CN104946267B

CN104946267B - Aligning agent for liquid crystal, liquid crystal orientation film and its preparation method, liquid crystal display element, phase difference film and its preparation method, polymer and compound

Info

Publication number: CN104946267B
Application number: CN201510121594.6A
Authority: CN
Inventors: 樫下幸志; 杉山文隆
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2014-03-24
Filing date: 2015-03-19
Publication date: 2019-06-11
Anticipated expiration: 2035-03-19
Also published as: KR102204588B1; TWI633375B; KR20150110317A; TW201537272A; JP6458484B2; CN104946267A; JP2015194697A

Abstract

The present invention provides a kind of aligning agent for liquid crystal, liquid crystal orientation film and its preparation method, liquid crystal display element, phase difference film and its preparation method, polymer and compound.Aligning agent for liquid crystal of the invention contains the polymer (P) with part-structure represented by following formula (1) on main chain.In formula (1), W¹And W²To have the divalent cyclic group of phenyl ring, cyclohexane ring etc. in ring skeleton；X¹For singly-bound ,-O- ,-COO- ,-CO- etc.；X²For-O- ,-COO- ,-CO- etc.；R¹For singly-bound, alkane diyl of carbon number 1~20 etc.；R²For singly-bound ,-COO-, alkane diyl of carbon number 1~5 etc.；The integer that p is 0~2；When p=0, W¹Ring skeleton be not phenyl ring；In W¹And W²In the case where being the phenylene for being substituted or being unsubstituted, R¹It is not singly-bound.Aligning agent for liquid crystal of the invention can make the image retention characteristic to the coating of substrate, the rub resistance of film and liquid crystal display element good.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and its preparation method, liquid crystal display element, phase difference film And its preparation method, polymer and compound

Technical field

The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method, liquid crystal display element, phase difference films And its manufacturing method, polymer and compound.

Background technique

In the past, liquid crystal display element had developed different more such as the physical property of electrode structure or liquid crystal molecule, manufacturing step Kind driving method, such as it has been known that there is: twisted nematic (Twisted Nematic, TN) type or STN Super TN (Super- Twisted Nematic, STN) type, vertical orientation (Vertical Alignment, VA) type, coplanar switching (In-Plane Switching, IPS) type, the various liquid crystal display elements of fringing field switching (Fringe Field Switching, FFS) type etc.. These liquid crystal display elements have the liquid crystal orientation film be orientated liquid crystal molecule.With regard to heat resistance, mechanical strength and liquid For the good aspects of various characteristics such as brilliant compatibility, the material of liquid crystal orientation film is sub- usually using polyamic acid or polyamides Amine.

In recent years, the LCD TV of big picture and fine becomes main body, in addition smart phone or tablet personal computer This kind of the universal of small-sized display terminal such as (tablet personal computer) is in progress, thus to liquid crystal display High precision require further increase.In addition, propose to have more to seek the display quality of liquid crystal display to improve in the past Kind aligning agent for liquid crystal (for example, referring to patent document 1).Disclosing in patent document 1 has following technology: using and contains following polymer Polymer composition polyimide resin film is formed on substrate, to resulting polyimide resin film implement friction treatment and Liquid crystal orientation film is made, the polymer passes through 3,3 '-dimethyl -4,4 '-benzidines, 4,4- bis- (4- amino-benzene oxygens) The diamines containing biphenyl structural such as biphenyl is obtained with reacting for tetracarboxylic dianhydride.The technology recorded in the patent document 1 In, even if when consumingly carrying out friction treatment the reduction at tilted alignment angle can also be inhibited, so that uniform liquid crystal can be realized Display.

In addition, in liquid crystal display element use a variety of optical materials, wherein for eliminate display coloring purpose or The purpose of display color and contrast than the visual angle interdependence changed with visual direction is eliminated, and uses phase difference film.Institute The known film with liquid crystal orientation film and liquid crystal layer of phase difference film is stated, the liquid crystal orientation film is formed in triacetyl cellulose The surface of the substrates such as (triacetyl cellulose, TAC) film, the liquid crystal layer pass through on the surface of the liquid crystal orientation film Polymerizable liquid crystal is set to harden and be formed.In addition, in recent years, when making the liquid crystal orientation film in phase difference film, utilizing following light Alignment method: by organic film to the radioactivity-sensitive for being formed in substrate surface irradiate the radioactive ray of polarisation or non-polarized come Assign liquid crystal aligning ability；And propose that there are many phase difference film liquid to make liquid crystal orientation film using the method Brilliant alignment agent (for example, referring to patent document 2)

[existing technical literature]

[patent document]

No. 3365563 bulletins of [patent document 1] Japanese Patent No.

[patent document 2] Japanese Patent Laid-Open 2012-37868 bulletin

Summary of the invention

[the problem of invention is to be solved]

The present inventor et al. is studied, as a result clear: the liquid formed by the aligning agent for liquid crystal recorded in patent document 1 The orientation restraint of the liquid crystal molecule of brilliant alignment films is simultaneously insufficient, such as is being applied to the transverse electrics such as IPS mode or FFS mode field side In the case where the liquid crystal display element of formula, it is easy to produce image retention or burns print.In addition, assigning liquid to film by friction treatment In the case where brilliant alignment capability, require to stablize i.e. rub resistance relative to friction to improve the orientation restraint of liquid crystal molecule It is high.On the other hand, if importing upright and outspoken structure in the polymer in order to improve rub resistance, there is the coating of aligning agent for liquid crystal Property (printing) reduce worry.

The present invention is formed in view of the project, and one of its goals is to provide one kind to make the coating to substrate, painting The rub resistance of film and the good aligning agent for liquid crystal of the image retention characteristic of liquid crystal display element.In addition, another object is to provide A kind of aligning agent for liquid crystal of the good phase difference film of available liquid crystal aligning.

[means to solve the problem]

The artificial project of the solution prior art as described above of the inventors of the present invention and carried out making great efforts research, as a result send out It is existing, by making the component of polymer of aligning agent for liquid crystal contain the polymer with specific structure, can to solve the problem, thus complete At the present invention.Specifically, through the invention come provide aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method below, Liquid crystal display element, phase difference film and its manufacturing method, polymer and compound.

An aspect of of the present present invention is to provide a kind of aligning agent for liquid crystal, and contain has following formula (1) represented on main chain Part-structure polymer (P).

[changing 1]

(in formula (1), W¹And W²It is separately that phenyl ring, cyclohexane ring, pentamethylene ring or pyridine ring are set as ring skeleton Divalent cyclic group；X¹For singly-bound ,-O-, *-COO-, *-OCO- ,-CO-, *-NR¹⁰CO- or *-CONR¹⁰(wherein, R¹⁰For hydrogen original The alkyl of son or carbon number 1~3, " * " is indicated and W¹Associative key)；X²For-O-, *-COO-, *-OCO- ,-CO-, *-NR¹¹CO- Or *-CONR¹¹(wherein, R¹¹For hydrogen atom or the alkyl of carbon number 1~3, " * " is indicated and W²Associative key)；R¹For singly-bound, carbon number 1~20 alkane diyl, the alkene diyl of carbon number 2~20, a part of the alkene diyl of the alkane diyl of carbon number 1~20 or carbon number 2~20 Hydrogen atom is substituted one of the alkene diyl of the alkane diyl or carbon number 2~20 of divalent base or carbon number 1~20 made of base replaces Divalent base made of dividing methylene warp-O- or-S- to replace；R²For singly-bound ,-O-, *-COO-, *-OCO- ,-CO-, *-NR¹²CO-、*- CONR¹²(wherein, R¹²For hydrogen atom or the alkyl of carbon number 1~3, " * " is indicated and W¹Associative key), the alkane diyl of carbon number 1~5, A part of hydrogen atom of the alkene diyl of the alkene diyl of carbon number 2~5, the alkane diyl of carbon number 1~5 or carbon number 2~5 is substituted base substitution Made of a part of methylene warp-O- or-S- of alkene diyl of alkane diyl or carbon number 2~5 of divalent base or carbon number 1~5 take Divalent base made of generation；P indicates 0~2 integer；Wherein, when p=0, W¹For cyclohexane ring, pentamethylene ring or pyridine ring are set as The divalent cyclic group of ring skeleton；In W¹And W²In the case where being the phenylene for being substituted or being unsubstituted, R¹It is not singly-bound)

An aspect of of the present present invention is to provide a kind of liquid crystal orientation film formed using the aligning agent for liquid crystal.In addition, mentioning For a kind of liquid crystal display element comprising the liquid crystal orientation film and the phase difference film comprising the liquid crystal orientation film.In addition, another On the one hand to provide a kind of manufacturing method of phase difference film, the manufacturing method includes: that the liquid crystal aligning is coated on substrate Agent and the step of form film；The step of light irradiation is carried out to the film；And it is applied on the film after light irradiates Cloth polymerizable liquid crystal and the step of make its hardening.

An aspect of of the present present invention is to provide a kind of polymer, is selected from sub- by polyamic acid, poly amic acid ester and polyamides At least one of group polymer composed by amine, and make the monomer polymerization containing compound represented by following formula (d) and It obtains.Additionally, it is provided one kind is by the compound represented by following formula (d).

[changing 2]

(in formula (d), X³And X⁴It is separately singly-bound ,-O-, *-COO-, *-OCO- ,-CO-, *-NR¹⁴CO- or *- CONR¹⁴(wherein, R¹⁴For hydrogen atom or the alkyl of carbon number 1~3, " * " indicates the associative key with aminophenyl)；R³For carbon number 1~ 20 alkane diyl, the alkene diyl of carbon number 2~20, phenylene, piperidines diyl, the alkane diyl of carbon number 1~20 or carbon number 2~20 alkene A part of hydrogen atom of diyl is substituted the alkane diyl or carbon number 2~20 of divalent base or carbon number 1~20 made of base replaces Divalent base made of a part of methylene warp-O- of alkene diyl or-S- replaces；R⁴And R⁵Separately for halogen atom or The alkyl or alkoxy of carbon number 1~6；Q is 0 or 1；M and n is separately 0~4 integer；In R⁴、R⁵There are multiple feelings Under condition, multiple R⁴、R⁵It can distinguish identical also different；W¹、W²、X¹、X²、R¹、R²And p is synonymous with the formula (1) respectively)

[The effect of invention]

Using aligning agent for liquid crystal of the invention, can make to the coating of substrate, the rub resistance of film and liquid crystal display member The image retention characteristic of part is good.In addition, can get the good phase difference film of liquid crystal aligning using aligning agent for liquid crystal of the invention.

Detailed description of the invention

Fig. 1 is the schematic configuration diagram of FFS type liquid crystal display element.

Fig. 2 (a)~Fig. 2 (b) is the plane signal of the top electrode used when the manufacture of friction orientation liquid crystal display element Figure.Fig. 2 (a) is the top view of top electrode, and Fig. 2 (b) is the magnified partial view of top electrode.

Fig. 3 is the figure for indicating the driving electrodes of 4 systems.

Fig. 4 (a)~Fig. 4 (b) is the floor map of the top electrode used when the manufacture of light orientation liquid crystal display element. Fig. 4 (a) is the top view of top electrode, and Fig. 4 (b) is the magnified partial view of top electrode.

[explanation of symbol]

10: liquid crystal display element

11a, 11b: glass substrate

12: liquid crystal orientation film

13: top electrode

14: insulating layer

15: hearth electrode

16: liquid crystal layer

C1: part enclosed by the dotted line

D1: the line width of electrode

D2: interelectrode distance

Specific embodiment

Hereinafter, to each ingredient contained in aligning agent for liquid crystal of the invention and optionally and arbitrarily deploy other at Divide and is illustrated.

Aligning agent for liquid crystal of the invention contains the polymer with part-structure represented by the formula (1) on main chain (P) it is used as component of polymer.

W in the formula (1)¹And W²It is cyclic annular for phenyl ring, cyclohexane ring, pentamethylene ring or pyridine ring are set as ring skeleton divalent Base.In addition, " the n valence cyclic group " in the so-called present invention is from the atom of ring is constituted (in W¹And W²In the case where be carbon atom) in N valence base made of n hydrogen atom is removed, there can also be substituent group in loop section.

W¹And W²Concrete example can for example enumerate: Isosorbide-5-Nitrae-phenylene, 1,3- phenylene, 1 or 4 cyclohexylidene, the Asia 1,3- hexamethylene Base, 1,3- cyclopentylene, pyridine -2,5- diyl or the loop section in each base import divalent base made of substituent group etc..This Outside, W¹And W²The substituent group that can have of ring skeleton can for example enumerate halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom Deng), the alkyl of carbon number 1~6, the alkoxy of carbon number 1~6 etc..W¹And W²It can be mutually the same also different.

Wherein, just for the high aspect of the reduction effect of exchange (alternating current, AC) image retention, W¹And W²It is excellent It is selected as W at least¹Ring skeleton be set as cyclohexane ring, with regard to synthesis easness and cost aspect for, preferably by W¹And W²'s Ring skeleton is set as phenyl ring.

In W¹And W²In the case where cyclohexylidene, the divalent organic group that is bonded on cyclohexane ring can for cis- spatial configuration or Either one or two of trans geometric configuration, but for the high aspect of the improvement of AC image retention characteristic, preferably trans geometric configuration, More preferably anti-form-1,4- hexylidene.

X¹For singly-bound ,-O-, *-COO-, *-OCO- ,-CO-, *-NR¹⁰CO- or *-CONR¹⁰(wherein, R¹⁰For hydrogen atom or The alkyl of carbon number 1~3, " * " is indicated and W¹Associative key).Preferably singly-bound ,-O-, *-COO-, *-OCO-, *-NHCO-, *-N (CH₃) CO-, *-CONH- or *-CON (CH₃)-, more preferably singly-bound ,-O-, *-COO- or *-OCO-.X²For-O-, *- COO-、*-OCO-、-CO-、*-NR¹¹CO- or *-CONR¹¹(wherein, R¹¹For hydrogen atom or the alkyl of carbon number 1~3, " * " is indicated With W²Associative key).Preferably-O-, *-COO-, *-OCO-, *-NHCO-, *-N (CH³) CO-, *-CONH- or *-CON (CH³)-, more preferably-O-, *-COO- or *-OCO-.

R¹For singly-bound, the alkane diyl of carbon number 1~20, the alkene diyl of carbon number 2~20, the alkane diyl of carbon number 1~20 or carbon number 2 A part of hydrogen atom of~20 alkene diyl is substituted the alkane diyl or carbon number of divalent base or carbon number 1~20 made of base replaces Divalent base made of a part of methylene warp-O- of 2~20 alkene diyl or-S- replaces.

Herein, the concrete example of the alkane diyl of carbon number 1~20 can for example enumerate methylene, ethylidene, propane diyl, butane two Base, pentane diyl, hexane diyl, heptane diyl, octane diyl, nonane diyl, decane diyl, dodecane diyl, the tetradecane two Base, pentadecane diyl, hexadecane diyl, octadecane diyl etc., these can be that straight-chain is also branch-like.Preferably straight chain Shape.In addition, the concrete example of the alkene diyl of carbon number 2~20 can for example enumerate ethenylidene, propylene diyl, butylene diyl, amylene two Base, hexene diyl, heptene diyl, octene diyl, nonene diyl, decene diyl, laurylene diyl, tetradecene diyl, ten pentaenes Diyl, hexadecylene diyl, octadecylene diyl etc..These can be that straight-chain is also branch-like, but preferably straight-chain.

The substituent group that the alkane diyl and alkene diyl can have can for example enumerate halogen atom, alkoxy etc..

For the aspect that can make rub resistance and favorable solubility, R¹Preferably the alkane diyl of carbon number 1~20, carbon number 2 A part of hydrogen atom of the alkene diyl of~20 alkene diyl, the alkane diyl of carbon number 1~20 or carbon number 2~20 be substituted base replace and At divalent base or a part of methylene warp-O- or-S- of alkene diyl of alkane diyl or carbon number 2~20 of carbon number 1~20 take Divalent base, more preferably the alkane diyl of carbon number 1~20 made of generation.

Difficult visibility (the resistance to frame for just making the display on the sealant periphery in rub resistance and liquid crystal display element uneven Unevenness) for good viewpoint, R¹R in the case where not for singly-bound¹Carbon number be preferably 2 or more.In addition, just making polymer Favorable solubility aspect for, preferably carbon number is 10 hereinafter, more preferably 8 hereinafter, especially preferably 6 or less.

R²For singly-bound ,-O-, *-COO-, *-OCO- ,-CO-, *-NR¹²CO-、*-CONR¹²(wherein, R¹²For hydrogen atom or The alkyl of carbon number 1~3, " * " is indicated and W¹Associative key), the alkane diyl of carbon number 1~5, the alkene diyl of carbon number 2~5, carbon number 1~ A part of hydrogen atom of 5 alkane diyl or the alkene diyl of carbon number 2~5 is substituted divalent base or carbon number 1~5 made of base replaces Alkane diyl or carbon number 2~5 alkene diyl a part of methylene warp-O- or-S- replace made of divalent base.Herein, carbon number 1 The concrete example of~5 alkane diyl can enumerate the R¹Illustration in carbon number 1~5 base, the alkene diyl of carbon number 2~5 it is specific Example can enumerate the R¹Illustration in carbon number 2~5 base.In addition, R²The substituent group that middle alkane diyl and alkene diyl can have is for example Halogen atom, alkoxy etc. can be enumerated.

For the high aspect of the improvement of the AC image retention characteristic of liquid crystal display element and resistance to frame unevenness, R²It is preferred that For singly-bound, *-COO-, *-OCO-, *-NHCO-, *-N (CH₃)CO-、*-CONH-、*-CON(CH₃)-(" * " indicates and W¹Combination Key) or the alkane diyl of carbon number 1~3 or the hydrogen atom of the alkane diyl replace through fluorine atom made of divalent base, more preferably singly Key, *-COO- or *-OCO-.

The integer that p is 0~2, for the deliquescent aspect of polymer, p is preferably 0 or 1.

For the viewpoint of the AC image retention characteristic of liquid crystal display element and the deliquescent balance of polymer, "-W¹-(R²- W²) base represented by p- " is preferably cyclohexylidene, bicyclohexylidene base, "-Ar¹-Ar²-”(Ar¹For phenylene, Ar²For sub- hexamethylene Base) or "-Ar³-COO-Ar⁴-”(Ar³And Ar⁴It is separately phenylene or cyclohexylidene).

In the formula (1), in the case where p=0, W¹For there is cyclohexane ring, pentamethylene ring or pyridine ring in ring skeleton Divalent cyclic group.

In W¹And W²In the case where being the phenylene for being substituted or being unsubstituted, R¹It is not singly-bound, as carbon number 1~20 Alkane diyl, the alkene diyl of carbon number 2~20, the alkene diyl of the alkane diyl of carbon number 1~20 or carbon number 2~20 a part of hydrogen atom It is substituted a part of methylene of the alkene diyl of the alkane diyl or carbon number 2~20 of divalent base or carbon number 1~20 made of base replaces Divalent base made of base warp-O- or-S- replace.In W¹And W²Ring skeleton be phenyl ring in the case where, pass through the main chain in polymer Middle importing spacer structures, so that the improvement of coating, rub resistance and image retention characteristic etc. is high, therefore preferably.

In R¹In the case where singly-bound, p is preferably 1 or 2.In this case, with regard to gained liquid crystal display element resistance to frame not For the high aspect of the improvement of equal property and image retention characteristic preferably.

The concrete example of part-structure represented by the formula (1) can for example enumerate following formula (1-1)~formula (1-30) respectively Represented structure etc..

[changing 3]

[changing 4]

[changing 5]

Represented by the formula (1-1)~formula (1-6), formula (1-10)~formula (1-23) and formula (1-27)~formula (1-30) difference Part-structure in, the spatial configuration of the divalent organic group being bonded on cyclohexane ring can be either one or two of trans- and cis-.In addition, In polymer (P), can also have both trans- and cis- as the formula (1-1)~formula (1-6), formula (1-10)~formula (1-23) And formula (1-27)~represented part-structure of formula (1-30) difference.About the spatial configuration, relative to 1 point of polymer (P) The formula (1-1)~formula (1-6), formula (1-10)~formula (1-23) and formula (1-27) possessed by son~formula (1-30) difference institute's table The part-structure shown adds up to, and trans- ratio is preferably 50 moles of % or more, more preferably 70 moles of % or more, particularly preferably For 90 moles of % or more.

The main chain (main framing) of the polymer (P) can for example be enumerated comprising polyamic acid, polyimides, polyamic acid The skeleton of ester, polyester, polyamide etc..In addition, in the present invention, " main chain " of so-called polymer refers to be repeated by monomer The structure for being bonded and being formed.The polymer (P) can be suitable for selection according to purposes of aligning agent for liquid crystal etc. in these Polymer one kind or two or more and use.Such polymer (P) can have the formula (1) represented by using in monomer Structure compound polymerization and obtain.

Wherein preferably polymer (P) is selected from the group as composed by polyamic acid, polyimides and poly amic acid ester At least one of.

[polyamic acid (P)]

In the case where the polymer (P) is polyamic acid (hereinafter also referred to as " polyamic acid (P) "), the polyamides Amino acid (P) can for example be obtained and reacting tetracarboxylic dianhydride with diamines.Specifically, can be for example, by following method And obtain: (i) will have the tetracarboxylic dianhydride of structure represented by the formula (1) (hereinafter also referred to as " specific tetrabasic carboxylic acid two Acid anhydride ") for monomer and the method that is polymerize；(ii) there will be the diamines of structure represented by the formula (1) (hereinafter, also referred to as For " specific diamines ") for monomer and the method that is polymerize；(iii) by the specific tetracarboxylic dianhydride and the specific diamines The method being polymerize for monomer.

(specific tetracarboxylic dianhydride)

Specific tetracarboxylic dianhydride used in the method (i) and method (iii) can for example enumerate aliphatic tetrabasic carboxylic acid two Acid anhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride etc..It is represented that preferred concrete example can for example enumerate following formula (t) Compound etc..

[changing 6]

(in formula (t), A¹¹And A¹²It is separately phenyl ring or cyclohexane ring；X¹³And X¹⁴Be separately singly-bound ,- O-、*-COO-、*-OCO-、-CO-、*-NR¹⁵CO- or *-CONR¹⁵(wherein, R¹⁵For hydrogen atom or the alkyl of carbon number 1~3, " * " Indicate the associative key with the phenyl ring with anhydride group)；R¹³For singly-bound, the alkane diyl of carbon number 1~20, the alkene diyl of carbon number 2~20, A part of hydrogen atom of the alkene diyl of the alkane diyl or carbon number 2~20 of carbon number 1~20 be substituted base replace made of divalent base or Divalent made of a part of methylene warp-O- or-S- of the alkene diyl of the alkane diyl or carbon number 2~20 of person's carbon number 1~20 replace Base；R is 0 or 1；Wherein, R¹³When for singly-bound, r=0；W¹、W²、X¹、X²、R¹、R²And p is synonymous with the formula (1) respectively)

The X of the formula (t)¹³And X¹⁴Preferably singly-bound ,-O-, *-COO- or *-OCO-.About R¹³Concrete example and preferably Base can apply the R¹Explanation.

The concrete example of compound represented by the formula (t) can for example enumerate following formula (an-1)~formula (an-6) institute respectively The compound etc. of expression.

[changing 7]

The formula (an-3)~represented compound of formula (an-6) difference can be used the divalent being bonded with cyclohexane ring organic The spatial configuration of base is that trans- compound and spatial configuration are any of cis- compound, or trans- body can also be used And the mixture of cis- body.

1 kind or suitable choosing in addition, specific tetracarboxylic dianhydride used in the synthesis of the polyamic acid can be used alone It selects two or more and uses.

(other tetracarboxylic dianhydrides)

It, can be by using the tetrabasic carboxylic acid for not having structure represented by the formula (1) in monomer in the method (ii) The polymerization of dianhydride (hereinafter also referred to as " other tetracarboxylic dianhydrides ") and synthesize the polyamic acid (P).In addition, the method (i) And in method (iii), tetracarboxylic dianhydride used in synthesis can be used alone the specific tetracarboxylic dianhydride, but can also with it is specific Tetracarboxylic dianhydride is used together other tetracarboxylic dianhydrides.

Other described tetracarboxylic dianhydrides can for example enumerate aliphatic tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic series Tetracarboxylic dianhydride etc..As the concrete example of these tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydride can for example be enumerated: butane tetracarboxylic acid Dianhydride etc.；

Ester ring type tetracarboxylic dianhydride can for example enumerate: 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 2,3,5- tricarboxylic basic rings penta Guanidine-acetic acid dianhydride, 5- (2,5- dioxotetrahydro furans -3- base) -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans -1,3- bis- Ketone, 5- (2,5- dioxotetrahydro furans -3- base) -8- methyl -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans -1,3- diketone, 3- oxabicyclo [3.2.1] octane -2,4- diketone -6- loop coil -3 '-(tetrahydrofuran -2 ', 5 '-diketone), 5- (2,5- dioxos Tetrahydro -3- furyl) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, 3,5,6- tri- carboxyl -2- carboxymethyl group norbornanes - 2:3,5:6- dianhydride, bicyclic [3.3.0] octane -2,4,6,8- tetrabasic carboxylic acid 2:4,6:8- dianhydrides, bicyclic [2.2.1] heptane -2,3, 5,6- tetrabasic carboxylic acid 2:3,5:6- dianhydrides, 4,9- dioxa tricyclic [5.3.1.0^2,6] hendecane -3,5,8,10- tetrones, 1,2,4,5- Cyclopentanetetracarboxylic's dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides, ethylenediamine tetra-acetic acid dianhydride, ring penta Alkane tetracarboxylic dianhydride, ethylene glycol bis- (trimellitic anhydride esters), 1,3-PD bis- (trimellitic anhydride esters) etc.；

Aromatic tetracarboxylic dianhydride can for example be enumerated: pyromellitic acid anhydride etc.；In addition to this, Japan Patent also can be used The tetracarboxylic dianhydride recorded in special open 2010-97188 bulletin.These chemical combination in addition, other tetracarboxylic dianhydrides can be used alone 1 kind of object or two or more is applied in combination.

It can make liquid crystal aligning and for the aspect of the favorable solubility of solvent, the synthesis of the polyamic acid (P) Used in other tetracarboxylic dianhydrides preferably contain selected from by bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid 2:3,5:6- Dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides, 5- (2,5- dioxotetrahydro furans Mutter -3- base) -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans -1,3- diketone, 5- (2,5- dioxotetrahydro furans -3- base) - 8- methyl -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans -1,3- diketone, bicyclic [3.3.0] octane -2,4,6,8- tetrabasic carboxylic acids At least one of group composed by 2:4,6:8- dianhydride, cyclopentanetetracarboxylic's dianhydride and pyromellitic acid anhydride compound.

The total amount of tetracarboxylic dianhydride used in synthesis relative to polyamic acid (P), in the case where the method (i) The use ratio of specific tetracarboxylic dianhydride is preferably set as 3 moles of % or more, is more preferably set as 5 moles of % or more, especially excellent It is selected as being set as 10 moles of % or more.There is no particular restriction for the upper limit value of the use ratio, can be in 100 moles of % ranges below Interior any setting.

In addition, the use ratio of the specific tetracarboxylic dianhydride in the case where the method (iii) can be according to specific diamines Use ratio and be suitable for setting, but the total amount relative to tetracarboxylic dianhydride used in the synthesis of polyamic acid (P), such as can set For 0.5 mole of % or more, it is preferably set as 1 mole of % or more, 3 moles of % or more is more preferably set as, is especially preferably set as 5 Mole % or more.

(specific diamines)

Specific diamines used in the synthesis of the polyamic acid (P) can for example enumerate aliphatic diamine, ester ring type diamines, Aromatic diamine etc..It is wherein preferably aromatic diamine, specifically preferably compound represented by following formula (d).

[changing 8]

The X of the formula (d)³And X⁴Preferably singly-bound ,-O-, *-COO- or *-OCO-.Wherein, in R¹The case where for singly-bound Under, X³And X⁴Particularly preferably singly-bound.About R³Concrete example and preferred base can apply the R¹Explanation.M and n are preferably 0。

The concrete example of compound represented by the formula (d) can for example enumerate following formula (D-1)~formula (D-36) institute respectively The compound etc. of expression.

[changing 9]

[changing 10]

[changing 11]

[changing 12]

The formula (D-1)~formula (D-3), formula (D-5), formula (D-7), formula (D-8), formula (D-10)~formula (D-24) and formula (D-29) spatial configuration of the divalent organic group being bonded on cyclohexane ring can be used to be to~formula (D-35) for represented compound respectively Trans- compound and spatial configuration is cis- either one or two of compound, or the mixing of trans- body and cis- body can also be used Object.Using the formula (D-1)~formula (D-3), formula (D-5), formula (D-7), formula (D-8), formula (D-10)~formula (D-24) and formula (D-29) in the case where the represented compound of~formula (D-35) difference, the ratio of trans- body (is preferably being used two or more Compound in the case where be its total amount) be set as 50 moles of % or more, be more preferably set as 70 moles of % or more, particularly preferably To be set as 90 moles of % or more.Specific diamines used in the synthesis of the polyamic acid can be used alone the 1 of these compounds Kind is suitable for selecting two or more and using.

In addition, in the formula (D-1)~represented compound of formula (D-36) difference, formula (D-5) and formula (D-10)~formula (D-17) represented compound is equivalent to the R with the formula (1) respectively¹For singly-bound and part-structure that p is 1 or 2 two Amine.

(other diamines)

In the method (i), by monomer using do not have the formula (1) represented by structure diamines (hereinafter, Also referred to as " other diamines ") polymerization and synthesize the polyamic acid (P).In addition, in the method (ii) and method (iii), Diamines used in synthesis can be used alone the specific diamines, but can also be used together other diamines with specific diamines.

Other described diamines can for example be enumerated: aliphatic diamine, ester ring type diamines, aromatic diamine, diamino organosilicon Oxygen alkane etc..As the concrete example of these diamines, aliphatic diamine can for example be enumerated: m-xylene diamine, 1,3- propane diamine, four methylenes Base diamines, five methylene diamine, hexamethylene diamine etc.；

Ester ring type diamines can for example be enumerated: Isosorbide-5-Nitrae-diaminocyclohexane, 4,4 '-di-2-ethylhexylphosphine oxides (cyclohexylamine), the bis- (ammonia of 1,3- Ylmethyl) hexamethylene etc.；

Aromatic diamine can for example be enumerated: o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 4,4 '-diamino-diphenyl first Alkane, 4,4 '-diamino diphenyl sulfides, 4,4 '-diamino-diphenyl amine, 1,7- bis- (4- amino-benzene oxygen) heptane, 2,2 '-two 4,4 '-benzidine of methyl -, 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines, 4,4 '-diamino-diphenyl ethers, 2, Bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2-, bis- (4- aminophenyl) fluorenes of 9,9-, bis- [4- (4- amino-benzene oxygen) benzene of 2,2- Base] hexafluoropropane, 2,2- bis- (4- aminophenyl) hexafluoropropane, 4,4 '-(to phenylenediisopropylidene) dianils, Isosorbide-5-Nitrae-are bis- (4- amino-benzene oxygen) benzene, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 2,6-diaminopyridine, N, bis- (the 4- aminobenzenes of N '- Base)-benzidine, 3,5- diaminobenzoic acid, dodecyloxy -2,4- diaminobenzene, dodecyloxy -2,5- diaminobenzene, Cholesteric alkyl oxy -3,5- diaminobenzene, cholesteric alkyl oxy -2,4- diaminobenzene, 3,5- diaminobenzoic acid cholesteric alkyl Bis- (the 4- amino benzoyl oxygroup) cholestane of ester, 3,6-, 4- (4 '-trifluoromethoxy benzoyloxy) cyclohexyl -3,5- bis- Aminobenzoate, 2,4- diamino-N, N- diallyl aniline, 4- aminobenzyl amine, 1- (2,4- diamino-phenyl) piperazine- 4- carboxylic acid, 1,3- bis- (N- (4- aminophenyl) piperidyl) propane, 1- (4- aminophenyl) -2,3- dihydro -1,3,3- trimethyl - 1H- indenes -5- amine, 1- (4- aminophenyl) -2,3- dihydro -1,3,3- trimethyl -1H- indenes -6- amine, 4- aminophenyl -4 '-amino Benzoic ether, 4,4 '-[4,4 '-propane -1,3- diyls are bis- (piperidines-Isosorbide-5-Nitrae-diyl)] diphenylamines and following formula (D-1a)

[changing 13]

(in formula (D-1a), X^IAnd X^IIIt is separately singly-bound ,-O- ,-COO- or-OCO-, R^IFor the alkane of carbon number 1~3 Diyl, R^IIFor the alkane diyl of singly-bound or carbon number 1~3；A is 0 or 1, the integer that b is 0~2, the integer that c is 1~20, and d is 0 or 1； Wherein, a and b will not be simultaneously for 0)

Represented compound etc.；

Diamino organosiloxane can for example be enumerated: 1,3- bis- (3- aminopropyl)-tetramethyl disiloxanes etc.；Except this with Outside, the diamines recorded in Japanese Patent Laid-Open 2010-97188 bulletin can be used.

"-X in the formula (D-1a)^I-(R^I-X^II)_d" represented by divalent base it is preferred are as follows: the alkane diyl of carbon number 1~3, *- O-, *-COO- or *-O-C₂H₄- O- (associative key and diamino-phenyl for wherein, being labeled with " * " are bonded).Base "-C_cH_2c+1" Concrete example can for example be enumerated: methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, Positive decyl, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, positive ten Eight alkyl, NSC 77136 base, n-eicosane base etc..2 amino in diamino-phenyl are preferably located at relative to other bases 2,4- or 3,5-.

The concrete example of compound represented by the formula (D-1a) can for example enumerate following formula (D-1-1)~formula (D-1-4) Represented compound etc. respectively.

[changing 14]

1 kind or suitable of these compounds in addition, other diamines used in the synthesis of the polyamic acid can be used alone It preferably selects two or more and uses.

The total amount of diamines used in synthesis relative to polyamic acid (P), it is specific in the case where the method (ii) The use ratio of diamines is preferably set as 3 moles of % or more, is more preferably set as 5 moles of % or more, is especially preferably set as 10 Mole % or more.There is no particular restriction for the upper limit value of the use ratio, can arbitrarily set in the range of 100 moles of % or less It is fixed.The case where seeking the improvement as brought by the addition of other diamines (such as voltage retention, liquid crystal aligning etc.) Under, the use ratio of the specific diamines is preferably set as 95 moles of % or less.

In addition, the use ratio of the specific diamines in the case where the method (iii) can be according to specific tetracarboxylic dianhydride's Use ratio and be suitable for setting, but the total amount relative to diamines used in the synthesis of polyamic acid (P), such as 0.5 can be set as Mole % or more, is preferably set as 1 mole of % or more, is more preferably set as 3 moles of % or more, be especially preferably set as 4 and rub You are % or more.

In the system for the liquid crystal display element that aligning agent for liquid crystal of the invention is used for TN type, STN type or vertical orientating type In the case where making, at least part of the polymer (P) contained in the aligning agent for liquid crystal can be set as following polymer, institute Stating polymer has the base that pre-tilt angle presentation capability can be assigned to film (hereinafter also referred to as " showing property of pre-tilt angle base ").Pre-dumping Angle showing property base can for example enumerate the alkyl of carbon number 4~20, the fluoroalkyl of carbon number 4~20, the alkoxy of carbon number 4~20, carbon number 17~51 base with steroid skeleton, base with multiring structure etc..

Such as in order to obtain the polyamic acid (P) with pre-tilt angle showing property base, the importing with regard to pre-tilt angle showing property base is held For the aspect of Yi Du, preferably by monomer composition containing with showing property of pre-tilt angle base diamines polymerization and into Row.Specifically, can be synthesized by using the diamines with showing property of the pre-tilt angle base as other diamines.

Using the diamines with showing property of pre-tilt angle base, the sight that just shows pre-tilt angle characteristic sufficiently high For point, usage amount is preferably set as 3 moles of % or more relative to whole diamines used in synthesis, is more preferably set as 5 Mole %~70 mole %.

Liquid crystal aligning ability is being assigned using optical alignment method to the film for using aligning agent for liquid crystal of the invention and making In the case of, at least part of the polymer (P) contained in the aligning agent for liquid crystal can be set as having light orientation structure Polymer.Herein, so-called light orientation structure is the concept comprising both light orientation base and breakdown type light orientation portion.It is specific and The base that light orientation is shown by photoisomerization or photodimerization, photodegradation etc. can be used in speech, light orientation structure, such as It can enumerate: make containing azobenzene or derivatives thereof as the base containing azobenzene of basic framework, containing cinnamic acid or derivatives thereof For the base with cinnamic acid structure of basic framework, containing chalcone or derivatives thereof as basic framework containing chalcone Base is made containing benzophenone or derivatives thereof as the base containing benzophenone of basic framework, containing cumarin or derivatives thereof The base containing cumarin for basic framework, the structure containing polyimides containing polyimides or derivatives thereof as basic framework Deng.

In the case where the polyamic acid (P) has light orientation structure, the light orientation structure is preferably decomposed Type light orientation portion specifically preferably has the polymer of bicyclic [2.2.2] octene skeleton or cyclobutane skeleton.With bicyclic The polyamic acid (P) of [2.2.2] octene skeleton or cyclobutane skeleton can by using bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- In tetracarboxylic dianhydride and cyclobutane tetracarboxylic dianhydride at least any one obtained as other tetracarboxylic dianhydrides.

[synthesis of compound represented by the formula (1)]

Compound represented by the formula (1) can be by synthesizing the well-established law proper combination of organic chemistry.Its an example can Be listed below method: about the specific diamines, synthesis replaces the level-one amino in formula (d) and has among the dinitro of nitro Then body goes back original system using appropriate, the nitro of resulting dinitro intermediate is carried out amination.

The method for synthesizing the dinitro intermediate can be suitable for selection according to compound as a purpose.Such as it can pass through Be used alone in following method a kind or method proper combination of more than two kinds is synthesized: making that there is "-W¹-(R²-W²) p- " institute The compound of the hydroxyl of the base of expression with have "-X³-R¹" represented by base and nitrobenzophenone the side reacted of carboxylic acid Method；Make that there is "-W¹-(R²-W²) base represented by p- " hydroxyl compound with there is "-(R³-X⁴) base represented by q- " And the method that the carboxylic acid of nitrobenzophenone is reacted；Make that there is "-W¹-(R²-W²) base represented by p- " carboxylic acid with have "- X³-R¹" represented by base and nitrobenzophenone hydroxyl the method reacted of compound；Make that there is "-W¹-(R²-W²)p-” The carboxylic acid of represented base with have "-(R³-X⁴) compound of hydroxyl of base and nitrobenzophenone represented by q- " reacted Method；Make that there is "-R¹-X¹-W¹-(R²-W²) carboxylic acid and the nitrophenol or derivatives thereof of base represented by p- " reacted Method；Make that there is "-R¹-X¹-W¹-(R²-W²) base represented by p- " halide and nitrophenol or derivatives thereof carry out it is anti- The method answered；Make that there is "-W¹-(R²-W²)p-X²-R³" represented by base carboxylic acid and nitrophenol or derivatives thereof carry out it is anti- The method answered；Make that there is "-W¹-(R²-W²)p-X²-R³" represented by base halide and nitrophenol or derivatives thereof carry out The method of reaction；Make that there is "-X³-R¹" represented by base and nitrobenzophenone halide with have "-W¹-(R²-W²) p- " institute table The method that the compound of the hydroxyl of the base shown is reacted；Make that there is "-X⁴-R³" represented by base and nitrobenzophenone halogenation Object with have "-W¹-(R²-W²) base represented by p- " hydroxyl the method reacted of compound；Make that there is "-R¹-W¹- (R²-W²) base represented by p- " hydroxyl the method reacted with nitrobenzoyl chloride of compound；Make that there is "-R¹- W¹-(R²-W²) base represented by p- " the method reacted with nitrobenzene formyl rate of level-one amine；Make that there is "-R¹-W¹-(R²- W²) base represented by p- " the method etc. reacted of acyl chlorides compound and 4- nitroaniline or derivatives thereof.

Reaction to obtain the dinitro intermediate preferably carries out in organic solvent.Organic solvent herein is only If solvent reaction not impacted, such as methanol, ethyl alcohol, tetrahydrofuran, toluene, methylene chloride, two can be enumerated Methyl sulfoxide, dimethylformamide, dimethyl acetamide, n-methyl-2-pyrrolidone etc..In addition, the reaction optionally may be used It carries out in the presence of a catalyst.

The reduction reaction of the dinitro intermediate be preferably capable in organic solvent, using such as palladium carbon, platinum oxide, The catalyst such as zinc, iron, tin, nickel are implemented.Organic solvent used herein can for example enumerate ethyl acetate, toluene, tetrahydrofuran, Alcohol system etc..Wherein, the synthesis sequence of specific diamines is not limited to the method.

[synthesis of polyamic acid (P)]

The tetracarboxylic dianhydride of the synthetic reaction of polyamic acid (P) and the use ratio of diamines are supplied to preferably relative to two The anhydride group of 1 equivalent of amino of amine, tetracarboxylic dianhydride becomes 0.2 equivalent~2 equivalents ratio, more preferably becomes 0.3 equivalent The ratio of~1.2 equivalents.

In the synthesis of polyamic acid (P), can also be used together with tetracarboxylic dianhydride as described above and diamines appropriate Molecular weight regulator synthesizes the polymer of end modified type.It, can be lossless by synthesizing the polymer of the end modified type Further improve to The effect of invention the coating (printing) of aligning agent for liquid crystal.

Molecular weight regulator can for example enumerate the single acid anhydride of the acid such as maleic anhydride, phthalic anhydride, itaconic anhydride, benzene The monoamine compounds such as amine, cyclohexylamine, n-butylamine, monoisocyanate compounds such as phenyl isocyanate, isocyanic acid naphthalene ester etc..Phase For total 100 parts by weight of used tetracarboxylic dianhydride and diamines, the use ratio of molecular weight regulator is preferably set For 20 parts by weight hereinafter, being more preferably set as 10 parts by weight or less.

The synthetic reaction of polyamic acid preferably carries out in organic solvent.The organic solvent used when reaction can for example arrange Lift aprotic polar solvent, phenol system solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon etc..In these organic solvents, it is preferable to use 1 kind in the group as composed by aprotic polar solvent and phenol system solvent (organic solvent of the first group) with On, or one or more of organic solvent selected from the first group with selected from being made of alcohol, ketone, ester, ether, halogenated hydrocarbon and hydrocarbon One or more of group's (organic solvent of the second group) mixture.For the latter, relative to the first group Organic solvent and the second group organic solvent total amount, the use ratio of the organic solvent of the second group is preferably 50 Weight % hereinafter, more preferably 40 weight % hereinafter, especially preferably 30 weight % or less.

Particularly preferably using selected from by n-methyl-2-pyrrolidone, n,N-dimethylacetamide, N, N- dimethyl formyl Amine, dimethyl sulfoxide, gamma-butyrolacton, tetramethylurea, hexamethylphosphoramide, metacresol, xylenol and halogenation phenol institute group At one or more of group be used as solvent, or a kind or more of these solvents is preferably used in the range of the ratio With the mixture of other organic solvents.

The usage amount (a) of organic solvent is preferably to be set as total amount (a+b) relative to reaction solution, tetracarboxylic dianhydride and The total amount (b) of diamines becomes the amount of 0.1 weight of weight %~50 %.The reaction temperature of the synthetic reaction of polyamic acid is preferred It is -20 DEG C~150 DEG C, more preferably 0 DEG C~100 DEG C.In addition, the reaction time is preferably 0.1 hour~24 hours, more preferably 0.5 hour~12 hours.

As previously discussed, it obtains reaction solution made of polyamic acid (P) dissolution.The reaction solution can be supplied directly to The preparation of aligning agent for liquid crystal is available to aligning agent for liquid crystal after can also separating polyamic acid contained in reaction solution (P) Preparation, or the preparation of aligning agent for liquid crystal can also be available to after purification to separated polyamic acid (P).Right Polyamic acid (P) carries out dehydration closed-loop in the case where polyimides is made, and can be supplied directly to be dehydrated by the reaction solution Ring-closure reaction is available to dehydration closed-loop reaction after can also separating polyamic acid contained in reaction solution (P), or also Dehydration closed-loop reaction can be available to after purification to separated polyamic acid (P).The separation of polyamic acid and pure Change can be carried out according to well known method.

[poly amic acid ester (P)]

Poly amic acid ester (hereinafter also referred to as poly amic acid ester (P)) as the polymer (P) for example can be by following Method obtains: compound, the acetal system of [I] by making the polyamic acid (P) obtained by the synthetic reaction and hydroxyl The method that the esterifying agents such as compound, halide, compound containing epoxy group are reacted；[II] make tetracarboxylic acid acid diesters and diamines into The method of row reaction；The method etc. that [III] reacts tetracarboxylic acid acid diesters dihalide with diamines.

Herein, the concrete example as esterifying agent used in method [I], the compound of hydroxyl can for example be enumerated: methanol, The alcohols such as ethyl alcohol, propyl alcohol, phenols such as phenol, cresols etc.；Acetal based compound can for example enumerate n,N-Dimethylformamide diethyl Base acetal, N, N- diethylformamide diethyl acetal；Halide can for example be enumerated: bromomethane, bromic ether, bromo 18 Alkane, chloromethane, chlorooctadecane, 1,1,1- tri- fluoro- 2- iodoethane etc.；Compound containing epoxy group can for example enumerate epoxy third Alkane etc..

Tetracarboxylic dianhydride can be carried out open loop and be obtained by tetracarboxylic acid acid diesters used in method [II] by using the alcohols ?.In addition, tetracarboxylic acid acid diesters dihalide used in method [III] can be by making the tetrabasic carboxylic acid two obtained as described above Ester is reacted with the chlorinating agent appropriate such as thionyl chloride and is obtained.Diamines used in method [II] and method [III] is preferred For other described diamines optionally can also be used comprising the specific diamines.In addition, poly amic acid ester (P) can only have amide Acrylate structure, the partial esterification object for being also possible to amic acid structure and amic acid esters structure and depositing.

[polyimides (P)]

Polyimides (hereinafter also referred to as polyimides (P)) as the polymer (P) for example can be by institute as above It states the polyamic acid (P) synthesized like that and carries out dehydration closed-loop, and be subject to imidizate and obtain.

The polyimides (P) can be to whole amic acid knot possessed by the polyamic acid (P) as its predecessor Structure carries out complete acid imide compound made of dehydration closed-loop, is also possible to only be dehydrated to a part of amic acid structure to close Ring, the part acid imide compound for making amic acid structure and imide ring structure and depositing.Contained in aligning agent for liquid crystal of the invention The acid imide rate of polyimides be preferably 30% or more, more preferably 40%~99%, especially preferably 50%~99%. The acid imide rate is will be relative to the total of the quantity of the quantity and imide ring structure of the amic acid structure of polyimides Imide ring structure quantity shared by ratio be indicated with percentage.Herein, a part of imide ring can be different Imide ring.

The dehydration closed-loop of polyamic acid is preferably carried out using following methods: the method heated to polyamic acid, Or polyamic acid is dissolved in organic solvent, dehydrating agent and dehydration closed-loop catalyst are added in the solution, optionally The method heated.Wherein, later approach is preferably utilized.

In the method for adding dehydrating agent and dehydration closed-loop catalyst in the solution of polyamic acid, dehydrating agent is for example The acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride can be used.The usage amount of dehydrating agent is preferably the amide relative to polyamic acid 1 mole of sour structure and be set as 0.01 mole~20 moles.Dehydration closed-loop catalyst for example can be used: pyridine, collidine, two The tertiary amines such as picolin, triethylamine.The usage amount of dehydration closed-loop catalyst preferably relative to 1 mole of used dehydrating agent and It is set as 0.01 mole~10 moles.Organic solvent used in dehydration closed-loop reaction can be enumerated as synthesizing polyamides acid Organic solvent and the organic solvent illustrated.The reaction temperature of dehydration closed-loop reaction is preferably 0 DEG C~180 DEG C, more preferably 10 DEG C ~150 DEG C.Reaction time is preferably 1.0 hours~120 hours, more preferably 2.0 hours~30 hours.

The reaction solution for containing polyimides (P) is obtained in this way.The reaction solution can be supplied directly to liquid crystal and take It, can also be to be available to aligning agent for liquid crystal after removal dehydrating agent and dehydration closed-loop catalyst in autoreaction solution to the preparation of agent Preparation, be available to the preparation of aligning agent for liquid crystal after polyimides can also being separated, or can also will be separated poly- Acid imide is available to the preparation of aligning agent for liquid crystal after purification.These purification process can be carried out according to well known method.In addition, Polyimides (P) can be obtained by the imidizate of poly amic acid ester (P).

Polyamic acid (P), poly amic acid ester (P) and the polyimides (P) obtained in this way is preferably worked as it When the solution that concentration is 15 weight % is made, there is 20mPas~1, the solution viscosity of 800mPas more preferably has The solution viscosity of 50mPas~1,500mPas.In addition, the solution viscosity (mPas) of the polymer is for using this The polymerization that the good solvent (such as gamma-butyrolacton, n-methyl-2-pyrrolidone etc.) of polymer is 15 weight % the concentration for preparing Object solution is worth obtained by measuring at 25 DEG C using E type rotational viscometer.

Utilization gel permeation chromatography (the Gel of the polyamic acid (P), poly amic acid ester (P) and polyimides (P) Permeation Chromatography, GPC) measure polystyrene conversion weight average molecular weight (Mw) be preferably 1, 000~500,000, more preferably 2,000~300,000.In addition, the quantity of Mw and the polystyrene conversion measured using GPC Molecular weight distribution (Mw/Mn) represented by the ratio of average molecular weight (Mn) is preferably 15 hereinafter, more preferably 10 or less.Pass through place It can ensure that the good orientation and stability of liquid crystal display element in such molecular weight ranges.

Aligning agent for liquid crystal of the invention contains the polymer (P), but can also optionally contain other compositions.It can make an addition to Other polymers, the intramolecular that other compositions in the aligning agent for liquid crystal can for example be enumerated other than the polymer (P) have Compound (hereinafter referred to as " compound containing epoxy group "), the functional silanes compound, metal-chelating of at least one epoxy group Compounds, hardening accelerator, surfactant etc..

[other polymers]

The other polymers can use to improve solution properties or electrical characteristics.The other polymers are in main chain The upper polymer without part-structure represented by the formula (1), is not particularly limited about its main framing.Specifically, Such as it can enumerate polyamic acid, polyimides, poly amic acid ester, polysiloxane, polyester, polyamide, cellulose is derivative Object, polyacetals, polystyrene derivative, poly- (styrene-phenylmaleimide) derivative, poly- (methyl) acrylate Etc. the polymer for being set as main framing.Wherein, it is preferably selected from by polyamic acid, poly amic acid ester, polyimides and poly-organosilicon At least one of group composed by oxygen alkane polymer.Other polymers can be synthesized by known method.In addition, In the case where assigning liquid crystal aligning ability using optical alignment method to the film for using aligning agent for liquid crystal of the invention and being formed, It can be used the polymer with the light orientation structure as the other polymers.

In the case where making an addition to other polymers in aligning agent for liquid crystal, it polymerize relative to contained in aligning agent for liquid crystal Total 100 parts by weight of object, the allotment ratio of the other polymers are preferably set as 50 parts by weight hereinafter, being more preferably set as Below 0.1 parts by weight~40 parts by weight, especially preferably 0.1 parts by weight~30 parts by weight.

[compound containing epoxy group]

Compound containing epoxy group can make to improve liquid crystal orientation film with cementability or the electrical characteristics of substrate surface With.This compound containing epoxy group can for example be enumerated: ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, third Hexanediol diglycidyl ether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol 2-glycidyl Ether, 1,6- hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2,2- dibromo Neopentylglycol diglycidyl ether, N, N, N ', bis- (N, the N- 2-glycidyls of N '-four glycidyl group-m-xylene diamine, 1,3- Base amino methyl) hexamethylene, N, N, N ', four glycidyl group -4 N ' -, 4 '-diaminodiphenyl-methanes, N, N- 2-glycidyl Base-benzyl amine, N, N- glycidyl-aminomethyl cyclohexane, N, N- diglycidyl-cyclo-hexylamine etc., as excellent The compound of choosing.In addition to this, No. 2009/096598 record of International Publication No. can be used in the example of the compound containing epoxy group Polysiloxane containing epoxy group.

In the case where making an addition to these epoxides in aligning agent for liquid crystal, relative to contained in aligning agent for liquid crystal Total 100 parts by weight of polymer, the allotment ratio of the epoxide are preferably set as 40 parts by weight hereinafter, more preferably It is set as 0.1 parts by weight~30 parts by weight.

[functional silanes compound]

The functional silanes compound can for improve aligning agent for liquid crystal printing purpose and use.This function Property silane compound can for example be enumerated: 3- TSL 8330,3-aminopropyltriethoxysilane, 2- aminopropan Base trimethoxy silane, 2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- TSL 8330, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- ureido-propyl trimethoxy silane, 3- ureido-propyl three Ethoxysilane, N- ethoxy carbonyl -3- TSL 8330, N- tri-ethoxy silylpropyl triethylene three Amine, 10- trimethoxy silane base-Isosorbide-5-Nitrae, tri- azepine decane of 7-, 9- trimethoxy silane base -3,6- diaza nonyl acetic acid esters, 9- trimethoxy silane base -3,6- diaza methyl pelargonate, N- benzyl -3- TSL 8330, N- phenyl -3- ammonia Base propyl trimethoxy silicane, glycidoxypropyl methyltrimethoxysilane, 2- glycidoxypropyl ethyl trimethoxy silicon Alkane, 3- glycidoxypropyltrimewasxysilane etc..

In the case where making an addition to these functional silanes compounds in aligning agent for liquid crystal, relative in aligning agent for liquid crystal Total 100 parts by weight of contained polymer, the allotment ratio of the functional silanes compound be preferably set as 2 parts by weight with Under, more preferably it is set as 0.02 parts by weight~0.2 parts by weight.

[meal chelate compounds]

The meal chelate compounds are in the case where the component of polymer of aligning agent for liquid crystal has epoxy construction, out Contain in the purpose for the mechanical strength for guaranteeing the film formed by low-temperature treatment in aligning agent for liquid crystal (especially phase difference film With aligning agent for liquid crystal) in.The meal chelate compounds are preferably the pentanedione using the metal in aluminium, titanium and zirconium Complex compound or acetoacetate complex compound.Specifically, can for example enumerate: diisopropoxy oacetic acid aluminium, three (acetyl Benzylacetone acid) aluminium, three (oacetic acid) aluminium, bis- (oacetic acid) titaniums of diisopropoxy, the bis- (acetyl of diisopropoxy Benzylacetone acid) titanium, three-n-butoxyethyl acetoacetate zirconiums, bis- (oacetic acid) zirconiums of two-n-butoxies etc..It is adding It is described relative to total 100 parts by weight of the constituent comprising epoxy construction in the case where the meal chelate compounds The use ratio of meal chelate compounds is preferably 50 parts by weight hereinafter, more preferably 0.1 parts by weight~40 parts by weight, especially Preferably 1 parts by weight~30 parts by weight.

[hardening accelerator]

In the case that the hardening accelerator is that the component of polymer in aligning agent for liquid crystal has epoxy construction, in order to protect Card is formed by the mechanical strength of liquid crystal orientation film and the ageing stability of liquid crystal aligning and contains (special in aligning agent for liquid crystal It is not phase difference film aligning agent for liquid crystal) in.The hardening accelerator for example can be used with phenylol, silanol group, mercapto, The compound of phosphate, sulfonic group, carboxyl, acid anhydride etc., wherein the preferably chemical combination with phenylol or silanol group Object.As its concrete example, the compound with phenylol can for example be enumerated: cyanophenol, nitrophenol, methoxyphenoxy benzene Phenol, thio phenoxy phenyl, 4- benzylphenol etc.；Compound with silanol group can for example be enumerated: trimethyl silicane alkanol, three Ethylsilane alcohol, 1,1,3,3- tetraphenyl -1,3- disiloxane glycol, Isosorbide-5-Nitrae-bis- (hydroxyl dimethylsilyl) benzene, triphenyl Silanol, three (p-methylphenyl) silanols, diphenyl silanodiol etc..In the case where adding hardening accelerator, relative to packet Total 100 parts by weight of constituent containing epoxy construction, the use ratio of the hardening accelerator be preferably 50 parts by weight with Under, more preferably 0.1 parts by weight~40 parts by weight, especially preferably 1 parts by weight~30 parts by weight.

[surfactant]

The surfactant can contain and take in liquid crystal to the purpose of the coating of substrate for aligning agent for liquid crystal is improved To in agent (especially phase difference film aligning agent for liquid crystal).This surfactant can for example be enumerated: nonionic surfactant, Anionic surfactant, cationic surfactant, amphoteric surfactant, silicone surfactant, polyalkylene oxide surface Activating agent, fluorine-containing surfactant etc..Relative to 100 parts by weight of total amount of aligning agent for liquid crystal, the use ratio of surfactant 10 parts by weight are preferably set as hereinafter, being more preferably set as 1 parts by weight or less.

In addition, other compositions other than the ingredient, can enumerate the change that intramolecular has at least one oxetanylmethoxy Close object or antioxidant etc..

The other compositions that aligning agent for liquid crystal of the invention is prepared to the polymer (P) and optionally uses are preferably It is dispersed or dissolved in liquid composition made of in solvent appropriate.

Used organic solvent can for example be enumerated: n-methyl-2-pyrrolidone, gamma-butyrolacton, butyrolactam, N, Dinethylformamide, n,N-dimethylacetamide, 4- hydroxy-4-methyl-2-pentanone, glycol monoethyl ether, butyl lactate, second Acid butyl ester, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, second two Alcohol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol two Methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethyl two Alcohol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, carbonic acid Sub- propyl ester etc..These solvents can be used alone or be used in mixed way two or more.

Solid component concentration (total weight of the ingredient other than the solvent of aligning agent for liquid crystal in aligning agent for liquid crystal of the invention Measure ratio shared of the total weight of the liquid crystal alignment agent) it allows for viscosity, volatility etc. suitably to select, preferably 1 weight Measure the range of the weight of %~10 %.That is, aligning agent for liquid crystal of the invention is in a manner of aftermentioned by being coated on substrate surface, preferably It is heated, and forms the film as liquid crystal orientation film or the film as liquid crystal orientation film.At this point, dense in solid component In the case that degree is less than 1 weight %, the film thickness of film becomes too small and is difficult to obtain good liquid crystal orientation film.On the other hand, In the case where solid component concentration is more than 10 weight %, the film thickness of film becomes excessive and is difficult to obtain good liquid crystal aligning Film, additionally, there are the viscosity of aligning agent for liquid crystal to increase and the tendency of coating decline.

According to the purposes of aligning agent for liquid crystal or on substrate, coating of liquid crystalline takes the range of particularly preferred solid component concentration To method used when agent and it is different.Such as the aligning agent for liquid crystal about liquid crystal orientation film, it is applied using rotator method In the case where being distributed on substrate, (total weight of the whole components other than solvent in aligning agent for liquid crystal exists solid component concentration Proportion in the total weight of aligning agent for liquid crystal) it is particularly preferably the range of 1.5 weight of weight %~4.5 %.Utilizing printing In the case where method, solid component concentration is particularly preferably set as to the range of 3 weight of weight %~9 %, thus by solution viscosity It is set as the range of 12mPas~50mPas.Using ink-jet method, particularly preferably solid component concentration is set For the range of 1 weight of weight %~5 %, thus solution viscosity is set as to the range of 3mPas~15mPas.The preparation present invention Aligning agent for liquid crystal when temperature be preferably 10 DEG C~50 DEG C, more preferably 20 DEG C~30 DEG C.In addition, about phase difference film Aligning agent for liquid crystal, for making the coating of aligning agent for liquid crystal and being formed by the viewpoint of film thickness appropriateness of film, liquid crystal is taken It is preferably the range of 0.2 weight of weight %~10 % to the solid component concentration of agent, more preferably 3 weight of weight %~10 %'s Range.

Liquid crystal orientation film can be manufactured by using the aligning agent for liquid crystal of the invention of the explanation.In addition, using this hair Bright aligning agent for liquid crystal is preferably applied to the liquid crystal of (liquid crystal cells use) used for liquid crystal display element come the liquid crystal orientation film that is formed The liquid crystal orientation film of alignment films and phase difference film.Hereinafter, being carried out to liquid crystal display element of the invention and phase difference film Explanation.

[liquid crystal display element]

Liquid crystal display element of the invention has the liquid crystal orientation film formed using the aligning agent for liquid crystal.Of the invention The action mode of liquid crystal display element is not particularly limited, such as can be applied to TN type, STN type, VA type (comprising vertical orientation- It is multidomain vertical orientation (Vertical Alignment-Multidomain Vertical Alignment, VA-MVA) type, vertical Vertically oriented (Vertical Alignment-Patterned Vertical Alignment, the VA-PVA) type of orientation-pattern Deng), IPS type, FFS type, the various motions mould such as optical compensation curved (optically compensation bend, OCB) type Formula.

Liquid crystal display element of the invention can for example come by the inclusion of the step of following step (1-1)~step (1-3) Manufacture.Step (1-1) uses different substrates according to required action mode.Step (1-2) and step (1-3) are each dynamic It is common in operation mode.

[step (1-1): the formation of film]

Firstly, then being heated to coated face and by being coated with aligning agent for liquid crystal of the invention on substrate in substrate Upper formation film.

(1-1A) manufacturing such as TN type, STN type or in the case where VA type liquid crystal display element, firstly, will be provided with Two pieces of substrates of patterned transparent conductive film in its each transparent conductive film forming face, are preferably utilized as a pair Flexographic printing process, method of spin coating, roll coater method or ink jet printing method are respectively coated aligning agent for liquid crystal of the invention. Substrate for example can be used: the glass such as float glass, soda-lime glass；Include polyethylene terephthalate, poly terephthalic acid fourth two The transparent substrate of the plastics such as ester, polyether sulfone, polycarbonate, poly- (ester ring type alkene).It is set to the electrically conducting transparent of the one side of substrate It includes tin oxide (SnO that film, which can be used,₂) nesa (NESA) film (PPG register of company, U.S. trade mark), include indium oxide-tin oxide (In₂O₃-SnO₂) tin indium oxide (indium tin oxide, ITO) film etc..In order to obtain patterned transparent conductive film, Such as using following methods: after forming the transparent conductive film of pattern-free, forming the method for pattern by being etched by light；It is formed saturating The method etc. of the mask with required pattern is used when bright conductive film.When coating of liquid crystalline alignment agent, in order to make substrate surface and The cementability of transparent conductive film and film is better, can also be pre-coated with official to the face for forming film in substrate surface, implementation The pre-treatment of energy property silane compound, functionality titanium compound etc..

After coating of liquid crystalline alignment agent, the purpose of for the sagging for preventing be coated with aligning agent for liquid crystal, preferably implement pre- It heats (prebake conditions).Prebake conditions temperature is preferably 30 DEG C~200 DEG C, and more preferably 40 DEG C~150 DEG C, particularly preferably 40 DEG C~ 100℃.The prebake conditions time is preferably 0.25 minute~10 minutes, more preferably 0.5 minute~5 minutes.Then, for by solvent Completely remove, optionally by the presence of polymer amic acid structure carry out hot-imide purpose, and implement firing (after Baking) step.Firing temperature (rear baking temperature) at this time is preferably 80 DEG C~300 DEG C, more preferably 120 DEG C~250 DEG C.Afterwards Baking time is preferably 5 minutes~200 minutes, more preferably 10 minutes~100 minutes.The film of the film formed as described above Preferably 0.001 μm~1 μm, more preferably 0.005 μm~0.5 μm of thickness.

(1-1B) manufacturing IPS type or in the case where FFS type liquid crystal display element, by being provided with comprising through pattern Electrode forming surface, the opposite base with not set electrode for turning to the substrate of the transparent conductive film of interdigitated electrode structure or the electrode of metal film In the one side of plate, it is respectively coated aligning agent for liquid crystal of the invention, then each coated face is heated to form film.About this When the substrate used and the material of transparent conductive film, coating method, coating after heating condition, transparent conductive film or metal The pre-treatment of the patterning method, substrate of film and the preferred film thickness for being formed by film are identical as (1-1A).Metal The film comprising metals such as chromium for example can be used in film.

Under any case of (1-1A) and (1-1B), by the coating of liquid crystalline alignment agent on substrate after, Organic solvent removal is formed into liquid crystal orientation film or as the film of liquid crystal orientation film.At this point, by after film is formed Further progress heating, and make the polyamic acid deployed in aligning agent for liquid crystal of the invention, poly amic acid ester and polyimides Dehydration closed-loop reaction carry out, so that the film of further imidizate be made.

[step (1-2): alignment capability imparting processing]

In the case where manufacturing TN type, STN type, IPS type or FFS type liquid crystal display element, implement to the step (1-1) The film of middle formation assigns the processing of liquid crystal aligning ability.The alignment capability of liquid crystal molecule is imparted on film and shape as a result, At liquid crystal orientation film.Alignment capability imparting processing can be enumerated: have using twisting cohesion including, for example, fibers such as nylon, artificial silk, cottons The roller of cloth irradiates the light of the radioactive ray of polarisation or non-polarized to film to the friction treatment that film rubs to certain orientation Orientation process etc..It on the other hand, can be by formation in the step (1-1) in the case where manufacturing VA type liquid crystal display element Film is directly used as liquid crystal orientation film, can also implement alignment capability imparting processing to the film.In addition, because using liquid of the invention The rub resistance of the brilliant resulting film of alignment agent is good, limits so high orientation can be assigned to film by friction treatment Power.

In light orientation processing, the wavelength comprising 150nm~800nm for example can be used to the radioactive ray that film is irradiated The ultraviolet light and luminous ray of light.In the case where radioactive ray are polarisation, it can be linear polarization and be also possible to part polarisation.Separately Outside, in the case where used radioactive ray are linear polarization or part polarisation, real estate can be shone from vertical direction It penetrates, can also be irradiated from inclined direction, or these irradiation combinations can also be carried out.In the radiation of irradiation non-polarized In the case where line, direction of illumination is set as inclined direction.

Used light source for example can be used: Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon resonance Lamp, xenon lamp, excimer laser etc..The ultraviolet light in optimal wavelength region can be by by light source and such as optical filter, diffraction grating Deng method etc. obtain.The exposure of radioactive ray is preferably 100J/cm²~50,000J/cm², more preferably 300J/ cm²~20,000J/cm².In addition, in order to improve the reactive illumination that can be carried out while heating to film to film It penetrates.Temperature when heating is usually 30 DEG C~250 DEG C, preferably 40 DEG C~200 DEG C, more preferably 50 DEG C~150 DEG C.

In addition, can be to being handled below the liquid crystal orientation film further progress after friction treatment, so that liquid crystal orientation film be made to exist Each region has different liquid crystal aligning abilities: making liquid crystal aligning by a part irradiation ultraviolet light to liquid crystal orientation film The processing of the pre-tilt angle variation in a part of region of film；Or after a part of liquid crystal aligning film surface forms resist film, Friction treatment is carried out to the direction different from friction treatment just now, then removes the processing of resist film.In this case, can Improve the visual field characteristic of resulting liquid crystal display element.The liquid crystal orientation film for being suitable for VA type liquid crystal display element can be also applicable in (Polymer sustained alignment, PSA) type liquid crystal display element is orientated in polymer stabilizing.

[step (1-3): liquid crystal cells are constructed]

By 2 pieces of substrates for preparing to be formed with liquid crystal orientation film in this way, and match between 2 pieces of oppositely disposed substrates Liquid crystal is set to manufacture liquid crystal cells.When manufacturing liquid crystal cells, such as 2 kinds of methods below can be enumerated.First method be it is previous The method known.Firstly, in such a way that respective liquid crystal orientation film is opposite, across gap (cell gap) by 2 pieces of substrate opposite directions The peripheral portion of 2 pieces of substrates is bonded by configuration using sealant, is infused in by substrate surface and the cell gap of sealant division After entering filling liquid crystal, injection hole is sealed, thus can manufacture liquid crystal cells.In addition, second method is referred to as liquid crystal drip-injection (One Drop Fill, ODF) mode method.Regulation on one of substrate in 2 pieces of substrates for being formed with liquid crystal orientation film Position, be coated with such as ultraviolet light photopolymerization sealant, and then in liquid crystal alignment film surface as defined in several position dropping liquids After crystalline substance, it is bonded another piece of substrate in such a way that liquid crystal orientation film is opposite, and liquid crystal is spread out in the entire surface of substrate, then It to the entire surface irradiating ultraviolet light of substrate, cures the sealant, thus can manufacture liquid crystal cells.In the feelings using any method Under condition, preferably by the liquid crystal cells manufactured in this way, and then liquid crystal used in being heated to become it is each to After the temperature of same sex phase, it is slowly cooled down to room temperature, to remove flow orientation when liquid crystal filling.

The bonding agent as liquid crystal can be used and usually used bonding agent in sealant, such as can be used and contain curing agent Epoxy resin etc..In addition, sealant can also be used and then the epoxy resin etc. containing the alumina balls as spacer.

Liquid crystal can enumerate nematic crystal (nematic liquid crystal) and disc-like liquid crystal (smectic Liquid crystal), wherein preferably nematic crystal, such as can be used: schiff bases (Schiffbase) are liquid crystal, oxidation It is liquid that azo (azoxy), which is liquid crystal, biphenyl system liquid crystal, cyclohexylbenzene system liquid crystal, ester system liquid crystal, terphenyl (terphenyl), Crystalline substance, biphenyl hexamethylene system liquid crystal, pyrimidine system liquid crystal, dioxanes system liquid crystal, double-octane system liquid crystal, cubane (cubane) are liquid Crystalline substance etc..Alternatively, it is also possible to add in these liquid crystal following substance to use such as cholesteryl chloride (cholesteryl Chloride), cholesteryl nonanoate (cholesteryl nonanoate), cholesteryl carbonate (cholesteryl The cholesteryl liquid crystals (cholesteric liquid crystal) such as carbonate)；As trade name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) is come the chiral agent (chiral agent) sold；To decyloxy benzylidene-to amino -2- The ferroelectricities such as methyl butyl cinnamate (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) Liquid crystal (ferroelectric liquid crystal) etc..

Moreover, liquid crystal display element of the invention can be obtained and the outer surface in liquid crystal cells is bonded polarizer. The polarizer for fitting in the outer surface of liquid crystal cells can be enumerated: be referred to as the polarisation of " H film " with the clamping of cellulose acetate protective film Polarizer made of film or comprising itself polarizer of H film, should " H film " be on one side making polyvinyl alcohol while extending orientation It absorbs film made of iodine.

[phase difference film]

Then, to using aligning agent for liquid crystal of the invention to be illustrated come the method for manufacturing phase difference film.Manufacturing this hair When bright phase difference film, dust or electrostatic just can be not only inhibited to generate in step, but also uniform liquid crystal orientation film can be formed Aspect, and can when the irradiation in radioactive ray using photomask appropriate and be randomly formed liquid crystal on substrate and take For in terms of the different multiple regions in direction, optical alignment method is preferably utilized.Specifically, can be via following step (2-1)~step (2-3) is manufactured.

[step (2-1): utilizing the formation of the film of aligning agent for liquid crystal]

Firstly, aligning agent for liquid crystal of the invention is coated on substrate and forms film.Substrate used herein can be suitable for Illustrate includes triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyamides The transparent substrate of the synthetic resin such as amine, polyimides, polymethyl methacrylate, polycarbonate.In these substrates, TAC is usual Protective layer as the light polarizing film in liquid crystal display element.In addition, good with regard to the low aspect of the hygroscopicity of solvent, optical characteristics For the aspect of aspect and low cost, polymethyl methacrylate is preferably used as the substrate of phase difference film.In addition, to It, can also be in substrate surface in order to keep the adhesion of substrate surface and film better in the substrate of coating of liquid crystalline alignment agent Implement conventionally known pre-treatment in the face for forming film.

In most cases, phase difference film is applied in combination with light polarizing film.At this point, special in order to play required optics Property, it is necessary to will be controlled relative to the precise angle of the polarizing axis of light polarizing film as specific direction, to be bonded phase difference film.Therefore, Herein, by the way that the liquid crystal orientation film on the direction of predetermined angular with liquid crystal aligning ability is formed in TAC film or poly- methyl On the substrates such as methyl acrylate, can omit while controlling its angle step phase difference film fitted in light polarizing film. In addition, thus, it is possible to help to improve the productivity of liquid crystal display element.There is liquid in order to be formed on the direction of predetermined angular The liquid crystal orientation film of brilliant alignment capability, it is preferable to use aligning agent for liquid crystal of the invention is carried out using optical alignment method.

Coating of the aligning agent for liquid crystal on substrate can be using suitable coating method, such as can be used: roll coater method, Rotator method, print process, ink-jet method, rod coater method, extrusion die (extrusion die) method, direct gravure coater (direct gravure coater) method, chamber knife type coater (chamber doctor coater) method, hectograph intaglio plate apply Cloth machine (offset gravure coater) method, single roller kiss-coating machine (single roll kiss coater) method, use Trans- kiss-coating machine (reverse kiss coater) method of the gravure roll of path, 3 trans- roll-coater methods, 4 it is trans- Roll-coater method, slit die (slot die) method, Kohler coater method, dextrorotation roll coater method, blade coater, scraper Formula coating machine (knife coater) method, impregnation coater, MB coater, the trans- coater of MB etc..

After coating, (baking) is heated to coated face and forms film.Heating temperature at this time is preferably set as 40 DEG C ~150 DEG C, more preferably it is set as 80 DEG C~140 DEG C.Heating time is preferably set as 0.1 minute~15 minutes, more preferably sets It is 1 minute~10 minutes.The film thickness for the film being formed on substrate is preferably 1nm~1,000nm, and more preferably 5nm~ 500nm。

[step (2-2): light irradiation step]

Then, by assigning liquid crystal aligning energy to film to the film irradiation light being formed on substrate in this way Power is to be made liquid crystal orientation film.Herein, the light irradiated can for example enumerate the ultraviolet of the light comprising 150nm~800nm wavelength Line, luminous ray etc..It preferably include the ultraviolet light of the light of 300nm~400nm wavelength in these light.Irradiation light can be partially Light is also possible to non-polarized.Polarisation preferably uses the light comprising linear polarization.

In the case where used light is polarisation, the irradiation of light can be carried out to real estate from vertical direction, it can also be with The irradiation of light is carried out from inclined direction, or these can also be irradiated combination and carried out.In the case where irradiating non-polarized, it is necessary to Real estate is irradiated from inclined direction.

Used light source can for example be enumerated: Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon resonance Lamp, xenon lamp, mercury-xenon lamp (Hg-Xe lamp) etc..Polarisation can by by these light sources with such as optical filter, diffraction grating simultaneously Method etc. obtains.

The exposure of light is preferably set as 0.1mJ/cm²More than and less than 1,000mJ/cm², more preferably it is set as 1mJ/cm² ~500mJ/cm², especially preferably it is set as 2mJ/cm²~200mJ/cm²。

[step (2-3): the formation of liquid crystal layer]

Then, it on the film in this way after light irradiates, is coated with polymerizable liquid crystal and makes its hardening.Shape as a result, At the film (liquid crystal layer) comprising polymerizable liquid crystal.Polymerizable liquid crystal as used herein is hit by heating and illumination At least one kind of liquid-crystal compounds or liquid-crystal composition for handling to be polymerize.This polymerizable liquid crystal can be used existing known Liquid crystal, specifically, can for example enumerate non-patent literature 1 (" can UV hardening liquid crystal and its apply (UV-Curable Liquid Crystals and Their Application) ", " liquid crystal ", the phase (1999) of volume 3 the 1st, page 34 to the 42nd Page) in record nematic crystal.Alternatively, it is also possible to be: cholesterol liquid crystal；Collar plate shape liquid crystal；Torsion added with chiral agent Nematic alignment-type liquid crystal etc..Polymerizable liquid crystal is also possible to the mixture of various liquid crystal compound.Polymerizable liquid crystal can also be Composition comprising well known polymerization initiator or solvent appropriate etc..

When being coated with polymerizable liquid crystal as described above on being formed by liquid crystal orientation film, such as rod coater can be used The suitable coating method such as method, roll coater method, rotator method, print process, ink-jet method.

Then, the film to the polymerizable liquid crystal formed in this way implements a kind hit selected from heating and illumination Thus the film is hardened and forms liquid crystal layer by above processing.By these handle overlapping carry out, can get good orientation because And it is preferred that.

The heating temperature of film can suitably be selected according to the type of used polymerizable liquid crystal.Such as using Merck In the case where the RMS03-013C of company's manufacture, preferably 40 DEG C~80 DEG C of range at a temperature of heated.When heating Between preferably 0.5 minute~5 minutes.

Irradiation light is preferably using the ultraviolet light of the non-polarized of the wavelength with 200nm~500nm range.The exposure of light Preferably it is set as 50mJ/cm²~10,000mJ/cm², more preferably it is set as 100mJ/cm²~5,000mJ/cm²。

The thickness for being formed by liquid crystal layer is suitably set according to required optical characteristics.Such as it is in manufacture wavelength In the case where 1/2 wavelength plate of the visible light of 540nm, the phase difference that selection is formed by phase difference film becomes 240nm~300nm Thickness, if 1/4 wavelength plate, then selected phase difference becomes the thickness of 120nm~150nm.It can get the liquid of target phase difference The thickness of crystal layer is different according to the optical characteristics of used polymerizable liquid crystal.Such as in the RMS03- manufactured using Merck In the case where 013C, to manufacture 1/4 wavelength plate with a thickness of 0.6 μm~1.5 μm of range.

The phase difference film obtained in this way is preferably used as the phase difference film of liquid crystal display element to apply.Using having There is no restriction to its action mode for the liquid crystal display element of the phase difference film manufactured using aligning agent for liquid crystal of the invention, such as It can be applied to various modes well known to TN type, STN type, IPS type, FFS type, VA type etc..The phase difference film is to being configured at liquid The lateral surface of the polarizer depending on recognizing side of crystal display element, attach phase difference film in substrate-side face come using.It is therefore preferable that To be set as following aspect: the substrate of phase difference film being set as TAC system or acrylic acid substrate, makees the substrate of the phase difference film also It is functioned for the protective film of light polarizing film.

Herein, the method for producing phase difference film on an industrial scale has roll-to-roll mode.The method is from strip The coiling body of base material film rolls out film, on the film rolled out using continuous step to be formed liquid crystal orientation film processing, The processing and the optionally processing of lamination protective film for being coated with polymerizable liquid crystal on liquid crystal orientation film and being hardened, and will The method that film after the step is recycled in the form of coiling body.It is formed using aligning agent for liquid crystal of the invention Phase difference film is good to the adhesion of substrate, even if in the situation for carrying out the phase difference film in the form of coiling body to take care of etc. Under, liquid crystal orientation film is also difficult to remove with substrate.Therefore, product when manufacturing phase difference film is can inhibit in the way of roll-to-roll The decline of yield, for productive viewpoint it is also preferred that.

Liquid crystal display element of the invention can be effectively applied to a variety of devices, such as can be used for: clock and watch, portable game Gaming machine, word processor (word processor), notes type personal computer (note type personal Computer), auto-navigation system, video camera (camcorder), personal digital assistant (Personal Digital Assistant, PDA), it is digital camera (digital camera), mobile phone, smart phone (smartphone), various The various display devices of monitor, LCD TV, information display etc..

[embodiment]

Hereinafter, being illustrated using embodiment to further progress of the present invention, but the present invention is not limited to these realities Apply example.

In embodiment below and synthesis example, the weight average molecular weight of polymer is measured using the following method The solution viscosity of Mw, acid imide rate and epoxide equivalent and polymer solution.In addition, following sometimes by change represented by Formula X It closes object and is referred to as " compound X ".

[the weight average molecular weight Mw of polymer]

Mw is the polystyrene scaled value measured using the GPC of the following conditions.

Tubing string: Tosoh (Tosoh) (stock) manufacture, TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 DEG C

Pressure: 68kgf/cm²

[the acid imide rate of polymer]

Solution containing polyimides is put into pure water, resulting precipitating is fully dried under reduced pressure at room temperature Afterwards, it is dissolved in deuterodimethylsulfoxide, using tetramethylsilane as primary standard substance, measures at room temperature¹H- nuclear magnetic resonance (¹H- Nuclear magnetic resonance,¹H-NMR).According to resulting¹H-NMR spectrum is found out using following numerical expressions (1) Acid imide rate.

Acid imide rate (%)=(1-A¹/A²×α)×100 (1)

(in numerical expression (1), A¹It is the peak area of the proton from NH base occurred near chemical shift 10ppm, A²It is Peak area from other protons, α are 1 of other protons relative to the NH base in the predecessor (polyamic acid) of polymer The number ratio of proton)

[epoxide equivalent]

Epoxide equivalent is measured using the hydrochloric acid recorded in JIS C 2105-methyl ethyl ketone method.

[solution viscosity of polymer solution]

Using E type rotational viscometer, the solution viscosity (mPas) of polymer solution is measured at 25 DEG C.

[embodiment 1-1: the synthesis of compound (DA-1)]

According to following processes 1, Lai Hecheng compound (DA-1).

[changing 15]

[embodiment 1-2: the synthesis of compound (DA-2)]

According to following processes 2, Lai Hecheng compound (DA-2).

[changing 16]

[embodiment 1-3: the synthesis of compound (DA-3)]

According to following processes 3, Lai Hecheng compound (DA-3).

[changing 17]

[embodiment 1-4: the synthesis of compound (DA-4)]

According to following processes 4, Lai Hecheng compound (DA-4).

[changing 18]

[embodiment 1-5: the synthesis of compound (DA-5)]

According to following processes 5, Lai Hecheng compound (DA-5).

[changing 19]

In addition, 4,4 '-dihydroxy dicyclohexyls used in reaction use the constitutional isomer of cis- body and trans- body Mixture is synthesized.

[embodiment 1-6: the synthesis of compound (DA-6)]

According to following processes 6, Lai Hecheng compound (DA-6).

[changing 20]

[embodiment 1-7: the synthesis of compound (AN-4)]

According to following processes 7, Lai Hecheng compound (AN-4).

[changing 21]

[embodiment 1-8: the synthesis of compound (DA-14)]

According to following processes 8, Lai Hecheng compound (DA-14).

[changing 22]

[embodiment 1-9: the synthesis of compound (DA-15)]

According to following processes 9, Lai Hecheng compound (DA-15).

[changing 23]

[embodiment 2-1: the synthesis of polymer (PA-1)]

By 1 as tetracarboxylic dianhydride, 2,3,4- cyclobutane tetracarboxylic dianhydride 9.62g are (relative to used in synthesis two 100 molar part of whole amount of amine is 93 molar parts) and compound (DA-1) 12.83g as diamines (relative in synthesis 100 molar part of whole amount of the diamines used is 50 molar parts) and 1, bis- (4- amino-benzene oxygen) the pentanone 7.55g of 5- (relative to 100 molar part of whole amount of diamines used in synthesis is 50 molar parts) it is dissolved in n-methyl-2-pyrrolidone (N-methyl- 2-pyrrolidone, NMP) 85g and gamma-butyrolacton (γ-butyrolactone, GBL) 85g in the mixed solvent, at 30 DEG C It is lower react within 6 hours.Then, reaction mixture is injected into excessive methanol, precipitates reaction product.It will return It is (following thus to obtain polyamic acid under reduced pressure with 40 DEG C of progress drying in 15 hours after the sediment of receipts is cleaned with methanol Referred to as polymer (PA-1)) 28.3g.Resulting polymer (PA-1) is formed with NMP: GBL=50: 50 solvent and is prepared into 15 weight % measure the viscosity of the solution, result 561mPas.In addition, the polymer solution is stood 3 days at 20 DEG C, As a result gelation is not generated, and storage stability is good.

[embodiment 2-2~embodiment 2-11 and synthesis example 1: the synthesis of polyamic acid]

In the embodiment 2-1, in addition to tetracarboxylic dianhydride and diamines used in reacting type and quantitative change more Other than as described in following table 1, polyamic acid is obtained in a manner of identical with embodiment 2-1.In addition, about tetracarboxylic dianhydride, Numerical value in table 1 indicates the use ratio (mole %) of the whole amount relative to tetracarboxylic dianhydride used in reaction, about two Amine, the numerical value in table 1 indicate the use ratio (mole %) of the whole amount relative to diamines used in reaction.For embodiment Obtained in polymer solution, stand 3 days at 20 DEG C respectively, as a result do not generate gelation, storage stability is good.

[table 1]

The abbreviation of tetracarboxylic dianhydride and diamines in table 1 are as described below.

(tetracarboxylic dianhydride)

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

AN-2: pyromellitic acid anhydride

AN-3:2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides

AN-5:5- (2,5- dioxotetrahydro furans -3- base) -8- methyl -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans It mutters -1,3- diketone

AN-6: bicyclic [33.0] octane -2,4,6,8- tetrabasic carboxylic acid 2:4,6:8- dianhydrides

AN-7:5- (2,5- dioxotetrahydro furans -3- base) -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans -1,3- bis- Ketone

(diamines)

DA-7:4,4 '-bis- (4- amino-benzene oxygen) biphenyl

DA-8:4,4 '-diaminodiphenyl-methanes

Bis- (4- amino-benzene oxygen) pentanes of DA-9:1,5-

DA-10:4,4 '-diamino-diphenyl amine

DA-11:3,5- diaminobenzoic acid

DA-12:3,5- diaminobenzoic acid cholesteric Arrcostab

DA-13:4- (tetradecyloxyaniline) benzene -1,3- diamines

In addition, polymer (PA-9), particularly suitable for TN type liquid crystal display element, polymer (PA-10) is suitable for VA type (vertical orientating type) liquid crystal display element.

[embodiment 2-12: the synthesis of polymer (PI-1)]

By 2 as tetracarboxylic dianhydride, 3,5- tricarboxylic cyclopentyl acetic acid dianhydride 16.43g are (relative to used in synthesis 100 molar part of whole amount of diamines is 98 molar parts) and compound (DA-1) 18.21g as diamines (relative to synthesis Used in 100 molar part of whole amount of diamines be 50 molar parts) and compound (DA-9) 15.36g (relative to being used in synthesis Diamines 100 molar part of whole amount be 50 molar parts) be dissolved in the NMP of 200g, at room temperature carry out 6 hours react.After And the NMP of additional 250g, it adds pyridine 11.6g and acetic anhydride 14.97g and carries out 5 hours dehydration closed-loop reactions at 80 DEG C. Then, reaction mixture is injected into excessive methanol, precipitates reaction product.By the sediment recycled with methanol After being cleaned, under reduced pressure with 40 DEG C of progress drying in 15 hours, thus to obtain the polyimides of acid imide rate about 68% (PI-1).Resulting polyimides (PI-1) is prepared into 15 weight % using NMP.The viscosity of the solution is measured, result is 893mPa·s。

[synthesis example 2: the synthesis of polysiloxane (S-1)]

In the reaction vessel for having blender, thermometer, addition funnel and the cooling tube that flows back, 2- (3,4- rings are put into Oxygen cyclohexyl) ethyl trimethoxy silane 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, it carries out at room temperature Mixing.Thereto, 30 minutes are spent from addition funnel to mix, exist under reflux on one side on one side after deionized water 100g is added dropwise It carries out reacting for 6 hours at 80 DEG C.After reaction, organic layer is taken out, it is cleaned using 0.2 weight % aqueous ammonium nitrate solution Until the water after cleaning becomes neutral, then under reduced pressure by solvent and water distillation removal, thus with sticky transparent liquid The form of body obtains the polysiloxane with oxiranyl.To the polysiloxane with oxiranyl into Row¹H-NMR analysis, as a result near chemical shift (δ)=3.2ppm, obtains as theoretical strength based on oxiranyl Peak value confirms the side reaction for not generating oxiranyl in reaction.Measure the polysiloxane with oxiranyl Epoxide equivalent, result are 186g/ equivalent.

Then, in the three-necked flask of 100mL, the polysiloxane with oxiranyl of the acquisition is put into 9.3g, methyl iso-butyl ketone (MIBK) 26g, 4- phenoxy group cinnamic acid 3g and UCAT 18X (trade name, general sieve in Sanya (San-Apro) (stock) manufacture) 0.10g, it carries out reacting for 12 hours while stirring at 80 DEG C.After reaction, reaction mixture is put into Into methanol, sediment generated is recycled, which is dissolved in ethyl acetate and solution is made, which is washed After 3 times, solvent is distilled and is removed, thus being obtained in the form of white powder, there is oxiranyl and the poly- of cinnamic acid structure to have Organic siloxane (S-1) 6.3g.For the polysiloxane (S-1), the polystyrene measured using gel permeation chromatography The weight average molecular weight Mw of conversion is 3,500.

[embodiment 3-1: friction orientation FFS type liquid crystal display element]

(1) preparation of aligning agent for liquid crystal

100 parts by weight of polymer obtained in embodiment 2-1 as polymer (PA-1) are dissolved in comprising γ-Ding Nei The mixed solvent (GBL: NMP: BC=40: 40: 20 of ester (GBL), NMP and butyl cellosolve (Butyl Cellosolve, BC) (weight ratio)) in, the solution that solid component concentration is 3.5 weight % is made.The filter for being 0.2 μm using aperture is by the solution Filtering, thus prepares aligning agent for liquid crystal (R-1).

(2) evaluation of coating

Using rotator, the aligning agent for liquid crystal (R-1) of the preparation is coated on glass substrate, in 80 DEG C of heating plate After 1 minute prebake conditions of upper progress, carry out carrying out heating in 1 hour (rear baking) in 200 DEG C of baking ovens of nitrogen displacement in by library, Average film thickness, which is consequently formed, isFilm.The film is observed using the microscope that multiplying power is 100 times and 10 times, is adjusted Look into the presence or absence of film thickness unevenness and pin hole.Evaluation is to proceed as follows: even if the microscope using 100 times is seen The case where examining, not observing that film thickness is uneven and both pin holes is evaluated as coating " good ", micro- by 100 times of utilization Sem observation to film thickness is uneven and pin hole at least any one, but do not observed using 10 times of microscope film thickness it is uneven and The case where both pin holes, is evaluated as coating "available", will clearly observe film thickness unevenness and pin hole using 10 times of microscope At least any one the case where be evaluated as coating " bad ".In the present embodiment, even if the microscope using 100 times is not observed To both film thickness unevenness and pin hole, coating is " good ".

(3) evaluation of rub resistance

For the film of the acquisition, using the friction machine for the roller for having cotton with twisting cohesion, with roller revolving speed 1000rpm, Platform movement speed 20cm/ seconds, hair indentation length 0.4mm implement 7 friction treatments.Gained is observed using optical microscopy Substrate on caused foreign matter (fragment of film) is eliminated by friction, calculate in the region for measuring 500 μm of 500 μ m Foreign matter number.Evaluation is to proceed as follows: the situation that foreign matter number is 3 or less being evaluated as rub resistance " good ", by 4 Above and 7 or less situations are evaluated as rub resistance "available", and 8 or more situations are evaluated as rub resistance " bad ".Its It as a result is that the rub resistance of the film is " good ".

(4) manufacture of the FFS type liquid crystal display element of friction treatment is utilized

Make FFS type liquid crystal display element 10 shown in FIG. 1.Firstly, by there is the glass base of electrode pair in wherein one side Plate 11a, with the opposite glass substrate 11b of not set electrode as a pair of, the electrode is to being sequentially formed with without pattern Hearth electrode 15, the silicon nitride film as insulating layer 14 and the patterned top electrode 13 for comb teeth-shaped, then in glass substrate In the one side in the face and opposite glass substrate 11b with transparent electrode of 11a, it is respectively coated using rotator in (1) The aligning agent for liquid crystal (R-1) of preparation forms film.Then, which is carried out to 1 minute prebake conditions in 80 DEG C of heating plate Afterwards, it has carried out carrying out heating in 15 minutes (rear baking) in the baking oven of nitrogen displacement with 230 DEG C in by library, forming average film thickness is Film.The floor map of used top electrode 13 is shown in Fig. 2 (a)~Fig. 2 (b) herein.In addition, Fig. 2 (a) be top electrode 13 top view, Fig. 2 (b) is the enlarged drawing of the part C1 enclosed by the dotted line of Fig. 2 (a).In the present embodiment, The line width d1 of electrode is set as 4 μm, interelectrode distance d2 is set as 6 μm.The structure of driving electrodes used in being shown in Fig. 3 At.In this case, hearth electrode 15 works as common electrode and acts on the driving electrodes of all 4 systems, the drive of 4 systems The region of moving electrode respectively becomes pixel region.

Then, using cotton, each surface for the film being formed on glass substrate 11a, glass substrate 11b is implemented at friction Reason, is made liquid crystal orientation film 12.In Fig. 2 (b), the direction of friction will be implemented to the film being formed on glass substrate 11a with arrow Head indicates.Then, the outer rim in the face with liquid crystal orientation film of a substrate in a pair of of substrate is coated with as sealant After " XN-21-S " (trade name) (Mitsui Chemicals, Inc.'s system is made), by the substrate with substrate 11a, substrate 11b frictional direction that This is bonded as antiparallel mode across 3.5 μm of diameter of spacer, and cures the sealant.Then, it is injected from liquid crystal Mouth injects liquid crystal MLC-6221 (Merck & Co., Inc.'s manufacture) between a pair of of substrate, forms liquid crystal layer 16.In turn, in substrate 11a, substrate The outside two sides of 11b is bonded polarizer (diagram is omited) in the mutually orthogonal mode of the polarization direction of 2 pieces of polarizers, thus makes Liquid crystal display element 10.

(5) evaluation of liquid crystal aligning

It is disconnected when connecting to observe with 50 times of multiplying power using microscope for the FFS type liquid crystal display element of the manufacture The presence or absence of the abnormal area in light and shade variation when opening (ONOFF) (applying releasing) 5V voltage.Evaluation is as follows It carries out: will not observe and be evaluated as liquid crystal aligning " good " the case where abnormal area, it will be observed that the case where abnormal area comments Valence is liquid crystal aligning " bad ".Liquid crystal aligning " good " in the liquid crystal display element.

(6) evaluation of voltage retention

For the FFS type liquid crystal display element of the manufacture, with the application time of 60 microseconds, 167 milliseconds at 23 DEG C After span (span) applies the voltage of 5V, the voltage retention (VHR) from applying and releasing after 167 milliseconds is measured, result is 99.6%.In addition, using the VHR-1 of Dongyang Te Kenika (Toyo Technica) (stock) manufacture as measurement device.

(7) the uneven patience (resistance to frame unevenness) on sealant periphery

For the FFS type liquid crystal display element of the manufacture, after being taken care of 30 days under conditions of 25 DEG C, 50%RH, to hand over Galvanic electricity pressure 5V is driven, and lighting state is observed.Evaluation is to proceed as follows: if not recognizing brightness on sealant periphery Poor (more black or whiter) is then evaluated as resistance to frame unevenness " good ", though luminance difference is recognized, after lighting within 10 minutes Luminance difference disappearance is then evaluated as "available", even if the case where capable of also recognizing luminance difference by 10 minutes is evaluated as " bad ".Its It as a result is the luminance difference for not recognizing the liquid crystal display element, resistance to frame unevenness is judged as " good ".

(8) pre-tilt angle characteristic

For the FFS type liquid crystal display element of the manufacture, measured by using the crystallization rotary process of He-Ne laser light The inclined angle in self-reference substrate face of liquid crystal molecule, using the value as pretilt theta.Crystallization rotary process is according to non-patent literature 2 (T.J. Schaefer (T.J.Scheffer) et al. " applied physics magazine (Journal of Applied Physics, J.Appl.Phys.) " page 1783 (1977) of volume 48) and the (" day of wild (F.Nakano) et al. in F. of non-patent literature 3 This application physics magazine (Japanese Journal of Applied Physics, JPN.J.Appl.Phys.) " volume 19 Page 2013 (1980)) in the method recorded carry out.

The case where by pretilt theta less than 1.0 °, is evaluated as pre-tilt angle evaluation " good ", and 1.0 ° or more of situation is evaluated as Pre-tilt angle evaluates " bad ", as a result, the pre-tilt angle of the liquid crystal display element is 0.5 °, is judged as pre-tilt angle characteristic " good ".

(9) contrast after driving stress evaluates (evaluation of AC image retention characteristic)

Other than the outside two sides in substrate is not bonded in terms of polarizer, carry out and (4) identical operation, system Make FFS type liquid crystal cells.For the FFS type liquid crystal cells, after alternating voltage 10V driving 30 hours, using in light source and light Device between amount detector configured with polarizer and analyzer, to measure, minimum represented by following numerical expressions (2) is opposite to be penetrated Rate (%).

Minimum relative permeability (%)=(β-B⁰)/(B¹⁰⁰-B⁰)×100 (2)

(in numerical expression (2), B⁰For blank and the transit dose of the light under Nicol crossed；B¹⁰⁰For blank and parallel The transit dose of light under Nicol prism；β is that liquid crystal is clamped between polarizer and analyzer under Nicol crossed Show element and become the smallest light transmission capacity)

The black level of dark state is indicated with the minimum relative permeability of liquid crystal display element, in FFS type liquid crystal display In element, the black level under dark state is smaller, then contrast is more excellent.By minimum relative permeability being evaluated as less than 1.0% AC image retention characteristic " good " is evaluated as "available" more than and less than 1.5% for 1.0%, and 1.5% or more is evaluated as " no It is good ".As a result, the minimum relative permeability of the liquid crystal display element is that 0.2%, AC image retention characteristic is judged as " good ".

[embodiment 3-2~embodiment 3-8 and comparative example 1]

In the embodiment 3-1, other than respectively using the ingredient of type shown in following table 2 as polymer, Aligning agent for liquid crystal is prepared in a manner of identical with embodiment 3-1, and manufactures FFS type liquid crystal display element to carry out various comment Valence.Evaluation result is shown in following table 2.In addition, the numerical value of amount of polymers indicates each polymer phase for liquid crystal aligning in table 2 The allotment ratio (parts by weight) of whole 100 parts by weight of component of polymer in agent.

[table 2]

As shown in table 2, in embodiment 3-1~embodiment 3-8, about the coating of aligning agent for liquid crystal, the rub resistance of film Property, liquid crystal aligning, voltage retention, the uneven patience on sealant periphery, pre-tilt angle characteristic and AC image retention characteristic are " good It is good " or "available" as a result, and achieving the balances of various characteristics.In contrast, in the liquid crystal display element of comparative example 1, coating Though property and rub resistance are the evaluation of "available", voltage retention, the uneven patience on sealant periphery, pre-tilt angle characteristic and AC are residual As characteristic is the result poorer than embodiment.

In addition, using in the embodiment with the polymer (P) of part-structure represented by the formula (1), resistance to frame is not Equal property become " good " though or the reasons why "available" do not determine, speculate one reason are as follows: utilize the spacer in polymer (P) Structure (- R¹) and mesomorphic structure (- W¹-(R²-W²) p-) and hydrophobicity improves, and water absorption rate declines, thus hydrolytic resistance is able to Improve, as a result can inhibit uneven generation.

[embodiment 4-1: light orientation FFS type liquid crystal display element]

(1) preparation of aligning agent for liquid crystal

100 parts by weight of polymer obtained in embodiment 2-2 as polymer (PA-2) are dissolved in comprising γ-Ding Nei The mixed solvent (GBL: NMP: BC=40: 40: 20 of ester (GBL), n-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) (weight ratio)) in, the solution that solid component concentration is 3.5 weight % is made.The filter for being 0.2 μm using aperture is to the solution It is filtered, thus prepares aligning agent for liquid crystal (R-9).

(2) evaluation of the concave-convex surface of coated film

The aligning agent for liquid crystal (R-9) of the preparation is coated on glass substrate using rotator, in 80 DEG C of heating plate After 1 minute prebake conditions of upper progress, heating in 200 DEG C of baking oven of nitrogen displacement (rear baking) 1 hour has been carried out in by library, by This forms average film thicknessFilm.Come using atomic force microscope (Atomic Force Microscopy, AFM) The film is observed, is measured center average roughness (Ra).Evaluation is to proceed as follows: will be evaluated less than the case where 2.0nm For concave-convex surface " good ", 2.0nm is evaluated as "available" more than and less than the case where 5.0nm, the situation of 5.0nm or more is commented Valence is " bad ".In the present embodiment, Ra 0.9nm, concave-convex surface is " good ".

(3) evaluation of orientation

To the film of the acquisition, Hg-Xe lamp and Glan-Taylor prism (Glan-Taylor prism) self-reference substrate method are used The polarisation ultraviolet light 300J/cm of open-wire line of the line direction irradiation comprising 313nm², implement orientation process.Use jasmine Li Te (MORITEX) the liquid crystal aligning film detection apparatus (bearing (LayScan) in Leix) of company's manufacture, to the substrate with alignment films It measures refractive anisotrop (nm).Evaluation is to proceed as follows: the situation of 0.020nm or more is evaluated as " good ", The case where situation for being less than 0.020nm and 0.010nm or more is evaluated as "available", will be less than 0.010nm is evaluated as " bad ".Its As a result it is that the substrate is 0.036nm, is " good ".

(4) manufacture of the FFS type liquid crystal display element of optical alignment method is utilized

Firstly, on each surface of a pair of of glass substrate 11a, glass substrate 11b in the same manner as (4) of the embodiment 3-1, The aligning agent for liquid crystal (R-9) prepared in (1) is respectively coated using rotator, to form film.Then, which is existed After carrying out 1 minute prebake conditions in 80 DEG C of heating plate, carried out in by library nitrogen displacement baking oven in 230 DEG C heating (after Baking) 15 minutes, forming average film thickness isFilm.The floor map of used top electrode 13 is shown herein In Fig. 4 (a)~Fig. 4 (b).In addition, Fig. 4 (a) is the top view of top electrode 13, Fig. 4 (b) is the enclosed by the dotted line of Fig. 4 (a) The enlarged drawing of part C1.It in the present embodiment the use of line width d1 with electrode is 4 μm, interelectrode distance d2 is 6 μm and powers on The substrate of pole.In addition, (4) of top electrode 13 and the embodiment 3-1 are used in the same manner electrode A, electrode B, electrode C and electrode D 4 systems driving electrodes (referring to Fig. 3).

Then, to each surface of the film, using Hg-Xe lamp and Glan-Taylor prism self-reference substrate normal direction respectively according to Penetrate the polarisation ultraviolet light 300J/cm of the open-wire line comprising 313nm², to obtain a pair of of substrate with liquid crystal orientation film.At this point, Polarisation ultraviolet irradiation direction is set as self-reference substrate normal direction, and projected on substrate with the plane of polarisation of polarisation ultraviolet light and At the direction of line segment become the mode in direction of the four-headed arrow in Fig. 4 (a)~Fig. 4 (b) and set plane of polarisation direction, it is laggard Row photo-irradiation treatment.

Then, the periphery in the face with liquid crystal orientation film of 1 piece of substrate in the substrate, is coated with using screen painting It is the epoxy resin adhesive of 5.5 μm of alumina balls that being added, which has diameter, makes the liquid crystal alignment film surface of a pair of of substrate opposite later, Become parallel mode towards the direction that substrate projects with the polarisation of polarisation ultraviolet light and substrate is overlapped crimping, with 1 at 150 DEG C Hour makes bonding agent thermmohardening.Then, the liquid crystal " MLC- of Merck & Co., Inc.'s manufacture is filled from liquid crystal injecting port to substrate gap After 6221 ", epoxy resin adhesive encapsulated liquid crystals inlet is utilized.It thereafter, will in order to eliminate flow orientation when liquid crystal injection It is slowly cooled to room temperature after being heated to 150 DEG C.

Then, FFS type liquid crystal display element is manufactured by being bonded polarizer on the outside two sides of substrate.At this point, wherein 1 Block polarizer is that the projection direction with its polarization direction with the polarisation of the polarisation ultraviolet light of liquid crystal orientation film towards substrate is parallel Mode attaches, and another 1 piece of polarizer is attached in its polarization direction mode orthogonal with the polarization direction of previous polarizer.

(5) evaluation of liquid crystal aligning

For the light orientation FFS type liquid crystal display element of the manufacture, it is carried out similarly with (5) of the embodiment 3-1 The evaluation of liquid crystal aligning.As a result, liquid crystal aligning is " good " in the liquid crystal display element.

(6) evaluation of voltage retention

For the light orientation FFS type liquid crystal display element of the manufacture, measured in the same manner as (6) of the embodiment 3-1 Voltage retention (VHR) simultaneously evaluates voltage retention.As a result, VHR is 99.4%.

(7) resistance to frame unevenness

For the light orientation FFS type liquid crystal display element of the manufacture, evaluated in the same manner as (7) of the embodiment 3-1 Resistance to frame unevenness.As a result, not recognizing luminance difference in the liquid crystal display element, resistance to frame unevenness is judged as " good It is good ".

(8) AC image retention is evaluated

The evaluation of AC image retention is carried out similarly with (9) of the embodiment 3-1.In addition, in the evaluation of AC image retention, with the reality (9) for applying a 3-1, which are used in the same manner, not to be bonded the liquid crystal cells of polarizer and is evaluated.As a result, minimum relative permeability It is 0.1%, contrast-response characteristic is judged as " good ".

[embodiment 4-2 and embodiment 4-3]

In the embodiment 4-1, other than respectively using the ingredient of type shown in following Table 3 as polymer, Aligning agent for liquid crystal is prepared in a manner of identical with embodiment 4-1, and manufactures FFS type liquid crystal display element to carry out various comment Valence.Evaluation result is shown in following Table 3.In addition, the numerical value of amount of polymers indicates each polymer phase for liquid crystal aligning in table 3 The allotment ratio (parts by weight) of whole 100 parts by weight of component of polymer in agent.

[table 3]

[embodiment 5-1: phase difference film]

(1) preparation of aligning agent for liquid crystal

By poly organo obtained in 100 parts by weight of polymer obtained in embodiment 2-2 (PA-2) and synthesis example 2 5 parts by weight of alkane (S-1) are dissolved in the mixed solvent comprising NMP and BC (NMP: BC=50: 50 (weight ratio)), be made solid at Dividing concentration is the solution of 5.5 weight %.The solution is filtered using the filter that aperture is 0.2 μm, thus prepares liquid crystal Alignment agent (R-10).

(2) manufacture of phase difference film

On the one side as the TAC film of substrate, the aligning agent for liquid crystal (R- of the preparation is coated with using rod coater 10), with 120 DEG C are toasted 2 minutes and form film thickness as the film of 100nm in baking oven.Then, to the film coated surface, Hg- is used Xe lamp and Glan-Taylor prism, self-reference substrate normal vertically irradiate the polarisation ultraviolet light 10mJ/cm of the open-wire line comprising 313nm².After And after the filter for being 0.2 μm using aperture is filtered polymerizable liquid crystal (RMS03-013C, Merck & Co., Inc.'s manufacture), benefit With rod coater, which is coated on the film after light irradiation, to form the film of polymerizable liquid crystal.? Temperature is adjusted in 50 DEG C of baking oven after baking 1 minute, using Hg-Xe lamp, includes to coated surface irradiation from vertical direction The ultraviolet light 1,000mJ/cm of the non-polarized of the open-wire line of 365nm², so that polymerizable liquid crystal is hardened and is formed liquid crystal layer, thus manufacture Phase difference film.

(3) evaluation of liquid crystal aligning

For the phase difference film manufactured in (2), by aobvious using the visual and polarisation under Nicol crossed Micro mirror (multiplying power is 2.5 times), the presence or absence of observation abnormal area, to evaluate liquid crystal aligning.Evaluation is to proceed as follows: will It is good in visual lower orientation, and the case where not observing abnormal area under petrographic microscope, to be evaluated as liquid crystal aligning " good It is good "；The case where observing abnormal area under visually, but observing abnormal area under petrographic microscope, is evaluated as liquid crystal Orientation "available"；The case where observing abnormal area under visual and petrographic microscope, is evaluated as liquid crystal aligning " no It is good ".As a result, the phase difference film is be evaluated as liquid crystal aligning " good ".

(4) adhesion

Using the phase difference film manufactured in (2), to the adhesion of the film and substrate that are formed by aligning agent for liquid crystal into Row evaluation.Firstly, using the equally spaced spacer for having guiding element, using cutter, from the face of the liquid crystal layer side of phase difference film Notch is cut, forms 10 × 10 grid patterns in the range of 1cm × 1cm.The depth of each notch is from liquid crystal layer table Until face reaches near the midpoint of substrate thickness.Then, touch glassine paper in a manner of covering the entire surface of the grid pattern After adhesive tape, the cellophane tape is removed.Pass through visually cutting to observe the grid pattern after removing under Nicol crossed Oral area evaluates adhesion.Evaluation is to proceed as follows: will be in the cross part of part and grid pattern along incision line The case where not confirming removing is divided to be evaluated as adhesion " good "；By the number relative to grid pattern entirety, in the part Observe that the case where grid purpose number of removing is less than 15% is evaluated as adhesion "available"；It will be relative to grid pattern entirety Number is evaluated as adhesion " bad " in the situation that the grid purpose number of the partially observable removing is 15% or more.Its It as a result is that the phase difference film is adhesion " good ".

Claims

1. a kind of aligning agent for liquid crystal, containing polymer (P), the polymer (P) is selected from by polyamic acid, poly amic acid ester And at least one of group polymer composed by polyimides, and made containing compound represented by following formula (d) Monomer polymerization and obtain,

In formula (d), W¹For the cyclohexylidene for being substituted or being unsubstituted；W²For by phenyl ring, cyclohexane ring, pentamethylene ring or pyridine Ring is set as the divalent cyclic group of ring skeleton；X¹、X³、X⁴It is separately singly-bound ,-O-, *-COO-, *-OCO- ,-CO-, *- NR¹⁰CO- or *-CONR¹⁰, wherein R¹⁰For hydrogen atom or the alkyl of carbon number 1~3, " * " is indicated and W¹Or the combination of aminophenyl Key；X²For-O-, *-COO-, *-OCO- ,-CO-, *-NR¹¹CO- or *-CONR¹¹, wherein R¹¹For hydrogen atom or carbon number 1~3 Alkyl, " * " is indicated and W²Associative key；R¹For singly-bound, the alkane diyl of carbon number 1~20, the alkene diyl of carbon number 2~20, carbon number 1~ A part of hydrogen atom of 20 alkane diyl or the alkene diyl of carbon number 2~20 is substituted divalent base or carbon number 1 made of base replaces Divalent base made of a part of methylene warp-O- or-S- of~20 alkane diyl or the alkene diyl of carbon number 2~20 replace；R²For list Key ,-O-, *-COO-, *-OCO- ,-CO-, *-NR¹²CO-、*-CONR¹², the alkane diyl of carbon number 1~5, carbon number 2~5 alkene two A part of hydrogen atom of the alkene diyl of base, the alkane diyl of carbon number 1~5 or carbon number 2~5 be substituted base replace made of divalent base or Divalent base made of a part of methylene warp-O- or-S- of the alkene diyl of the alkane diyl or carbon number 2~5 of person's carbon number 1~5 replace, Wherein, R¹²For hydrogen atom or the alkyl of carbon number 1~3, " * " is indicated and W¹Associative key；R³For the alkane diyl of carbon number 1~20, carbon The alkene diyl of number 2~20, phenylene, piperidines diyl, a part of the alkene diyl of the alkane diyl of carbon number 1~20 or carbon number 2~20 Hydrogen atom is substituted one of the alkene diyl of the alkane diyl or carbon number 2~20 of divalent base or carbon number 1~20 made of base replaces Divalent base made of dividing methylene warp-O- or-S- to replace；R⁴And R⁵It is separately halogen atom or the alkane of carbon number 1~6 Base or alkoxy；P is 1 or 2；Q is 0 or 1；M and n is separately 0~4 integer；In R⁴、R⁵In the case where multiple, Multiple R⁴、R⁵It can distinguish identical also different.

2. aligning agent for liquid crystal according to claim 1, in which: the R¹For the alkane diyl of carbon number 1~20, carbon number 2~20 A part of hydrogen atom of the alkene diyl of alkene diyl, the alkane diyl of carbon number 1~20 or carbon number 2~20 is substituted 2 made of base replaces A part of methylene warp-O- or-S- of the alkene diyl of the alkane diyl or carbon number 2~20 of valence base or carbon number 1~20 replaces Divalent base.

3. aligning agent for liquid crystal according to claim 1, in which: the polymer (P) is to make the list containing tetracarboxylic dianhydride Polymer obtained by body polymerization, and contain and be selected from by bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid 2:3,5:6- dianhydrides, 1, 2,3,4- cyclobutane tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, 5- (2,5- dioxotetrahydro furans -3- Base) -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans -1,3- diketone, 5- (2,5- dioxotetrahydro furans -3- base) -8- first Base -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans -1,3- diketone, bicyclic [3.3.0] octane -2,4,6,8- tetrabasic carboxylic acid 2:4, At least one of group composed by 6:8- dianhydride, cyclopentanetetracarboxylic's dianhydride and pyromellitic acid anhydride is used as the tetracarboxylic acid Acid dianhydride.

4. a kind of liquid crystal orientation film is formed using aligning agent for liquid crystal according to any one of claim 1 to 3.

5. a kind of liquid crystal orientation film is taken by being coated with liquid crystal according to any one of claim 1 to 3 on substrate Film is formed to agent, and light irradiation is carried out to the film and is obtained.

6. a kind of liquid crystal orientation film is to be coated with aligning agent for liquid crystal according to any one of claim 1 to 3 on substrate Afterwards, it carries out friction treatment and obtains.

7. a kind of manufacturing method of liquid crystal orientation film comprising: it is coated on substrate according to claim 1 to any one of 3 institutes The aligning agent for liquid crystal stated and the step of form film；And the step of liquid crystal aligning ability is assigned to film progress light irradiation Suddenly.

8. a kind of liquid crystal display element comprising: the liquid crystal orientation film according to any one of claim 4 to 6.

9. a kind of phase difference film comprising: liquid crystal orientation film according to claim 4 or 5.

10. a kind of manufacturing method of phase difference film comprising:

In the step of being coated with aligning agent for liquid crystal according to any one of claim 1 to 3 on substrate and forming film；

The step of light irradiation is carried out to the film；And

In the step of coating polymerizable liquid crystal on the film after light irradiates makes its hardening.

11. a kind of polymer, be in the group as composed by polyamic acid, poly amic acid ester and polyimides at least A kind of polymer, and be to make the monomer polymerization containing compound represented by following formula (d) and obtain,

12. a kind of compound is indicated by following formula (d),