 4 hours.This reaction solution is dropped in methyl alcohol (350ml) to the sediment of isolated by filtration gained.By this sediment washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (8).The acid imide rate of this polyimide is 58%, and number-average molecular weight is 20700, and weight-average molecular weight is 55100.

< embodiment 12>

By TCA (4.48g, 20.0mmol), A-3 (2.72g, 6.0mmol), p-PDA (0.65g, 6.0mmol) and DBA (1.22g, 8.0mmol) in NMP (27.2g), mix, 40 DEG C of reactions, after 6 hours, obtaining resin solid constituent concentration is the polyamic acid solution of 25.0 quality %.

In the polyimide solution obtaining (20.0g), add NMP, after dilution is 6 quality %, add acetic anhydride (1.90g) and pyridine (1.45g) as imidization catalyst, 80 DEG C of reactions 4 hours.This reaction solution is dropped in methyl alcohol (350ml) to the sediment of isolated by filtration gained.By this sediment washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (9).The acid imide rate of this polyimide is 55%, and number-average molecular weight is 21400, and weight-average molecular weight is 56900.

< embodiment 13>

By TDA (1.77g, 5.9mmol), A-2 (2.66g, 5.9mmol) and DBA (2.09g, 13.7mmol) in NMP (15.2g), mix, after 5.5 hours, add CBDA (2.68g 80 DEG C of reactions, 13.7mmol) and NMP (12.5g), 40 DEG C of reactions 6 hours, obtaining resin solid constituent concentration was the polyamic acid solution of 25.0 quality %.

In the polyimide solution obtaining (20.0g), add NMP, after dilution is 6 quality %, add acetic anhydride (4.50g) and pyridine (3.30g) as imidization catalyst, 90 DEG C of reactions 3.5 hours.This reaction solution is dropped in methyl alcohol (500ml) to the sediment of isolated by filtration gained.By this sediment washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (10).The acid imide rate of this polyimide is 82%, and number-average molecular weight is 19400, and weight-average molecular weight is 48300.

< embodiment 14>

By TDA (4.06g, 13.5mmol), A-3 (3.65g, 8.1mmol) and p-PDA (2.05g, 19.0mmol) in NMP (20.5g), mix, after 5.5 hours, add CBDA (2.65g 80 DEG C of reactions, 13.5mmol) and NMP (16.8g), 40 DEG C of reactions 6 hours, obtaining resin solid constituent concentration was the polyamic acid solution of 25.0 quality %.

In the polyimide solution obtaining (20.5g), add NMP, after dilution is 6 quality %, add acetic anhydride (1.95g) and pyridine (1.50g) as imidization catalyst, 80 DEG C of reactions 4 hours.This reaction solution is dropped in methyl alcohol (350ml) to the sediment of isolated by filtration gained.By this sediment washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (11).The acid imide rate of this polyimide is 56%, and number-average molecular weight is 21100, and weight-average molecular weight is 52500.

< comparative example 1>

By BODA (2.36g, 9.4mmol), AP18 (2.13g, 5.7mmol) and DBA (2.01g, 13.2mmol) in NMP (14.0g), mix, after 4 hours, add CBDA (1.85g 80 DEG C of reactions, 9.4mmol) and NMP (11.0g), 40 DEG C of reactions 6 hours, obtaining resin solid constituent concentration was the polyamic acid solution (12) of 25.0 quality %.The number-average molecular weight of this polyamic acid is 24200, and weight-average molecular weight is 74100.

< comparative example 2>

Add NMP to the polyamic acid solution (12) obtaining in synthesis example 1 in (20.0g), after dilution is 6 quality %, add acetic anhydride (4.50g) and pyridine (3.20g) as imidization catalyst, 90 DEG C of reactions 3.5 hours.This reaction solution is dropped in methyl alcohol (450ml) to the sediment of isolated by filtration gained.By this sediment washed with methanol, at 100 DEG C of drying under reduced pressure, obtain polyimide powder (13).The acid imide rate of this polyimide is 80%, and number-average molecular weight is 19900, and weight-average molecular weight is 51600.

For the polyamic acid and the polyimide that obtain in embodiment 4～14, comparative example 1 and 2, gather 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, record the preparation example of aligning agent for liquid crystal.For the aligning agent for liquid crystal of gained, gather and be shown in table 38.

[table 38]

[making of liquid crystal orientation film], [the hydrophobicity evaluation of liquid crystal orientation film], [invasion on the liquid crystal orientation film of liquid crystal is evaluated], [making (conventional box) of liquid crystal cell], [making (PSA box) of liquid crystal cell] and [evaluation of tilt angle] are carried out as follows.

The characteristic of the each liquid crystal orientation film obtaining in embodiment 15～25, comparative example 3 and 4 in addition, gathers and is shown in table 39～42.

In table 39, represent the hydrophobic evaluation result of liquid crystal orientation film, in table 40, represent the evaluation result of the invasion on the liquid crystal orientation film of liquid crystal, in table 41, represent the evaluation result of the tilt angle that uses conventional box, in table 42, represent the evaluation result of the tilt angle that uses PSA box.

[making of liquid crystal orientation film]

Aligning agent for liquid crystal is spun on to the ito surface of the substrate with ITO electrode of 30mm × 40mm, on heating plate in 80 DEG C of heat treated 5 minutes, again in thermal cycle type cleaning oven in 230 DEG C of heat treated 30 minutes, obtain the substrate of the polyimide liquid crystal direct action membrane with thickness 100nm.

[the hydrophobicity evaluation of liquid crystal orientation film]

Use the substrate with liquid crystal orientation film obtaining in [making of liquid crystal orientation film], measured the contact angle with water.At this moment, higher with the contact angle of water, hydrophobicity is high, and lower with the contact angle of water, hydrophobicity is lower.Use automatic contact angle meter CA-Z type (the consonance (Association of interface science Co., Ltd. and interface science society) system with the mensuration of the contact angle of water).

[invasion on the liquid crystal orientation film of liquid crystal is evaluated]

Use the substrate with liquid crystal orientation film obtaining in [making of liquid crystal orientation film], measured the contact angle of liquid crystal.At this moment, measure the contact angle that drips the liquid crystal of liquid crystal after 10 seconds, the lower liquid crystal orientation film of contact angle of liquid crystal, the invasion on the liquid crystal orientation film of liquid crystal is better, the higher liquid crystal orientation film of contact angle of liquid crystal, the invasion on the liquid crystal orientation film of liquid crystal is poorer.Liquid crystal uses MLC-6608 (Merck Japanese firm (メ Le Network ジャパ Application society) system), and the mensuration of contact angle is used automatic contact angle meter CA-Z type (consonance interface science Co., Ltd. system).

[making (conventional box) of liquid crystal cell]

Aligning agent for liquid crystal is spun on to the ito surface of the substrate with ITO electrode of 30mm × 40mm, on heating plate in 80 DEG C of heat treated 5 minutes, again in thermal cycle type cleaning oven in 230 DEG C of heat treated 45 minutes, obtain the ito substrate of the polyimide liquid crystal direct action membrane with thickness 100nm.Rubbing device by roller footpath 120mm carries out friction treatment with the condition of roller rotating speed 1000rpm, roller gait of march 50mm/ second, the amount of pushing 0.1mm to the coated surface of this ito substrate with rayon cloth.

Prepare the ito substrate with liquid crystal orientation film of 2 gained, the sept that the mode inside being positioned at liquid crystal aligning face clips 6 μ m combines, will be bonding around with sealant, make sylphon.Inject MLC-6608 (Merck Japanese firm system) to this sylphon by decompression injection method, by inlet sealing, obtain liquid crystal cell (conventional box).

For the liquid crystal cell obtaining in embodiment and comparative example, observe the orientation homogeneity of liquid crystal is confirmed by polarizing microscope.These liquid crystal cells all do not follow the grinding of friction treatment bad with orientation, and liquid crystal is evenly orientated.

[making (PSA box) of liquid crystal cell]

Aligning agent for liquid crystal is spun on to the substrate with ITO electrode of pattern spacing 20 μ m of 10mm × 10mm and the ito surface of the substrate with ITO electrode of 10mm × 40mm, on heating plate in 80 DEG C of heat treated 5 minutes, again in thermal cycle type cleaning oven in 230 DEG C of heat treated 30 minutes, obtain the polyimide coating film of thickness 100nm.Clean after coated surface with pure water, in thermal cycle type cleaning oven, in 100 DEG C of heat treated 15 minutes, obtain the substrate with liquid crystal orientation film.

For this substrate with liquid crystal orientation film, the sept that the mode inside being positioned at liquid crystal aligning face clips 6 μ m combines, will be bonding around with sealant, make sylphon.Ratio taking the MLC-6608 with respect to 100 quality % as 0.3 quality % is mixed the polymerizable compound (1) representing with following formula in MLC-6608 (Merck Japanese firm system), inject this sylphon by decompression injection method, by inlet sealing, obtain liquid crystal cell again.

[changing 91]

For the liquid crystal cell of gained, in applying the voltage that exchanges 5V, use the metal halide lamp of illumination 60mW, the wavelength below shielding 350nm, carries out being scaled 20J/cm with 365nm ²ultraviolet ray irradiate, obtain the controlled liquid crystal cell (PSA box) of direction of orientation of liquid crystal.Temperature in irradiation unit during to liquid crystal cell irradiation ultraviolet radiation is 50 DEG C.

Ultraviolet pre-irradiation to this liquid crystal cell and the response speed of ultraviolet postradiation liquid crystal are measured.For response speed, measure the T90 → T10 of transmissivity 90% to transmissivity 10%.In the PSA box obtaining in embodiment and comparative example, compared with the liquid crystal cell of ultraviolet pre-irradiation, the fast response time of ultraviolet postradiation liquid crystal cell, so confirm that the direction of orientation of liquid crystal is controlled.

In addition, all liquid crystal cells are all observed and are confirmed that liquid crystal is evenly orientated by polarizing microscope.

[evaluation of tilt angle]

Carry out the mensuration of the tilt angle of the liquid crystal cell obtaining in [making (conventional box) of liquid crystal cell] and [making (PSA box) of liquid crystal cell].For tilt angle, after Liquid crystal pour, after 5 hours, measure after 5 minutes and in 120 DEG C of heat treated in 95 DEG C of heat treated.In addition, for after Liquid crystal pour, in 95 DEG C of heat treated, the irradiation of the liquid crystal cell after 5 minutes is scaled 10J/cm with 365nm ²ultraviolet ray after also measure.Tilt angle uses PAS-301 (the empty company of Ai Erxi (ELSICON society) system) at room temperature to measure.In addition, ultraviolet irradiation uses desk-top UV solidification equipment (HCT3B28HEX-1) (Sen En Optical Co., Ltd (セ Application ライト society) system) to carry out.

< embodiment 15>

The polyamic acid solution (1) that is 25.0 quality % to the resin solid constituent concentration obtaining in embodiment 4 adds NMP (12.9g) and BCS (18.8g) in (10.0g), stir 3 hours at 25 DEG C, obtain aligning agent for liquid crystal (1).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (1) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< embodiment 16>

Add NMP (18.8g) and BCS (23.0g) to the polyimide powder (2) obtaining in embodiment 5 in (2.51g), stir 8 hours at 25 DEG C, thereby obtain aligning agent for liquid crystal (2).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (2) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< embodiment 17>

The polyamic acid solution (3) that is 25.0 quality % to the resin solid constituent concentration obtaining in embodiment 6 adds NMP (11.4g) and BCS (21.9g) in (10.5g), stir 3 hours at 25 DEG C, obtain aligning agent for liquid crystal (3).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (3) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< embodiment 18>

Add NMP (22.9g) and BCS (18.8g) to the polyimide powder (4) obtaining in embodiment 7 in (2.50g), stir 8 hours at 25 DEG C, thereby obtain aligning agent for liquid crystal (4).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (4) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< embodiment 19>

Add NMP (21.0g) and BCS (21.0g) to the polyimide powder (5) obtaining in embodiment 8 in (2.52g), stir 8 hours at 25 DEG C, thereby obtain aligning agent for liquid crystal (5).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (5) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< embodiment 20>

Add NMP (25.0g) and BCS (16.7g) to the polyimide powder (6) obtaining in embodiment 9 in (2.50g), stir 8 hours at 25 DEG C, thereby obtain aligning agent for liquid crystal (6).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (6) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< embodiment 21>

The polyamic acid solution (7) that is 25.0 quality % to the resin solid constituent concentration obtaining in embodiment 10 adds NMP (15.0g) and BCS (16.7g) in (10.0g), stir 3 hours at 25 DEG C, obtain aligning agent for liquid crystal (7).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (7) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< embodiment 22>

Add NMP (27.1g) and BCS (14.6g) to the polyimide powder (8) obtaining in embodiment 11 in (2.50g), stir 8 hours at 25 DEG C, thereby obtain aligning agent for liquid crystal (8).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (8) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< embodiment 23>

Add NMP (22.9g) and BCS (18.8g) to the polyimide powder (9) obtaining in embodiment 12 in (2.50g), stir 8 hours at 25 DEG C, thereby obtain aligning agent for liquid crystal (9).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (9) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< embodiment 24>

Add NMP (25.0g) and BCS (16.7g) to the polyimide powder (10) obtaining in embodiment 13 in (2.50g), stir 8 hours at 25 DEG C, thereby obtain aligning agent for liquid crystal (10).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (10) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< embodiment 25>

Add NMP (23.1g) and BCS (18.9g) to the polyimide powder (11) obtaining in embodiment 14 in (2.52g), stir 8 hours at 25 DEG C, thereby obtain aligning agent for liquid crystal (11).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (11) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< comparative example 3>

The polyamic acid solution (12) that is 25.0 quality % to the resin solid constituent concentration obtaining in comparative example 1 adds NMP (10.9g) and BCS (21.0g) in (10.1g), stir 3 hours at 25 DEG C, obtain aligning agent for liquid crystal (12).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (12) of gained to carry out making and the various evaluation of box with above-mentioned condition.

< comparative example 4>

Add NMP (23.1g) and BCS (18.9g) to the polyimide powder (13) obtaining in comparative example 2 in (2.52g), stir 8 hours at 25 DEG C, thereby obtain aligning agent for liquid crystal (13).There is not muddiness or the abnormal conditions such as separate out, confirm as uniform solution in this aligning agent for liquid crystal.

Use the aligning agent for liquid crystal (13) of gained to carry out making and the various evaluation of box with above-mentioned condition.

[table 39]

[table 40]

[table 41]

[table 42]

From above-mentioned result, the liquid crystal orientation film being obtained by the aligning agent for liquid crystal of embodiments of the invention is compared with the liquid crystal orientation film being obtained by the aligning agent for liquid crystal of comparative example, even if be exposed to for a long time the irradiation of high temperature and light (ultraviolet ray), the variation of tilt angle is also little.This has all obtained same result in conventional box and PSA box.Particularly, not containing comparative example 3 and the comparative example 4 of particular side chain diamine compound, the variation that is exposed to for a long time the tilt angle after high temperature is large, and the variation of postradiation tilt angle that is exposed to light (ultraviolet ray) is large especially.

In addition, use in the situation that forms identical polyimide precursor and polyimide, in the embodiment that comprises particular side chain diamine compound, even if be exposed to for a long time after high temperature and light (ultraviolet ray), the variation of tilt angle is also little.Be specially the comparison of the conventional box of the embodiment 17 shown in table 41 and comparative example 3 and embodiment 18 and comparative example 4.In addition also has, the comparison of the PSA box of the embodiment 17 shown in table 42 and comparative example 3 and embodiment 18 and comparative example 4.

In addition, the liquid crystal orientation film being obtained by the aligning agent for liquid crystal of embodiments of the invention is compared with the liquid crystal orientation film being obtained by the aligning agent for liquid crystal of comparative example, and the contact angle of liquid crystal orientation film and water is large., the hydrophobicity of liquid crystal orientation film is high.Particularly, not containing comparative example 3 and the comparative example 4 of particular side chain diamine compound, the water contact angle of liquid crystal orientation film is little, and invasion poor (contact angle of liquid crystal is large) on the liquid crystal orientation film of liquid crystal.

In addition, use in the situation that forms identical polyimide precursor and polyimide, in the embodiment that comprises particular side chain diamine compound, the contact angle of liquid crystal orientation film and water is large, and the hydrophobicity of liquid crystal orientation film is high.In addition,, in the embodiment that comprises particular side chain diamine compound, the invasion on the liquid crystal orientation film of liquid crystal is good.Be specially the comparison of the evaluation of the water contact angle of the liquid crystal orientation film of the embodiment 17 shown in table 39 and comparative example 3 and embodiment 18 and comparative example 4.In addition also has, the comparison of the evaluation of the invasion on the liquid crystal orientation film of the embodiment 17 shown in table 42 and comparative example 3 and embodiment 18 and the liquid crystal of comparative example 4.

The possibility of utilizing in industry

The aligning agent for liquid crystal of the polymkeric substance that comprises the side chain with ad hoc structure of the application of the invention, even if can provide and be exposed to for a long time the liquid crystal orientation film that high temperature and illumination the variation of tilt angle also can not occur and can alleviate the liquid crystal aligning inequality producing in ODF mode, by using this liquid crystal orientation film, the liquid crystal display cells that display characteristic good reliability is high can be provided, can be used for liquid crystal TV set, TN element, STN element, TFT liquid crystal cell of large picture, fine etc.

In addition, the liquid crystal orientation film being obtained by aligning agent for liquid crystal of the present invention is also used in the manufacture that needs the liquid crystal display cells of irradiation ultraviolet radiation while making liquid crystal display cells.

Quote the full content of instructions, claims and specification digest of No. 2011-240340, the Japanese patent application of filing an application on November 1st, 2011 here as the announcement of instructions of the present invention.

Claims

1. aligning agent for liquid crystal, is characterized in that, comprise be selected from have the polyimide precursor of the side chain representing with following formula [1A] or [1B] and to this polyimide precursor carry out imidizate and at least a kind of polymkeric substance of polyimide;

[changing 1]

[changing 2]

2. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, described polyimide precursor is to make to comprise that two amine components of the diamine compound with the side chain representing with formula [1A] or formula [1B] react and obtain with tetrabasic carboxylic acid composition.

3. aligning agent for liquid crystal as claimed in claim 2, is characterized in that, described in there is the side chain representing with formula [1A] diamine compound represent with following formula [2A];

[changing 3]

4. aligning agent for liquid crystal as claimed in claim 3, is characterized in that, the described diamine compound representing with formula [2A] represents with following formula [2a]～formula [2d];

[changing 4]

5. aligning agent for liquid crystal as claimed in claim 2, is characterized in that, described in there is the side chain representing with formula [1B] diamine compound represent with following formula [2B];

[changing 5]

6. the aligning agent for liquid crystal as described in any one in claim 3～5, is characterized in that, the described diamine compound representing with formula [2A] or formula [2B] accounts for 5～80 % by mole in two amine components.

7. aligning agent for liquid crystal as claimed in claim 4, is characterized in that, the described diamine compound representing with formula [2a]～formula [2d] accounts for 5～80 % by mole in two amine components.

8. the aligning agent for liquid crystal as described in any one in claim 2～7, is characterized in that, described tetrabasic carboxylic acid composition is the tetracarboxylic dianhydride who represents with following formula [3];

[changing 6]

9. aligning agent for liquid crystal as claimed in claim 8, is characterized in that, described Z ₁the structure representing for the formula with following [3a]～formula [3j];

[changing 7]

10. the aligning agent for liquid crystal as described in any one in claim 1～9, is characterized in that, comprises the organic solvent of 80～99 quality % in aligning agent for liquid crystal.

11. aligning agent for liquid crystal as claimed in claim 10, is characterized in that, organic solvent comprises the poor solvent of 5～60 quality %.

12. liquid crystal orientation films, is characterized in that, are obtained by the aligning agent for liquid crystal described in any one in claim 1～11.

13. liquid crystal orientation films, is characterized in that, right to use requires the aligning agent for liquid crystal described in any one in 1～11 to obtain by ink-jet application method.

14. liquid crystal display cells, is characterized in that, have the liquid crystal orientation film described in claim 12 or 13.

15. liquid crystal orientation films as described in claim 12 or 13, it is characterized in that, liquid crystal display cells for thering is liquid crystal layer between a pair of substrate that possesses electrode and making through following operation: configuration packet is containing the liquid-crystal composition of the polymerizable compound of at least one party's polymerization by active energy beam and heat, to execute the alive described polymerizable compound polymerization that makes between described electrode simultaneously between described a pair of substrate.

16. liquid crystal display cells, is characterized in that, have the liquid crystal orientation film described in claim 15.

17. liquid crystal display cells as claimed in claim 16, it is characterized in that, make through following operation: between a pair of substrate that possesses electrode and described liquid crystal orientation film, there is liquid crystal layer, between described a pair of substrate, configuration packet is containing the liquid-crystal composition of the polymerizable compound by least one party's polymerization in active energy beam and heat, to execute the alive described polymerizable compound polymerization that makes between described electrode simultaneously.

18. liquid crystal orientation films as described in claim 12 or 13, it is characterized in that, liquid crystal display cells for thering is liquid crystal layer between a pair of substrate that possesses electrode and making through following operation: configuration packet is containing the liquid crystal orientation film of the polymerizable group of at least one party's polymerization by active energy beam and heat, to execute the alive described polymerizable group polymerization that makes between described electrode simultaneously between described a pair of substrate.

19. liquid crystal display cells, is characterized in that, have the liquid crystal orientation film described in claim 18.

20. liquid crystal display cells as claimed in claim 19, it is characterized in that, make through following operation: between a pair of substrate that possesses electrode, there is liquid crystal layer, between described a pair of substrate, configuration packet is containing the liquid crystal orientation film of the polymerizable group by least one party's polymerization in active energy beam and heat, to execute the alive described polymerizable group polymerization that makes between described electrode simultaneously.

21. diamine compounds that represent with described formula [2A].

22. diamine compounds that represent with described formula [2a]～formula [2d].

23. two amine components that make to comprise the described diamine compound representing with formula [2A] or formula [2B] react with tetrabasic carboxylic acid composition and must polyamic acid, or make this polyamic acid dehydration closed-loop and must polyimide.

24. two amine components that make to comprise the described diamine compound representing with formula [2a]～formula [2d] react with tetrabasic carboxylic acid composition and must polyamic acid, or make this polyamic acid dehydration closed-loop and must polyimide.