CN104140826B

CN104140826B - Aligning agent for liquid crystal, liquid crystal orientation film, phase retardation film and their manufacture method and liquid crystal display cells

Info

Publication number: CN104140826B
Application number: CN201410184011.XA
Authority: CN
Inventors: 樫下幸志; 林英治
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2013-05-09
Filing date: 2014-05-04
Publication date: 2018-01-23
Anticipated expiration: 2034-05-04
Also published as: CN104140826A; KR20140133428A; TW201443157A; KR102102211B1; JP6311343B2; TWI631184B; JP2014238564A

Abstract

The present invention provides a kind of aligning agent for liquid crystal, liquid crystal orientation film, phase retardation film and their manufacture method and liquid crystal display cells.The present invention, which provides one kind, polymer is fully dissolved, and can form the aligning agent for liquid crystal of liquid crystal orientation film by comparing the heating of low temperature.The aligning agent for liquid crystal of the present invention contains：Selected from least one of the group being made up of polyamic acid, polyimides, poly amic acid ester and polysiloxane polymer (A)；And include the solvent of the compound (p1) represented by following formula (1).

Description

Aligning agent for liquid crystal, liquid crystal orientation film, phase retardation film and their manufacture method and Liquid crystal display cells

Technical field

The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display cells, liquid crystal orientation film manufacturer The manufacture method of method, phase retardation film and phase retardation film, more particularly to one kind can make polyimides or polyamic acid etc. abundant Dissolving, and aligning agent for liquid crystal of liquid crystal orientation film etc. can be formed by comparing the heating of low temperature.

Background technology

Liquid crystal display cells are by will be provided with liquid crystal of the substrate surface formed with liquid crystal orientation film of nesa coating Substrate for display device is oppositely disposed, and so that the state of liquid crystal molecular orientation is enclosed and shape between above-mentioned a pair of substrates Into.The major axis that above-mentioned liquid crystal display cells are known as liquid crystal molecule continuously reverses 90 ° from one of substrate to another piece of substrate So-called twisted nematic (Twisted Nematic, TN) type element.In addition, develop：Pair higher than TN type elements can be realized The few coplanar switching (In- of STN Super TN (Super Twisted Nematic, STN) type element, visual angle interdependence than degree Plane Switching, IPS) type element, visual angle interdependence are few and do not need the vertical of friction treatment to take in the orientation of liquid crystal To (Vertical Alignment, VA) type element, the optics that visual angle interdependence is few and the high-speed response of image frame is excellent Compensated bend (Optically Compensated Bend, OCB) type liquid crystal display cells.

The liquid crystal orientation film used in these liquid crystal display cells is, for example, as shown in 1~patent document of patent document 3, is led to Crossing will make polyimides or polyamic acid dissolve and contain what is formed in 1-Methyl-2-Pyrrolidone or gamma-butyrolacton equal solvent Aligning agent for liquid crystal is coated on substrate, and then it is heated and formed.By using polyimides or polyamic acid conduct Aligning agent for liquid crystal, the excellent liquid crystal orientation films such as compatibility, the mechanical strength of heat resistance and liquid crystal can be obtained.

[prior art literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 9-241646 publications

[patent document 2] Japanese Patent Laid-Open 2001-305549 publications

[patent document 3] Japanese Patent Laid-Open 9-278724 publications

The content of the invention

Herein, in the case of aligning agent for liquid crystal being made making the dissolvings such as polyimides or polyamic acid, as described above, must 1-Methyl-2-Pyrrolidone or gamma-butyrolacton etc. must be used.It is believed that if using such a solvent, have by liquid crystal aligning Agent is coated on substrate and can produce improper situation after forming liquid crystal orientation film.

Specifically, 1-Methyl-2-Pyrrolidone or gamma-butyrolacton etc. are the solvents of higher boiling (such as 200 DEG C), are made In the case of such a high boiling solvent, it must be heated at high temperature when forming liquid crystal orientation film.

In addition, liquid crystal orientation film is formed on the substrate formed with colored filter.Such as using the sense containing dyestuff In the case of linear composition is radiated as colored filter, dyestuff is not because heat resistance is high, if so forming liquid crystal aligning The heating under high temperature is carried out during film, then dysgenic misgivings can be brought to colored filter by existing.

In addition, in the case of must for example carrying out the heating under high temperature when forming liquid crystal orientation film, manufacture in processing procedure Total amount of heat correspondingly increases, and causes the discharge rate of carbon dioxide correspondingly to increase.

It is a primary object of the present invention to provide that the polymer such as polyimides or polyamic acid can be made fully to dissolve, and energy It is enough to form the aligning agent for liquid crystal of liquid crystal orientation film by comparing the heating of low temperature.

Present inventor et al. is actively studied to complete the problem of prior art as described above, is as a result found, By using at least a portion of specific compound as solvent, the problem is can solve the problem that, so as to complete the present invention.Specifically For, provide following aligning agent for liquid crystal by the present invention.

To provide a kind of aligning agent for liquid crystal, it contains an aspect of of the present present invention：Selected from by polyamic acid, polyimides, poly- At least one of the group that amic acid esters and polysiloxane are formed polymer (A)；And include following formula (1) institute table The solvent for the compound (p1) shown.

[changing 1]

(in formula (1), R¹~R⁴Separately for straight-chain or branch-like carbon number 1~6 alkyl or in the hydrocarbon There is the base selected from least one of-O- ,-COO- and-OCO- between the C-C keys of base.)

By using at least a portion of compound (p1) as the solvent of aligning agent for liquid crystal, polyimides or poly- can be made Amic acid etc. fully dissolves, and can form liquid crystal orientation film by comparing the heating of low temperature.

Embodiment

The aligning agent for liquid crystal of the present invention is to include to be selected from by polyamic acid, polyimides, poly amic acid ester and poly-organosilicon At least one of the group that oxygen alkane is formed polymer (A) is used as component of polymer, and the polymer (A) is dissolved in solvent In form.Hereinafter, the aligning agent for liquid crystal is illustrated.

The polyamic acid of the present invention can be by making tetracarboxylic dianhydride be reacted with diamines to obtain.

[tetracarboxylic dianhydride]

The tetracarboxylic dianhydride of polyamic acid for synthesizing the present invention can for example enumerate：Aliphatic tetracarboxylic dianhydride, alicyclic ring Formula tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc..As the concrete example of these tetracarboxylic dianhydrides,

Aliphatic tetracarboxylic dianhydride can for example enumerate 1,2,3,4- butane tetracarboxylic acid dianhydrides 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, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphtho- [1,2-c] furans -1, 3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphtho- [1,2-c] furan Mutter -1,3- diketone, 3- oxabicyclos [3.2.1] octane -2,4- diketone -6- loop coils -3 '-(tetrahydrofuran -2 ', 5 '-diketone), 5- (2,5- dioxotetrahydro -3- furyls) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, 3,5,6- tri- carboxyl -2- carboxyl first Base norbornane -2：3,5：6- dianhydrides, 2, bicyclic [33.0] octane -2 of 4,6,8- tetracarboxylics：4,6：8- dianhydrides, 4,9- dioxas Three ring [5.3.1.0^2,6] hendecane -3,5,8,10- tetrones, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acids 2：3,5：6- bis- Acid anhydride, ring valeric acid dianhydride, cyclopentanetetracarboxylic's dianhydride etc.；

Aromatic tetracarboxylic acid's dianhydride can for example be enumerated：Pyromellitic acid anhydride etc.；In addition, Japan Patent also can be used Tetracarboxylic dianhydride described in JP 2010-97188 publications.1 kind or general in addition, the tetracarboxylic dianhydride can be used alone Two or more is applied in combination.

For the viewpoints such as dissolubility with regard to the transparency and in a solvent, the tetracarboxylic dianhydride for synthesis is preferably to include fat Ring type tetracarboxylic dianhydride.In addition, in ester ring type tetracarboxylic dianhydride, preferably include selected from the group being made up of following compound At least one of：2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydrochysene -2,5- dioxies Generation -3- furyls)-naphtho- [1,2-c] furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydrochysenes -2,5- Dioxo -3- furyls)-naphtho- [1,2-c] furans -1,3- diketone, bicyclic [3.3.0] octane -2 of 2,4,6,8- tetracarboxylics：4, 6：8- dianhydrides, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acids 2：3,5：6- dianhydrides, ring valeric acid dianhydride, 1,2,4,5- hexamethylenes Tetracarboxylic dianhydride and 1,2,3,4- cyclobutane tetracarboxylic dianhydrides, particularly preferably include and be selected from what is be made up of following compound At least one of group：2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides, bicyclic [3.3.0] octane -2 of 2,4,6,8- tetracarboxylics： 4,6：8- dianhydrides, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acids 2：3,5：6- dianhydrides, ring valeric acid dianhydride and 1,2,3,4- Cyclobutane tetracarboxylic dianhydride.

Comprising selected from by 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides, bicyclic [3.3.0] octane of 2,4,6,8- tetracarboxylics- 2：4,6：At least one of 8- dianhydrides and 1, the group that 2,3,4- cyclobutane tetracarboxylic dianhydrides are formed are used as the tetracarboxylic acid In the case of acid dianhydride, relative to the total amount of the tetracarboxylic dianhydride for synthesizing polyamides acid, the total of these compounds contains Amount is preferably 10 moles of more than %, more preferably 20 moles of %~100 mole %.

[diamines]

The diamines of polyamic acid for synthesizing the present invention can for example be enumerated：Aliphatic diamine, ester ring type diamines, aromatic series Diamines, diaminourea organosiloxane etc..As the concrete example of these diamines, aliphatic diamine can for example be enumerated：M-xylene diamine, 1,3- propane diamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine etc.；

Ester ring type diamines can for example be enumerated：Isosorbide-5-Nitrae-diaminocyclohexane, 4,4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine), 1,3- are double (amino methyl) hexamethylene etc.；

Aromatic diamine can for example be enumerated：P-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl Thioether, 1,5-diaminonaphthalene, 2,2 '-dimethyl -4,4 '-benzidine, 2,2 '-bis- (trifluoromethyl) -4,4 '-diaminourea connection Benzene, 2,7- diamino-fluorenes, 4, double [4- (4- amino-benzene oxygens) phenyl] propane of 4 '-diamino-diphenyl ether, 2,2-, 9,9- are double Double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of (4- aminophenyls) fluorenes, 2,2-, double (4- aminophenyls) hexafluoros third of 2,2- Alkane, 4,4 '-(to phenylenediisopropylidene) dianils, 4,4 '-(isopropylidene of metaphenylene two) dianils, Isosorbide-5-Nitrae-bis- (4- Amino-benzene oxygen) benzene, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, DAP, 3,4- diamino-pyridines, 2,4- bis- Aminopyrimidine, 3,6- proflavins, 3,6- diaminocarbazoles, N- methyl -3,6- diaminocarbazole, N- ethyl -3,6- diaminos Base carbazole, N- phenyl -3,6- diaminocarbazole, N, N '-bis- (4- aminophenyls)-benzidine, N, N '-bis- (4- aminophenyls) - N, N '-dimethylbenzidine, Isosorbide-5-Nitrae-bis--(4- aminophenyls)-piperazine, 1- (4- aminophenyls) -2,3- dihydros -1,3,3- front threes Base -1H- indenes -5- amine, 1- (4- aminophenyls) -2,3- dihydros -1,3,3- trimethyl -1H- indenes -6- amine, 3,5- diaminobenzene first Acid, cholesteric alkyl oxy -3,5- diaminobenzene, cholesteryl epoxide -3,5- diaminobenzene, cholesteric alkyl oxy -2,4- diamino Base benzene, cholesteryl epoxide -2,4- diaminobenzene, 3,5- diaminobenzoic acid cholesterics Arrcostab, 3,5- diaminobenzoic acid courages Double (the 4- amino benzoyls epoxide) cholestane of steroid alkenyl esters, 3,5- diaminobenzoic acid lanostane base ester, 3,6-, 3,6- are double (4- amino-benzene oxygens) cholestane, 4- (4 '-trifluoromethoxy benzoyloxy) cyclohexyl -3,5- diaminobenzoic acids ester, 4- Double (4- ((aminophenyl) methyl) benzene of (4 '-trifluoromethylbenzoyl epoxide) cyclohexyl -3,5- diaminobenzoic acid ester, 1,1- Base) -4- butyl cyclohexanes, double (4- ((aminophenyl) methyl) the phenyl) -4- heptylcyclohexanes of 1,1-, double (the 4- ((amino of 1,1- Phenoxy group) methyl) phenyl) -4- heptylcyclohexanes, double (4- ((aminophenyl) methyl) phenyl) -4- (the 4- heptyl hexamethylenes of 1,1- Base) hexamethylene, 2,4- diamino-Ns, N- diallyl anilines, 4- aminobenzyls amine, 3- aminobenzyls amine, methacrylic acid 2- Represented compound of (2,4- diamino phenoxy) ethyl ester difference etc.；

Diaminourea organosiloxane can for example be enumerated：1,3- double (3- aminopropyls)-tetramethyl disiloxanes etc.；Except this with Outside, the diamines described in Japanese Patent Laid-Open 2010-97188 publications also can be used.In addition, these diamines can be used alone 1 Two or more is applied in combination kind.

The diamines of polyamic acid for synthesizing the present invention, which particularly preferably uses, to be selected from represented by following formula (d-1) The compound and following formula (d-4) institute table represented by compound, following formula (d-3) represented by compound, following formula (d-2) At least one of the group that the compound shown is formed diamines (hereinafter also referred to " specific diamines ") synthesizes.

[changing 2]

(in formula (d-1), X¹And X²It is separately singly-bound ,-O- ,-S- ,-OCO- or-COO-, Y¹For oxygen atom or sulphur Atom, R¹And R²It is separately the alkane diyl of carbon number 1~3；N1 is 0 or 1, and in the case of n1=0, n2 and n3 are full Sufficient n2+n3=2 integer, in the case of n1=1, n2=n3=1；In formula (d-2), X³For singly-bound ,-O- or-S-, m1 0 ~3 integer；In the case of m1=0, m2 is 1~12 integer, in the case where m1 is 1~3 integer, m2=2；Formula (d-3) in, R³The monovalent hydrocarbon of straight-chain or branch-like for carbon number 1~12, R⁴For hydrogen atom or the straight chain of carbon number 1~12 The monovalent hydrocarbon of shape or branch-like, R⁵And R⁶It is separately hydrogen atom or methyl；In formula (d-4), X⁴And X⁵Separately For singly-bound ,-O- ,-COO- or-OCO-, R⁷For the alkane diyl of carbon number 1~3；The integer that a is 0 or 1, b are 0~2, c are 1~20 Integer, k be 0 or 1；Wherein, a and b will not be 0 simultaneously.)

(compound represented by formula (d-1))

In the formula (d-1), R¹And R²The alkane diyl of carbon number 1~3 can for example enumerate：Methylene, ethylidene, propane- 1,2- diyl, propane -1,3- diyl, propane -2,3- diyl etc..In these alkane diyls, preferably methylene, ethylidene or Propane -1,3- diyl.

X¹And X²For singly-bound ,-O- ,-S- ,-OCO- or-COO-.In addition, X¹With X²Can it is identical can also be different.These bases In, X¹And X²Preferably singly-bound ,-O- or-S-.

Y¹For oxygen atom or sulphur atom.Preferably oxygen atom.

In the case of n1=0,2 one-level amino can be bonded to same possessed by the compound represented by formula (d-1) On phenyl ring, 1 can also be respectively bonded in 2 different phenyl ring.On the other hand, in the case of n1=1,2 one-level amino exist Each bond 1 is distinguished on different phenyl ring.

The binding site of one-level amino on phenyl ring is not particularly limited.Such as the one-level amino on phenyl ring is 1 In the case of, relative to other bases, the binding site of above-mentioned one-level amino can be any one of 2- positions, 3- positions, 4- positions, preferably 3- Position or 4- positions, more preferably 4- positions.In addition, in the case that the one-level amino on phenyl ring is 2, it is above-mentioned relative to other bases The binding site of one-level amino can for example enumerate 2,4- positions, 2,5- positions etc., wherein preferably 2,4- positions.

In addition, the hydrogen atom on the phenyl ring that one-level amino is bonded can be through carbon number 1~10 monovalent hydrocarbon or the alkyl On the monad radical that substitutes through fluorine atom of at least one hydrogen atom or fluorine atom substituted.In this case monovalent hydrocarbon is for example It can enumerate：The alkyl of carbon number 1~10, alkenyl, cycloalkyl, aryl (phenyl etc.), aralkyl (benzyl etc.) etc..

As the preferred concrete example of the compound represented by the formula (d-1), n1=0 compound can for example be enumerated：4, 4 '-diamino-diphenyl amine, 2,4- diamino-diphenyl amine etc.；N1=1 compound can for example be enumerated：1,3- double (4- amino Benzyl) urea, double (4- aminophenethyls) ureas of 1,3-, 1,3- double (3- aminobenzyls) urea, 1- (4- aminobenzyls) -3- (4- amino Phenethyl) urea, double (2- (4- amino-benzene oxygens) ethyl) ureas of 1,3-, 1,3- double (3- (4- amino-benzene oxygens) propyl group) urea, 1,3- Double (2- aminobenzyls) ureas of double (4- aminobenzyls) thiocarbamides, 1,3-, double (2- aminophenethyls) ureas of 1,3-, double (2- (the 2- ammonia of 1,3- Base benzoyl epoxide) ethyl) urea, double (3- (the 2- amino benzoyls epoxide) propyl group) ureas of 1,3- etc..In addition, formula (the d- 1) these compounds can be used alone a kind or two or more is applied in combination by the compound represented by.

(compound represented by formula (d-2))

In the formula (d-2), X³For singly-bound ,-O- or-S-, preferably singly-bound or-O-.

In the case of m1=0, m2 is 1~12 integer.In this case, just make the heat resistance of resulting polymers good For viewpoint, preferably m2 is 1~10, more preferably 1~8.In addition, being maintained for good liquid crystal aligning, and make rub resistance Property good viewpoint for, preferably m1=0, for reducing the viewpoint of pre-tilt angle of liquid crystal molecule, m1 is preferably 1~3 Integer.

The binding site of one-level amino on phenyl ring is not particularly limited, and relative to other bases, each one-level amino is preferred For 3- positions or 4- positions, more preferably 4- positions.In addition, the hydrogen atom on the phenyl ring that one-level amino is bonded can be through carbon number 1~10 The monad radical or fluorine atom that at least one hydrogen atom on monovalent hydrocarbon or the alkyl substitutes through fluorine atom are substituted.

The preferred concrete example of compound represented by the formula (d-2) can for example be enumerated：Double (4- amino-benzene oxygens) methane, Double (4- amino-benzene oxygens) ethane, double (4- amino-benzene oxygens) propane, double (4- amino-benzene oxygens) butane, double (4- aminobenzene oxygen Base) pentane, double (4- amino-benzene oxygens) hexanes, double (4- amino-benzene oxygens) heptane, double (4- amino-benzene oxygens) octanes, double (4- Amino-benzene oxygen) it is nonane, double (4- amino-benzene oxygens) decane, double (4- aminophenyls) methane, double (4- aminophenyls) ethane, double It is (4- aminophenyls) propane, double (4- aminophenyls) butane, double (4- aminophenyls) pentanes, double (4- aminophenyls) hexanes, double (4- aminophenyls) heptane, double (4- aminophenyls) octanes, double (4- aminophenyls) nonanes, double (4- aminophenyls) decane, 1, 3- double (4- aminophenyls sulfydryl) propane, Isosorbide-5-Nitrae-bis- (4- aminophenyls sulfydryl) butane etc..In addition, the formula (d-2) is represented Compound the compound of these illustrations can be used alone to a kind or be used in mixed way two or more.

(compound represented by formula (d-3))

In the formula (d-3), R³The monovalent hydrocarbon of straight-chain or branch-like for carbon number 1~12.Its concrete example for example may be used Enumerate：The alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, octyl group, decyl；Ethene The alkenyls such as base, pi-allyl；The cycloalkyl such as cyclopenta, cyclohexyl；The aryl such as phenyl, tolyl；Aralkyl such as benzyl etc..R³Carbon Number is preferably 1~6, more preferably 1~3.In addition, R³Preferably chain alkyl, the preferably chain hydrocarbon comprising carbon-to-carbon double bond The alkenyls such as base, more preferably pi-allyl.

R⁴For the monovalent hydrocarbon of the straight-chain or branch-like of hydrogen atom or carbon number 1~12.The alkyl can be enumerated：Carbon number 1 ~12 chain alkyl, the alicyclic type hydrocarbon of carbon number 3~12, the aromatic hydrocarbyl of carbon number 5~12, its concrete example can be enumerated described R³Explanation in illustrated base.R⁴The preferably alkyl of hydrogen atom or carbon number 1~6, more preferably hydrogen atom or carbon number 1 ~3 alkyl, especially preferably hydrogen atom or methyl.

R⁵And R⁶It is separately hydrogen atom or methyl, it is preferably to be hydrogen atom.

In the diamino-phenyl of the formula (d-3), the binding site of 2 one-level amino is not particularly limited, relative to key Tie in the N- allylic structures on phenyl ring, preferably 2,4- positions or 2,5- position, more preferably 2,4- positions.In addition, one-level amino institute Hydrogen atom on the phenyl ring of bond can be through carbon number 1~10 monovalent hydrocarbon or the alkyl at least one hydrogen atom it is former through fluorine The monad radical or fluorine atom of son substitution are substituted.

The preferred concrete example of compound represented by the formula (d-3) can for example be enumerated：2,4- diamino-Ns, the allyls of N- bis- Base aniline, 2,5- diamino-Ns, N- diallyl anilines, following formula (d-3-1)~represented compound of formula (d-3-3) difference Deng.In these compounds, preferably using 2,4- diamino-Ns, N- diallyl anilines or 2,5- diamino-N, N- diene Propyl group aniline.

[changing 3]

(compound represented by formula (d-4))

In formula (d-4), "-X⁴-(R⁷-X⁵)_k- " represented by bilvalent radical be preferably 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" it is preferably straight-chain, its concrete example can for example be enumerated：Methyl, ethyl, n-propyl, normal-butyl, just Amyl group, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, positive ten Five alkyl, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base, n-eicosane base etc..

Relative to base " X⁴", 2 one-level amino in diamino-phenyl are preferably 2,4- positions or 3,5- position, and more preferably 2, 4- positions.In addition, hydrogen atom on the phenyl ring that one-level amino is bonded can through fluorine atom, carbon number 1~10 monovalent hydrocarbon or should Base that at least one hydrogen atom on alkyl substitutes through fluorine atom etc. is substituted.

The preferred concrete example of compound represented by the formula (d-4) can for example enumerate following formula (d-4-1)~formula (d-4- 11) represented compound of difference etc..

[change 41

Synthesize the present invention polyamic acid when, specific diamines can according to the drive pattern of manufactured liquid crystal display cells, It is appropriate from the compound to select to use.Specifically, can be made by using the compound represented by the formula (d-1) For the specific diamines, it is suitable for fringing field switching (Fringe Field Switching, FFS) type liquid crystal display to manufacture The aligning agent for liquid crystal of element.In addition, by using selected from the compound represented by the formula (d-2) and the formula (d-3) At least one of group that represented compound is formed, it can manufacture and be suitable for twisted nematic (Twisted Nematic, TN) type aligning agent for liquid crystal used for liquid crystal display element, by using the compound represented by the formula (d-4), energy Enough manufactures are suitable for the aligning agent for liquid crystal of vertical alignment-type liquid crystal display device.

[molecular weight regulator]

During synthesizing polyamides acid, appropriate point can be used while using tetracarboxylic dianhydride as described above and diamines Son measures conditioning agent to synthesize the polymer of end modified type.By forming the polymer of the end modified type, can not damage And further improve the coating (printing) of aligning agent for liquid crystal in the case of the effect of the present invention.

Molecular weight regulator can for example be enumerated：The single acid anhydride of acid, monoamine compound, monoisocyanate compound etc..It is used as these The concrete example of compound, the single acid anhydride of acid can for example be enumerated：Maleic anhydride, phthalic anhydride, itaconic anhydride, positive decyl fourth two Acid anhydrides, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc.；Monoamine compound example It can such as enumerate：Aniline, cyclo-hexylamine, n-butylamine, n-pentyl amine, n-hexyl amine, n-heptyl amine, n-octylamine etc.；Single isocyanide Ester compound can for example be enumerated：Phenyl isocyanate, isocyanic acid naphthyl ester etc..

Relative to used tetracarboxylic dianhydride and total 100 parts by weight of diamines, the use ratio of molecular weight regulator Preferably it is set to below 20 parts by weight, is more preferably set to below 10 parts by weight.

The tetracarboxylic dianhydride of synthetic reaction and the use ratio of diamines for being supplied to the polyamic acid of the present invention are preferably phase For the equivalent of amino 1 of diamines, the anhydride group of tetracarboxylic dianhydride turns into the ratio of the equivalent of 0.2 equivalent~2, more preferably turns into The ratio of the equivalent of 0.3 equivalent~1.2.

The synthetic reaction of polyamic acid is preferably carried out in organic solvent.Preferably -20 DEG C of reaction temperature now~ 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.

Herein, organic solvent can for example be enumerated：Aprotic polar solvent, phenol series solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, Hydrocarbon etc..

As the concrete example of these organic solvents, the aprotic polar solvent can for example be enumerated：N- methyl -2- pyrroles Alkanone, 1,3- dimethyl -2- imidazolidinones (1,3-dimethy1-2-imidazo1idinone), N- ethyl-2-pyrrolidones, DMA, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, hexamethyl phosphinylidyne three Compound represented by amine, following formula (1) etc.；The phenol series solvent can for example be enumerated：Phenol, metacresol, xylenol, benzene halide Phenol etc.；The alcohol can for example be enumerated：Methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propane diols, BDO, three second two Alcohol, glycol monoethyl ether etc.；

The ketone can for example be enumerated：Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc.；The ester can for example arrange Lift：Ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methoxy methyl propionate, ethoxy-propionic acid second Ester, diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate etc.；The ether can for example be enumerated：Diethyl Ether, isoamyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, Glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran etc.；

The halogenated hydrocarbon can for example be enumerated：Dichloromethane, 1,2- dichloroethanes, Isosorbide-5-Nitrae-dichloroetane, trichloroethanes, chlorine Benzene, o-dichlorohenzene etc.；The hydrocarbon can for example be enumerated：Hexane, heptane, octane, benzene,toluene,xylene etc..

In these organic solvents, it is preferable to use selected from the group being made up of aprotic polar solvent and phenol series solvent Group's one or more of (organic solvent of A groups), or more than a kind in the organic solvent selected from A groups with selected from The mixing of one or more of the group (organic solvent of B groups) being made up of alcohol, ketone, ester, ether, halogenated hydrocarbon and hydrocarbon Thing.In the latter case, relative to A groups organic solvent and B groups organic solvent total amount, B groups The use ratio of the organic solvent of group is preferably below 50 weight %, more preferably below 40 weight %, especially preferably 30 weights Measure below %.

The usage amount (a) of organic solvent is preferably to be set to the total amount (a+b) relative to reaction solution, tetracarboxylic dianhydride and two The total amount (b) of amine turns into the weight % of 0.1 weight %~50 amount.

The reaction solution for forming polyamic acid dissolving is obtained in the above described manner.The reaction solution can be supplied directly to liquid crystal The preparation of alignment agent, the preparation of aligning agent for liquid crystal can also will be available to after polyamic acid isolation contained in reaction solution, Or the polyamic acid isolated can also be available to the preparation of aligning agent for liquid crystal after purification.Closed by polyamic acid dehydration Ring and in the case of polyimides is made, the reaction solution can be supplied directly to dehydration closed-loop reaction, will can also be reacted Dehydration closed-loop reaction is available to after contained polyamic acid isolation in solution, or can also be pure by the polyamic acid isolated Dehydration closed-loop reaction is available to after change.The isolation of polyamic acid and purifying can be carried out according to known method.

Contained polyimides can be by the polyamide that will synthesize in the above described manner in the aligning agent for liquid crystal of the present invention Acid carries out dehydration closed-loop, is subject to imidizate and obtains.

The polyimides can all carry out amic acid structure possessed by the polyamic acid as its presoma Complete acid imide compound obtained by dehydration closed-loop or only by amic acid structure a part carry out dehydration closed-loop and make acyl Amino acid structure and imide ring structure and the part acid imide compound deposited.Polyimides in the present invention is preferably its imidizate Rate is more than 30%, more preferably 40%~99%, especially preferably 50%~99%.The acid imide rate is relative to polyamides The quantity of the amic acid structure of imines is total with the quantity of imide ring structure, by the ratio shared by the quantity of imide ring structure Example is expressed as a percentage.Herein, a part of of imide ring can be different imide ring.

The dehydration closed-loop of polyamic acid is preferably to be 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, is optionally entered The method of row heating.Wherein, later approach is preferably utilized.

In the method that dehydrating agent and dehydration closed-loop catalyst are added in the solution of polyamic acid, dehydrating agent for example may be used Use the acid anhydrides such as acetic anhydride, propionic andydride, TFAA.Relative to 1 mole of the amic acid structure of polyamic acid, dehydrating agent Usage amount is preferably to be set to 0.01 mole~20 moles.Dehydration closed-loop catalyst for example can be used：Pyridine, collidine (collidine), the tertiary amine such as two picolins (lutidine), triethylamine.Relative to used 1 mole of dehydrating agent, take off The usage amount of water ring-closing catalyst is preferably to be set to 0.01 mole~10 moles.Organic solvent used in dehydration closed-loop reaction The organic solvent illustrated as the organic solvent for synthesizing polyamides acid can be enumerated.The reaction temperature of dehydration closed-loop reaction is excellent Elect 0 DEG C~180 DEG C, more preferably 10 DEG C~150 DEG C as.Reaction time is preferably 1.0 hours~120 hours, more preferably 2.0 Hour~30 hours.

The reaction solution containing polyimides is obtained in the above described manner.The reaction solution can be supplied directly to aligning agent for liquid crystal Preparation, the system that aligning agent for liquid crystal is available to after dehydrating agent and dehydration closed-loop catalyst can also be removed in autoreaction solution It is standby, the preparation of aligning agent for liquid crystal is available to after can also polyimides be isolated, or can also be sub- by the polyamides isolated Amine is available to the preparation of aligning agent for liquid crystal after purification.These purification process can be carried out according to known method.

Contained poly amic acid ester can for example be obtained using following methods in the aligning agent for liquid crystal of the present invention：[I] is logical Cross the polyamic acid and the compound of hydroxyl that make to be obtained by the synthetic reaction, halide, compound containing epoxy radicals etc. The method for being reacted to synthesize；[II] makes the method that tetracarboxylic acid acid diesters are reacted with diamines；And [III] makes tetrabasic carboxylic acid two The method that ester dihalide is reacted with diamines.

Herein, the compound of the hydroxyl used in method [I] can for example be enumerated：The alcohols such as methanol, ethanol, propyl alcohol；Benzene Phenols such as phenol, cresols etc..In addition, halide can for example be enumerated：Bromomethane, bromoethane, bromo-octadecane, chloromethanes, chloro ten Eight alkane, 1,1,1- tri- fluoro- 2- iodoethane etc., the compound containing epoxy radicals is such as can enumerate expoxy propane.Make in method [II] Tetracarboxylic acid acid diesters for example can be by using the alcohols, by tetracarboxylic dianhydride illustrated in the synthesis of the polyamic acid Carry out open loop and obtain.In addition, the tetracarboxylic acid acid diesters dihalide used in method [III] can be by making to obtain in the above described manner The tetracarboxylic acid acid diesters chlorinating agent appropriate with thionyl chloride etc. reacted and obtained.Two used in method [II] and [III] Diamines illustrated in the synthesis of the polyamic acid etc. can be used in amine.In addition, poly amic acid ester can only have amic acid esters knot Structure or amic acid structure and amic acid esters structure and the partial esterification thing deposited.

Polyamic acid, polyimides and the poly amic acid ester obtained in the above described manner is preferably to work as to be made into concentration as 10 During weight % solution, there is 10mPas~3, the compound of 000mPas solution viscosity, more preferably have The compound of 20mPas~1,500mPas solution viscosity.In addition, the solution viscosity (mPas) of the polymer is Refer to, for good solvent (such as gamma-butyrolacton, METHYLPYRROLIDONE, 1, the 3- dimethyl -2- imidazoles using the polymer Alkanone, N- ethyl-2-pyrrolidones etc.) come the polymer solution that the concentration for preparing is 10 weight %, use E type rotary viscosities Meter, the value obtained by measure at 25 DEG C.It is in addition, sub- for polyamic acid contained in the aligning agent for liquid crystal of the present invention, polyamides Amine and poly amic acid ester, using gel permeation chromatography (Gel Permeation Chromatography, GPC) come what is determined The weight average molecular weight of polystyrene conversion is preferably 500~100,000, more preferably 1, and 000~50,000.

The polysiloxane of the present invention for example can be by by water-disintegrable silane compound, preferably appropriate organic Be hydrolyzed in the presence of solvent, water and catalyst or hydrolytic condensation and obtain.

Hydrolysable silanes compound for synthesizing polysiloxane can for example be enumerated：Methyl trichlorosilane, methyl three Methoxy silane, MTES, phenyl trichlorosilane, phenyltrimethoxysila,e, phenyl triethoxysilane, first Base dichlorosilane, methyl dimethoxysilane, methyldiethoxysilane, dimethyldichlorosilane, dimethylformamide dimethyl epoxide silicon Alkane, dimethyldiethoxysilane, diphenyl dichlorosilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, chlorine Dimethylsilane, methoxyl group dimethylsilane, ethyoxyl dimethylsilane, chlorine trimethyl silane, trimethylammonium bromide silane, iodine front three Base silane, methoxytrimethylsilane, ethoxytrimethylsilane, tetramethoxy-silicane, tetraethoxysilane, octadecyl three Chlorosilane, octadecyl trimethoxysilane, vinyl trichlorosilane, vinyltrimethoxy silane, vinyl triethoxyl Silane, allyltrichlorosilane, allyltrimethoxysilanis, allyltriethoxysilane,

3- glycidoxypropyltrimewasxysilanes, 3- glycidoxypropyls triethoxysilane, 3- shrink Glycerine epoxide hydroxypropyl methyl dimethoxysilane, 3- glycidoxypropyls diethoxy silane, 3- glycidol oxygen Base dimethylamine methoxylsilane, 3- glycidoxypropyls dimethylethoxysilane, 2- glycidoxypropyl ethyls Trimethoxy silane, 2- glycidoxypropyls ethyl triethoxysilane, 2- glycidoxypropyl ethyl-methyl dimethoxy silicon Alkane, 2- glycidoxypropyl ethyl-methyls diethoxy silane, 2- glycidoxypropyl ethyls dimethyl methoxy silane, 2- contractings Water glycerine epoxide ethyl dimethylethoxysilane, 4- glycidoxypropyls butyl trimethoxy silane, 4- glycidoxypropyls Butyl triethoxysilane, 4- glycidoxypropyl butyl methyls dimethoxysilane, 4- glycidoxypropyls butyl methyl two Ethoxysilane, 4- glycidoxypropyl Butyldimethyls methoxy silane, 4- glycidoxypropyl Butyldimethyl ethyoxyls Silane, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane, 2- (3,4- expoxycyclohexyl) ethyl triethoxy silicane Alkane, 3- (3,4- expoxycyclohexyl) propyl trimethoxy silicane, 3- (3,4- expoxycyclohexyl) propyl-triethoxysilicane, (methyl) acrylic acid (3- Ethyloxetane -3- bases) methyl esters, (methyl) acrylic acid (3- methy oxetane -3- bases) first Ester,

3- (methyl) acryloxypropyls trichlorosilane, 3- (methyl) acryloxypropyls trimethoxy silane, 3- (methyl) acryloxypropyl triethoxysilane, 2- (methyl) acryloyl-oxyethyls trichlorosilane, 2- (methyl) propylene Trimethylammonium trimethoxy silane, 2- (methyl) acryloyl-oxyethyls triethoxysilane, 4- (methyl) acryloxy Butyl trichlorosilane, 4- (methyl) acryloxies butyl trimethoxy silane, the ethoxy of 4- (methyl) acryloxies butyl three Base silane etc..In addition, " (methyl) acryloxy " is the implication for including " acryloxy " and " methacryloxy ".

Workable organic solvent can for example be enumerated when synthesizing polysiloxane：Hydrocarbon, ketone, ester, ether, alcohol etc..Herein, institute Stating hydrocarbon can for example enumerate：Toluene, dimethylbenzene etc.；The ketone can for example be enumerated：Methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl are just Amyl ketone, metacetone, cyclohexanone etc.；The ester can for example be enumerated：Ethyl acetate, n-butyl acetate, isoamyl acetate, the third two Alcohol methyl ether acetate, 3- methoxybutyls acetic acid esters, ethyl lactate etc.；The ether can for example be enumerated：Glycol dimethyl ether, second Glycol diethyl ether, tetrahydrofuran, dioxanes etc.；The alcohol can for example be enumerated：1- hexanols, 4- methyl -2- amylalcohols, ethylene glycol list first Ether, ethylene glycol monoethyl ether, ethylene glycol list-positive propyl ether, ethylene glycol list-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, third Glycol list-positive propyl ether etc..In these organic solvents, it is preferable to use water-insoluble organic solvent.In addition, these organic solvents It can be used alone and a kind or be used in mixed way two or more.

Relative to whole parts by weight of silane compound 100, the organic solvent in the case of the polysiloxane is synthesized Usage amount be preferably 10 parts by weight~10,000 parts by weight, more preferably 50 parts by weight~1,000 parts by weight.It is in addition, relative In used whole silane compounds, the usage amount of water when manufacturing the polysiloxane is preferably 0.5 times mole~ 100 times moles, more preferably 1 times mole~30 times moles.

Workable catalyst can for example be enumerated when synthesizing the polysiloxane：It is acid, alkali metal compound, organic Alkali, titanium compound, zirconium compounds etc..Herein, the acid can for example be enumerated：Hydrochloric acid, sulfuric acid, nitric acid, formic acid, ethanedioic acid, acetic acid, Trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid etc.；The alkali metal compound can for example be enumerated：Sodium hydroxide, potassium hydroxide, methanol Sodium, potassium methoxide, caustic alcohol, potassium ethoxide etc.；The organic bases can such as be enumerated：Such as ethylamine, diethylamide, piperazine, piperidines, pyrrole Cough up one-level~two level organic amine of alkane, pyrroles etc；Such as triethylamine, three-n-propyl amine, three-n-butylamine, pyridine, 4- bis- The three-level organic amine of dimethylaminopyridine, diazabicycloundecene etc；Level Four such as TMAH etc is organic Amine etc..

The catalyst is particularly preferably organic base.The usage amount of organic base is according to the reaction such as the species of organic base, temperature Condition etc. and it is different, can suitably set, but for example relative to whole silane compounds, preferably 0.01 times mole~3 times moles, More preferably 0.05 times mole~1 times mole.

Hydrolysis or hydrolysis-condensation reaction when manufacturing the polysiloxane come real preferably by following manner Apply：One kind or two or more by water-disintegrable silane compound is dissolved in organic solvent, by the solution of gained and organic base and Water is mixed, such as is heated using oil bath etc..

During hydrolysis-condensation reaction, heating-up temperature is preferably set to preferably less than 130 DEG C, more preferably 40 DEG C~ 100 DEG C, carry out the heating of preferably 0.5 hour~12 hours, more preferably 1 hour~8 hours., can be by mixed liquor in heating Stirring, can also be positioned under backflow.

After reaction terminates, preferably organic solvent layer isolated in autoreaction liquid is cleaned using water.During the cleaning, For cleaning operation becomes readily aspect, preferably by using including the water of a small amount of salt, such as 0.2 weight % or so Aqueous ammonium nitrate solution etc. is cleaned.Cleaning is carried out untill the water layer after cleaning turns into neutral, then, optionally using anhydrous After the drier such as calcium sulfate, molecular sieve dry organic solvent layer, solvent is removed, thus, it is possible to obtain as the poly- organic of target Siloxanes.In addition, the polysiloxane of the present invention can also use commercially available product.

Following compound can be used in contained polysiloxane in the aligning agent for liquid crystal of the present invention, and the compound passes through The reactive polysiloxane for making to be obtained by the condensation reaction is reacted with reactive compounds, so as in reactivity The structure from reactive compounds is imported with the side chain of polysiloxane to form.Herein, reactive polysiloxane Such as the polysiloxane with epoxy radicals, unsaturated double-bond, sulfydryl, amino etc. can be enumerated.In addition, reactive compounds example It can such as enumerate：Compound with chain alkyl, the knot with the ring (such as phenyl ring or cyclohexane ring etc.) for being connected with more than 2 The compound of structure, the compound with steroid skeleton, compound with unsaturated double-bond etc..Specifically, reactivityization Compound is such as the compound described in Japan Patent Patent 2013-77493 specifications can be used.

In addition, the reaction of reactive polysiloxane and reactive compounds can enter according to the well-established law of organic chemistry OK.For example, in the case where reactive polysiloxane has epoxy radicals, can be by using carboxylic acid as reactive chemical combination Thing, and the structure from reactive compounds is imported on the side chain of reactive polysiloxane.In addition, gathering in reactivity has , can be by using the compound with sulfydryl or amino as reactivity in the case that organic siloxane has unsaturated double-bond Compound, and the structure from reactive compounds is imported on the side chain of reactive polysiloxane.

It is excellent come the weight average molecular weight of the polystyrene conversion determined by GPC in the polysiloxane of the present invention Elect 500~100,000, more preferably 1 as, 000~30,000, especially preferably 1,000~20,000.

The compound (p1) that contained solvent is comprised at least represented by following formula (1) in the aligning agent for liquid crystal of the present invention is made For solvent composition.

[changing 5]

The R of formula (1)¹~R⁴In, the alkyl of carbon number 1~6 can be enumerated：Chain alkyl, aliphatic alkyl, the virtue of carbon number 1~6 Fragrant race's alkyl etc., these alkyl can be with saturations, can also be unsaturated, can be straight-chain or branch-like.R¹~R⁴'s Concrete example can for example be enumerated：The alkyl of the carbon numbers such as methyl, ethyl, n-propyl, isopropyl, butyl, amyl group, hexyl 1~6；Comprising 1 valency unsaturated alkyl of vinyl, pi-allyl etc. etc..Preferably R¹~R⁴For the chain alkyl of carbon number 1~6, more preferably carbon number 1~6 alkyl, especially preferably methyl.In addition, in formula (1), R¹~R⁴Can it is mutually identical can also be different.

The preferred concrete example of compound (p1) can for example enumerate compound (N, N, the 2- front three represented by following formula (1-1) Base propionamide).

[changing 6]

Relative to the total amount of solvent contained in aligning agent for liquid crystal, the content of compound (p1) be preferably 0.1 weight % with On, more preferably more than 1 weight %, especially preferably more than 5 weight %, particularly preferably more than 10 weight %.In addition, just print For the viewpoint of brush, relative to the total amount of solvent contained in aligning agent for liquid crystal, the upper limit of content be preferably 90 weight % with Under, more preferably below 85 weight %, especially preferably below 80 weight %.

In addition, for the viewpoint of concave-convex surface, relative to the total amount of solvent contained in aligning agent for liquid crystal, compound (p1) upper limit of content is preferably below 95 weight %, more preferably below 90 weight %.In addition, in compound (p1) sometimes Containing as the N- methyl-isobutyls acid amides of impurity, isobutylamides, isobutyronitrile, dimethyl amine etc..In the case of described, describedization The preferred scope of the containing ratio of compound (p1) is set to be subject to defined scope to the amount of the compound (p1) comprising the impurity.

[other solvents]

Other solvents beyond the compound (p1) can be used in the solvent of aligning agent for liquid crystal for preparing the present invention.Should Other solvents can for example be enumerated：METHYLPYRROLIDONE, gamma-butyrolacton, butyrolactam, DMF, DMA, 4- hydroxy-4-methyl-2-pentanones (diacetone alcohol), glycol monoethyl ether, butyl lactate, acetic acid fourth Ester, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol- Isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol diformazan Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol Monoethyl ether acetate, dipropylene glycol monomethyl ether (dipropylene glycol monomethyl ether, DPM), diisobutyl Ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, propylene carbonate, the tert-butyl alcohol, tert-pentyl alcohol, 3- fourths It is epoxide-N, N- dimethylpropionamide, 3- methoxyl groups-N, N- dimethylpropionamide, 3- hexyloxies-N, N- dimethylpropionamide, different Propoxyl group-N- isopropyls-propionamide, n-butoxy-N- isopropyls-propionamide, N- ethyl-2-pyrrolidones, N- propyl group -2- pyrroles Pyrrolidone, N- butyl -2-Pyrrolidone, N- (tert-butyl group) -2-Pyrrolidone, N- amyl groups -2-Pyrrolidone, N- methoxy propyls Base -2-Pyrrolidone, N- ethoxyethyl groups -2-Pyrrolidone, N- methoxybutyls -2-Pyrrolidone, 1,3- dimethyl -2- miaows Oxazolidone, ethylene acetate, propylene-glycol diacetate, diacetone alcohol, tert-butyl group alcohol, tert-pentyl alcohol etc..In addition, other solvents The solvent can be used alone a kind or be used in mixed way two or more.

For fully obtaining the viewpoint of effect as caused by allocating the compound (p1), relative to aligning agent for liquid crystal In contained solvent total amount, the contents of other solvents is preferably below 99 weight %, more preferably below 95 weight %, Especially preferably below 80 weight %.In addition, for making the good viewpoint of printing, relative to contained in aligning agent for liquid crystal The total amount of solvent, the lower limit of the content of other solvents is preferably more than 10 weight %, more preferably more than 15 weight %, especially It is preferably more than 20 weight %.

Though the aligning agent for liquid crystal of the present invention contains polymer as described above and solvent, it optionally can also be contained His composition.The other compositions can for example be enumerated：Other polymers, intramolecular beyond the polymer have at least one ring The compound (hereinafter referred to as " compound containing epoxy radicals ") of epoxide, functional silanes compound, free-radical generating agent etc..

[other polymers]

The other polymers can be used in improving solution properties or electrical characteristics.The other polymers can for example be enumerated： Polyester, polyamide, cellulose derivative, polyacetals, polystyrene derivative, poly- (styrene-phenylmaleimide) Derivative, poly- (methyl) acrylate etc..In the case where the other polymers are made an addition in aligning agent for liquid crystal, relative to this Whole amount of polymers in composition, the allotment ratio of the other polymers is preferably below 50 weight % more preferably 0.1 The weight % of weight %~40 weight %, especially preferably 0.1 weight %~30.

[compound containing epoxy radicals]

Compound containing epoxy radicals can be used in improving the cementability of liquid crystal orientation film and substrate surface.Herein, containing epoxy The compound of base can for example be enumerated：Ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propane diols 2-glycidyl Ether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6- hexylene glycols Diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2,2- dibromoneopentyl glycols two shrink Glycerin ether, N, N, N ', double (N, the N- diglycidyl amino methyl) rings of N '-four glycidyl group-m-xylene diamine, 1,3- Hexane, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl-methane, N, N- diglycidyls-benzyl amine, N, N- diglycidyls-aminomethyl cyclohexane, N, N- diglycidyl-cyclo-hexylamine etc..

In the case where these epoxides are made an addition 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 is preferably below 40 parts by weight more preferably 0.1 The parts by weight of parts by weight~30.

[functional silanes compound]

The functional silanes compound can use for the purpose for the printing for improving aligning agent for liquid crystal.This official Energy property silane compound can for example be enumerated：3- TSL 8330s, APTES, 2- amino Propyl trimethoxy silicane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- aminopropyl trimethoxy silicon Alkane, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, 3- ureido-propyl trimethoxy silanes, 3- urea groups third Ethyl triethoxy silicane alkane, N- ethoxy carbonyl -3- TSL 8330s, N- tri-ethoxy silylpropyls Sanya second Base triamine, 10- trimethoxy silanes base-Isosorbide-5-Nitrae, the azepine decane of 7- tri-, 9- trimethoxy silane base -3,6- diaza nonyl acetic acid Ester, 9- trimethoxy silane base -3,6- diazas methyl pelargonate, N- benzyl -3- TSL 8330s, N- phenyl - 3- TSL 8330s, glycidoxypropyl MTMS, 2- glycidoxypropyl ethyl trimethoxies Base silane, 3- glycidoxypropyltrimewasxysilanes etc..

In the case where these functional silanes compounds are made an addition in aligning agent for liquid crystal, relative to the total of polymer 100 parts by weight, the allotment ratio of the functional silanes compound is preferably more preferably 0.02 parts by weight below 2 parts by weight ~0.2 parts by weight.

[free-radical generating agent]

The free-radical generating agent is can be by irradiating luminous ray, ultraviolet, far ultraviolet, electron beam, X ray etc. Radioactive ray and the compound for producing free radical, can for the reaction for promoting free-radical reactive compound purpose and containing in liquid Brilliant alignment agent (particularly polymer stabilizing orientation (Polymer Sustained Alignment, PSA) mode-type liquid crystal display The aligning agent for liquid crystal of element manufacture) in.

There is no particular restriction for the free-radical generating agent, and existing known compound can be used.The tool of free-radical generating agent Style can for example be enumerated：Acetophenone, benzophenone, 1- hydroxycyclohexylphenylketones, 2,2- dimethoxy -2- phenyl acetophenones, Xanthone (xanthone), Fluorenone (fluorenone), benzaldehyde (benzaldehyde), anthraquinone (anthraquinone), Triphenylamine, carbazole, 3- methyl acetophenones, 4- chlorobenzophenones, meter Qi Le ketone, 1- (4- isopropyl phenyls) -2- hydroxyl -2- first Base propane -1- ketone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, sulphur Miscellaneous anthrone (thioxanthone), 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinyls-propane -1- ketone, diphenyl (2,4, 6- trimethoxybenzoys) phosphine oxide, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butanone -1,2,4,6- Trimethylbenzoy-dipheny phosphine oxide, double (2,4,6- trimethylbenzoyl) phenyl phosphine oxides, 1,2- acetyl caproyls, 1- [4- (thiophenyl) -, 2- (O- benzoyl oximes)], ethyl ketone, 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazoles -3- Base]-, 1- (O- acetyl oxime), Polymethylphenylsilane etc..Free-radical generating agent, which can be used alone, or to be combined two or more by a kind Use.

In the case where free-radical generating agent is made an addition in aligning agent for liquid crystal, relative to total 100 weight of polymer Part, the allotment ratio of the free-radical generating agent is preferably below 20 parts by weight, the parts by weight of more preferably 0.1 parts by weight~5.

Other contained additives also can be used in addition to described in aligning agent for liquid crystal：In aluminium, titanium and zirconium The meal chelate compounds such as the acetylacetonate complex or acetoacetate complex compound of metal, compound containing phenylol etc. are hard Change accelerator, surfactant, intramolecular have the compound of at least one oxetanyl, antioxidant etc..

Solid component concentration (total weight of the composition beyond the solvent of aligning agent for liquid crystal in the aligning agent for liquid crystal of the present invention Measure shared ratio in the gross weight of aligning agent for liquid crystal) allow for viscosity, volatility etc. suitably to select, preferably 1 weight Measure the weight % of %~10 scope.That is, aligning agent for liquid crystal of the invention in a manner of aftermentioned by being coated on substrate surface, preferably Heated, and form the film as liquid crystal orientation film or the film as liquid crystal orientation film, but now, in solid constituent In the case that concentration is less than 1 weight %, the thickness of film becomes too small and can not obtain good liquid crystal orientation film.The opposing party Face, in the case where solid component concentration is more than 10 weight %, the thickness of film becomes too much and can not obtain good liquid crystal Alignment films, in addition, the viscosity of aligning agent for liquid crystal increases and coating characteristics variation.

The scope of particularly preferred solid component concentration is according to the used method in coating of liquid crystalline alignment agent on substrate It is and different.Such as using in the case of method of spin coating, solid component concentration is particularly preferably the weight of 1.5 weight %~4.5 Measure % scope.Using in the case of flexographic printing process, solid component concentration is particularly preferably set to the weight of 3 weight %~9 % scope is measured, thus solution viscosity is set to 12mPas~50mPas scope.It is special in the case of using ink-jet method Solid component concentration You Xuanwei be set to the weight % of 1 weight %~5 scope, thus by solution viscosity be set to 3mPas~ 15mPas scope.

Temperature when preparing the aligning agent for liquid crystal of the present invention is preferably 10 DEG C~50 DEG C, more preferably 20 DEG C~30 DEG C.

The liquid crystal orientation film of the present invention is formed using the aligning agent for liquid crystal prepared in the above described manner.It is in addition, of the invention Liquid crystal display cells possess using the aligning agent for liquid crystal of the present invention and the liquid crystal orientation film that is formed.Using the liquid crystal of the present invention Show that the drive pattern of element is not particularly limited, can be applied to TN types, STN types, IPS types, FFS types, VA types, multidomain vertical orientation The multiple drive modes such as (Multi-domain Vertical Alignment, MVA) type.Hereinafter, to the liquid crystal display of the present invention The manufacture method of element is illustrated, and the manufacture method of the liquid crystal orientation film of the present invention is illustrated in the explanation.

The liquid crystal display cells of the present invention for example manufacture using the step of following (1)~(3).Step (1) is according to institute Need drive pattern and use different substrates.Step (2) and step (3) are common in each drive pattern.

[step (1)：The formation of film]

First, the aligning agent for liquid crystal of the present invention is coated with substrate, then coated face is heated, thus on substrate Form film.

(1-1) is patterned by being provided with the case of manufacture TN types, STN types or VA type liquid crystal display cells Two pieces of substrates of nesa coating in each transparent conductive film forming face of the substrate, preferably utilize glue as a pair Version printing method, method of spin coating, roll-coater method or ink jet printing method come be respectively coated the present invention aligning agent for liquid crystal.Liquid crystal Flexographic printing process in these described methods of the coating method of alignment agent preferably application.Herein, substrate for example can be used：Float glass process The glass such as glass, soda-lime glass；Comprising PET, polybutylene terephthalate, polyether sulfone, makrolon, The transparency carrier of plastics such as poly- (ester ring type alkene).The nesa coating for being arranged at the wherein one side of substrate can be used comprising oxidation Tin (SnO₂) nesa (NESA) film (PPG register of company of U.S. trade mark), include indium oxide-tin oxide (In₂O₃-SnO₂) oxygen Change indium tin (Indium Tin Oxide, ITO) film etc..In order to obtain patterned nesa coating, such as can utilize： After forming the nesa coating of pattern-free, the method for pattern is formed by being etched by light；Using tool when forming nesa coating There is method of the shade of required pattern etc..During coating of liquid crystalline alignment agent, in order that substrate surface and nesa coating and film Cementability it is better, can also to that should form the face of film in substrate surface, implementation be pre-coated with functional silanes compound, The pre-treatment of functionality titanium compound etc..

After coating of liquid crystalline alignment agent, the purpose of for the sagging for preventing be coated with alignment agent, preferably implement preheating (prebake conditions).Prebake conditions temperature is preferably 30 DEG C~200 DEG C, 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 solvent is complete Complete to remove, the amic acid structure that optionally will be present in polymer carries out the purpose of hot-imide, and it is (rear to dry to implement calcining It is roasting) step.Calcining (rear baking) temperature is preferably 80 DEG C~300 DEG C, more preferably 120 DEG C~250 DEG C.Post-bake times are excellent Elect as 5 minutes~200 minutes, more preferably 10 minutes~100 minutes.The thickness of the film formed in the above described manner is preferably 0.001 μm~1 μm, more preferably 0.005 μm~0.5 μm.

(1-2) in the case of manufacture IPS types or FFS type liquid crystal display cells, by being provided with comprising through pattern Turn to the electrode forming surface of the substrate of the nesa coating of interdigitated electrode structure or the electrode of metal film and be not provided with the opposite substrate of electrode One side, be respectively coated the present invention aligning agent for liquid crystal, then each coated face is heated to form film.On now making The pattern of heating condition, nesa coating or metal film after the material of substrate and nesa coating, coating method, coating The preferred thickness of change method, the pre-treatment of substrate and the film formed is identical with (1-1).Example can be used in metal film Such as include the film of chromium metal.

(1-1) and (1-2) it is any in the case of, by the coating of liquid crystalline alignment agent on substrate after, will have Solvent removes and is formed into the film of alignment films.Now, polymer contained in the aligning agent for liquid crystal of the present invention is Polyamic acid or for the imide amination polymer with imide ring structure and amic acid structure or for amic acid In the case of ester structure and the polymer of amic acid structure, it can also be dehydrated after film is formed by further heating Ring-closure reaction, the film of more imidizate is made.

[step (2)：Alignment capability imparting is handled]

Then, to the film being formed on substrate, friction treatment or photo-irradiation treatment are optionally carried out, thus to the painting Film assigns liquid crystal aligning ability.

First, on friction treatment, in the case of manufacture TN types, STN types, IPS types or FFS type liquid crystal display cells, Implement following friction treatment：The roller for including the cloth of fiber such as nylon, artificial silk, cotton using being wound with, to the step (1) film formed in is to fixed-direction friction.Thus, the alignment capability of liquid crystal molecule assigns to film and forms liquid crystal aligning Film.On the other hand, in the case where manufacturing VA type liquid crystal display cells, the film formed in the step (1) can directly be used Make liquid crystal orientation film, friction treatment can also be implemented to the film.

In addition, following handle further is carried out to the liquid crystal orientation film after friction treatment：Pass through one to liquid crystal orientation film Partial illumination ultraviolet and the processing for changing the pre-tilt angle in a part of region of liquid crystal orientation film；On liquid crystal orientation film surface After a part forms resist film, friction treatment is carried out to the direction different from friction treatment before, then removes resist The processing of film；So that liquid crystal orientation film has different liquid crystal aligning abilities in each region.In this case, institute can be improved Obtain the visual field characteristic of liquid crystal display cells.

On the other hand, in the case of using photo-irradiation treatment (optical alignment method), the substrate after being formed for film, pass through Polarisation or the radioactive ray of non-polarized are irradiated to coated surface, and liquid crystal aligning ability is assigned to the film.Herein, as radioactive ray, Such as the ultraviolet or luminous ray of the light comprising 150nm~800nm wavelength can be used.Wherein, preferably comprising 300nm The ultraviolet of the light of~400nm wavelength.In the case where used radioactive ray are polarisation (linear polarization or part polarisation), Light irradiation direction can be set to the direction vertical with coated surface, or imparting pre-tilt angle and be set to incline direction.The opposing party Face, in the case of the radioactive ray of irradiation non-polarized, it is necessary to light irradiation is carried out to coated surface from incline direction.

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, PRK etc..The ultraviolet in described optimal wavelength region can be by by light source and such as filter, diffraction grating And method etc. obtain.The exposure of radioactive ray is preferably 1J/m²Less than 20,000J/m², more preferably 10J/ m²~10,000J/m².In addition, according to light orientation processing, by carrying out light irradiation to the film being formed on substrate and to film Liquid crystal aligning ability is assigned, to make liquid crystal orientation film.

[step (3)：Liquid crystal cells are constructed]

Prepare 2 pieces of substrates formed with liquid crystal orientation film in the above described manner, by being configured between 2 pieces of oppositely disposed substrates Liquid crystal, to manufacture liquid crystal cells.In order to manufacture liquid crystal cells, such as following 2 kinds of methods can be enumerated.

First method is previously known method.First, by each liquid crystal orientation film in a manner of across gap (unit Gap) and 2 pieces of substrates are oppositely disposed, the periphery of 2 pieces of substrates is bonded using sealant, by substrate surface and sealant In the cell gap of division after injection filling liquid crystal, hand-hole is sealed, thus, it is possible to manufacture liquid crystal cells.In addition, second party Method is the method for referred to as liquid crystal drip-injection (One Drop Fill, ODF) mode.In 2 pieces of substrates formed with liquid crystal orientation film Predetermined portion on one of substrate, the sealant of such as ultraviolet light photopolymerization is coated with, and then on liquid crystal aligning film surface After liquid crystal is added dropwise in defined several positions, by liquid crystal orientation film to being bonded another piece of substrate in a manner of, and by liquid crystal in base Spread out in the entire surface of plate, then to the entire surface irradiating ultraviolet light of substrate, sealant is hardened, thus, it is possible to manufacture liquid crystal list Member.In the case of using any method, preferably by the liquid crystal cells to manufacturing in the above described manner, and then it is heated to After used liquid crystal turns into the temperature of isotropic phase, room temperature is slowly cooled down to, so as to which flowing when removing liquid crystal filling takes To.

Sealant is such as can be used the epoxy resin containing curing agent and as the alumina balls of sept.

Liquid crystal can enumerate nematic crystal (nematic liquid crystal) and smectic liquid crystal (smectic Liquid crystal), wherein preferably nematic crystal, such as can be used：Schiff bases (Schiff base) are liquid crystal, oxygen It is liquid crystal, biphenyl system liquid crystal, cyclohexylbenzene system liquid crystal, ester system liquid crystal, terphenyl (terphenyl) system to change azo (azoxy) Liquid crystal, biphenyl hexamethylene system liquid crystal, pyrimidine system liquid crystal, dioxanes system liquid crystal, double-octane system liquid crystal, cubane (cubane) system Liquid crystal etc..Alternatively, it is also possible to add following material in these liquid crystal to use：Such as cholesteryl chloride (cholesteryl Chloride), cholesteryl nonanoate (cholesteryl nonanoate), cholesteryl carbonate (cholesteryl The cholesteric liquid crystal (cholesteric liquid crystal) such as carbonate)；It is (silent with trade name " C-15 ", " CB-15 " The manufacture of gram (Merck) company) come the chiral agent sold；To decyloxy benzylidene-to amino-2-methyl butyl cinnamic acid ester (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) ferroelectric liquid crystals such as (ferroelectric liquid crystal) etc..

Then, can be by being bonded Polarizer in the outer surface of liquid crystal cells, and obtain the liquid crystal display member of the present invention Part.Fitting in the Polarizer of the outer surface of liquid crystal cells can enumerate：The inclined of " H films " is referred to as with the clamping of cellulose acetate diaphragm Polarizer that light film forms or comprising the H films Polarizer of itself, " the H films " is while making polyvinyl alcohol extension orientation While it is set to absorb the light polarizing film that iodine forms.

In addition, in the case where carrying out friction treatment to film, 2 pieces of substrates are with the mutual shape of frictional direction in each film It is oppositely disposed into defined angle, such as orthogonal or antiparallel mode.In addition, in the case where carrying out light irradiation to film, , can be by adjusting being irradiated in 2 pieces of substrates formed with liquid crystal orientation film if liquid crystal orientation film is horizontal alignment property The polarization direction angulation and the angle of each substrate and Polarizer of linear polarization radioactive ray, obtaining with TN types or The liquid crystal display cells of STN type liquid crystal cells.On the other hand, in the case where liquid crystal orientation film is vertical orientated property, to be formed The direction for having the easy axis of orientation in 2 pieces of substrates of liquid crystal orientation film turns into parallel mode Component units, on the unit, with inclined The mode of the polarization direction of the tabula rasa angle at 45 ° with easy axis of orientation shape is bonded Polarizer, is vertically taken thus, it is possible to be made to have To the liquid crystal display cells of type liquid crystal cells.

The liquid crystal display cells of the present invention can have to utilize polymer stabilizing orientation (Polymer Sustained Alignment, PSA) technology and be endowed the element of the liquid crystal orientation film of pre-tilt angle.This PSA mode liquid crystals display element example If manufactured using the method for comprising the following steps (I-1)~step (I-3).

The method comprised the following steps：

(I-1) aligning agent for liquid crystal is respectively coated on the conducting film of a pair of substrates with conducting film, is then added Heat and the step of form film；

(I-2) via the liquid crystal layer for including liquid crystal and photopolymerizable compound, by film in a manner of by above-mentioned formation The step of a pair of substrates for having the film configure and construct liquid crystal cells；And

(I-3) light irradiation is carried out to liquid crystal cells in the state of to conductive intermembranous application voltage possessed by a pair of substrates The step of.

On the step (I-1), it is after the material of used substrate and nesa coating, coating method, coating plus Heat condition, the patterning method of nesa coating or metal film, the preferred thickness of the pre-treatment of substrate and the film formed It is identical with (1-1).In addition, the film formed in the step (I-1) can be supplied directly to following steps, can also regard needs Following step is available to after carrying out friction treatment to coated surface.

In the step (I-2), when except the filling in the step (3) or liquid crystal is added dropwise, by by optical polymerism Compound (photopolymerization monomer) is used together to form beyond the liquid crystal layer comprising liquid crystal and photopolymerizable compound with liquid crystal, with Liquid crystal cells are constructed with the step (3) identical mode.Photopolymerizable compound can be used with acryloyl group, metering system Acyl group, vinyl etc. can carry out the compound of the functional group of radical polymerization.It is preferably multifunctional for the viewpoint of reactivity Property, wherein more preferably intramolecular with more than 2 acryloyl group and methylacryloyl at least any one.In addition, just For the viewpoint of orientation for stably maintaining liquid crystal molecule, photopolymerizable compound is preferably to have total 2 using intramolecular Compound of at least any of ring in cyclohexane ring and phenyl ring as liquid crystal skeleton more than individual.In addition, this optical polymerism Existing known compound can be used in compound.Relative to the total amount of used liquid crystal compounds, photopolymerizable compound Allotment ratio be preferably to be set to the weight % of 0.1 weight %~0.5.

In the step (I-3), after the constructing of liquid crystal cells, to conductive intermembranous application voltage possessed by a pair of substrates In the state of to liquid crystal cells irradiate radioactive ray.The voltage that this place applies can for example be set to 5V~50V DC voltage or friendship Flow voltage.The species of wavelength, light source on the radioactive ray that are irradiated, the explanation of the optical alignment method can be applied.The irradiation of light Amount is preferably 1,000J/m²Less than 200,000J/m², more preferably 1,000J/m²~150,000J/m².In addition, according to According to this polymer stabilizing orientation process, by carrying out light irradiation to the film being formed on substrate, and liquid crystal is assigned to film Alignment capability makes liquid crystal orientation film.

Then, Polarizer is bonded by the outer surface in liquid crystal cells, the liquid crystal display cells of the present invention can be obtained. On the explanation of Polarizer, described explanation can be applied.

Using the aligning agent for liquid crystal of the present invention come in the case of manufacturing phase retardation film, so that it may suppress in step dust or Electrostatic produce and formed uniform liquid crystal orientation film aspect, can by the irradiation of radioactive ray using appropriate light shield and For being randomly formed on substrate in terms of the different multiple regions in liquid crystal aligning direction, optical alignment method is preferably utilized.Example Such as, can be by manufacturing phase retardation film by following step (II-1)~step (II-3).

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

First, the aligning agent for liquid crystal of the present invention is coated on substrate and forms film.Substrate as used herein can fit Preferably illustrate comprising triacetyl cellulose (triacetyl cellulose, TAC), PET, poly- terephthaldehyde The transparent base of the synthetic resin such as sour fourth diester, polyether sulfone, polyamide, polyimides, polymethyl methacrylate, makrolon Plate.In these resins, TAC is typically used as the protective layer of the light polarizing film in liquid crystal display cells.It is in addition, low with regard to the hygroscopicity of solvent Aspect, for the aspect of the good aspect of optical characteristics and low cost, polymethyl methacrylate is preferably used as phase The substrate of poor film.In addition, the substrate used in coating for aligning agent for liquid crystal, in order that substrate surface and film is close Connecing property is better, can implement existing known pre-treatment to the face that film is formed in substrate surface.

As a rule, phase retardation film is applied in combination with light polarizing film.Now, in order to playing desired optics Characteristic, it is necessary to which critically control light polarizing film is bonded phase retardation film relative to the angle of polarizing axis in a particular direction.Therefore, Herein, by the way that the liquid crystal orientation film for having liquid crystal aligning ability on the direction of predetermined angular is formed at into TAC film or poly- methyl On the substrates such as methyl acrylate, the angle that phase retardation film is controlled in light polarizing film can be omitted in while being bonded the phase difference The step of film.In addition, the productivity thus, it is possible to be favorably improved liquid crystal display cells.In order to be formed in the direction of predetermined angular The upper liquid crystal orientation film with liquid crystal aligning ability, it is preferable to use aligning agent for liquid crystal of the invention, entered using optical alignment method OK.

Coating of the aligning agent for liquid crystal on substrate can utilize appropriate coating method, such as can use：Roll-coater method, rotation Turn device method, print process, ink-jet method, rod coater method, extrusion mould (extrusion die) method, direct gravure coater (direct Gravure coater) method, chamber knife type coater (chamber doctor coater) method, set gravure coating machine (offset gravure coater) method, single roller kiss coater (single roll kiss coater) method, using straight Reverse kiss coater (reverse kiss coater) method of the small gravure roll in footpath, three reverse roll coater methods, four Reverse roll coater method, slit die (slot die) method, gas knife coater, dextrorotation roll coater method, blade coating machine (blade coater) method, blade coating machine (knife coater) method, impregnation coater, MB coaters, MB are reversely applied Cloth machine method etc..

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

[step (II-2)：Light irradiation step]

Then, by the film irradiation light to being formed in the above described manner on substrate, and liquid crystal aligning energy is assigned to film Power.Thus, liquid crystal orientation film is made on substrate.The wavelength of light, the species of light, the used light source of this place irradiation are said The explanation that the bright light orientation using the step (2) is handled.The exposure of light is preferably to be set to 0.1mJ/cm²~1,000mJ/ cm², more preferably it is set to 1mJ/cm²~500mJ/cm², especially preferably it is set to 2mJ/cm²~200mJ/cm²。

[step (II-3)：The formation of liquid crystal layer]

Then, polymerizable liquid crystal is being coated with the film after light irradiation in the above described manner and is making its hardening.Thus, formed Film (liquid crystal layer) comprising polymerizable liquid crystal.Polymerizable liquid crystal as used herein be by heating and light irradiation at least A kind of liquid-crystal compounds or liquid-crystal composition for handling to be polymerize.Existing known liquid can be used in this polymerizable liquid crystal Crystalline substance, specifically, such as can enumerate non-patent literature 1 (《Can UV hardening liquid crystal and its apply (UV-Curable Liquid Crystals and Their Application)》,《Liquid crystal》, volume 3 No. 1 (1999), page 34~page 42) in remember The nematic crystal of load.Alternatively, it is also possible to be cholesterol liquid crystal, dish-type liquid crystal (discotic liquid crystal), add There is twisted nematic alignment-type liquid crystal of chiral agent etc..Polymerizable liquid crystal can be the mixture of plurality of liquid crystals compound.Polymerism Liquid crystal can also be and then containing the composition of known polymerization initiators, appropriate solvent etc..

When being coated with polymerizable liquid crystal as described above on the film formed using aligning agent for liquid crystal, such as rod can be used The appropriate coating methods such as coater, roll-coater method, circulator method, print process, ink-jet method.

Then, one in heating and light irradiation is implemented by the film of the polymerizable liquid crystal to being formed in the above described manner Handled more than kind, film hardening is formed liquid crystal layer.For obtaining the aspect of good orientation, preferably by these Manage overlapping progress.

The heating-up temperature of film can suitably select according to the species of used polymerizable liquid crystal.Such as using Merck (Merck) in the case of the RMS03-013C of company's manufacture, preferably heated at a temperature of 40 DEG C~80 DEG C of scope. Heat time is preferably 0.5 minute~5 minutes.

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

The thickness of the liquid crystal layer formed is suitably set according to required optical characteristics.Such as it is in manufacture wavelength In the case of 1/2 wavelength plate of 540nm visible ray, selecting the phase difference of formed phase retardation film turns into 240nm~300nm Thickness, if 1/4 wavelength plate, then selected phase difference turns into 120nm~150nm thickness.Obtain the liquid crystal of target phase difference Layer thickness used in the optical characteristics of polymerizable liquid crystal and it is different.Such as in the RMS03-013C manufactured using Merck In the case of, the thickness for manufacturing 1/4 wavelength plate is 0.6 μm~1.5 μm of scope.

The phase retardation film obtained in the above described manner is applied preferably as the phase retardation film of liquid crystal display cells.Using making With the aligning agent for liquid crystal of the present invention come the type of drive of the liquid crystal display cells of phase retardation film that manufactures and unrestricted, such as can Applied to various modes known to TN types, STN types, IPS types, FFS types, VA types etc..The phase retardation film is to being configured at liquid crystal The lateral surface of the Polarizer of the viewable side of display element, the face for attaching the substrate-side in phase retardation film use.It is therefore preferable that it is Even if the substrate of phase retardation film is set into TAC systems or acrylic acid base material, and the substrate of the phase retardation film is set to light polarizing film Diaphragm, also play the embodiment of function.

In addition, there is volume to volume mode on an industrial scale to produce the method for phase retardation film.This method is by with continuous Step come carry out it is following handle, and using the film after these steps as coiling body come the method that reclaims：From the base of strip Film is rolled out on the coiling body of material film, the processing of liquid crystal orientation film is formed on the film that this is rolled out；It is coated with liquid crystal orientation film poly- Conjunction property liquid crystal and the processing hardened；And the optionally processing of lamination diaphragm.Come using the aligning agent for liquid crystal of the present invention The phase retardation film of formation is good to the adhesion of substrate, as coiling body come in the case of taking care of etc., liquid crystal orientation film Also it is difficult to peel off with substrate.Decline therefore, it is possible to suppress product yield when using volume to volume mode to manufacture phase retardation film.

The liquid crystal display cells of the present invention can be effectively applied to a variety of devices, such as available for：Clock and watch, portable game Machine (portable game), word processor (word processor), notes type PC (note type Personal computer), it is auto-navigation system (car navigation system), video camera (camcorder), personal Digital assistants (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, intelligent hand The display device of machine, various monitors, LCD TV etc..

[embodiment]

Hereinafter, the present invention is further specifically described by embodiment, but the present invention is not limited to these realities Apply example.

The imidizate of the solution viscosity of each polymer solution in synthesis example, polyimides is determined using following methods Rate, weight average molecular weight and epoxide equivalent.

[solution viscosity of polymer solution]

Using defined solvent, 10 weight % solution is adjusted to for polymer concentration, using E type rotation viscometers, The solution viscosity (mPas) of polymer solution is determined at 25 DEG C.

[the acid imide rate of polyimides]

The solution of polyimides is put into pure water, it is molten after the precipitation of gained is fully dried under reduced pressure at room temperature Solution, using tetramethylsilane as primary standard substance, determines at room temperature in deuterodimethylsulfoxide¹H- nuclear magnetic resonance (¹H- Nuclear magnetic resonance,¹H-NMR).According to gained¹H-NMR spectrum, obtained 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 bases occurred near chemical shift 10ppm, A²It is Peak area from other protons, α are other protons relative to 1 of the NH bases in the presoma (polyamic acid) of polymer The number ratio of proton.)

[weight average molecular weight of polymer]

Weight average molecular weight is the polystyrene scaled value to determine using the gel permeation chromatography of following condition.

Tubing string：Eastern Cao's (Tosoh) (stock) manufacture, TSKgelGRCXLII

Solvent：Tetrahydrofuran

Temperature：40℃

Pressure：68kgf/cm²

[epoxide equivalent]

Epoxide equivalent is determined using the hydrochloric acid described in JIS C2105-methyl ethyl ketone method.

[synthesis example 1：The synthesis of polyimides (PI-1)]

Using as the 2 of tetracarboxylic dianhydride, 3,5- tricarboxylic cyclopentyl acetic acid dianhydride 22.4g (0.1 mole), as diamines P-phenylenediamine 8.6g (0.08 mole) and 3,5- diaminobenzoic acid cholesteric Arrcostab 10.5g (0.02 mole), is dissolved in N- first In base -2-Pyrrolidone (NMP) 166g, carry out reacting for 6 hours at 60 DEG C, obtain containing the molten of the weight % of polyamic acid 20 Liquid.Divide and take a small amount of gained polyamic acid solution, add NMP and the solution that polyamic acid concentration is 10 weight % is made, measure Obtained by solution viscosity be 90mPas.

Then, the additional NMP in the polyamic acid solution of gained, is made the solution that polyamic acid concentration is 7 weight %, adds Add pyridine 11.9g and acetic anhydride 15.3g, 4 hours dehydration closed-loop reactions are carried out at 110 DEG C.After dehydration closed-loop reaction, using new NMP by system solvent carry out solvent displacement (by this operation, by the pyridine used in dehydration closed-loop reaction and acetic anhydride Remove to outside system；It is same as below), it is derived from the weight % of the polyimides for being about 68% containing acid imide rate (PI-1) 26 Solution.Divide and take a small amount of gained polyimide solution, add NMP and the solution that polyimides concentration is 10 weight % is made, Solution viscosity obtained by measure is 45mPas.Then, reaction solution is injected into excessive methanol, generates reaction Thing precipitates.The sediment is cleaned with methanol, is dried 15 hours with 40 DEG C under reduced pressure, is derived from polyimides (PI-1).

[synthesis example 2：The synthesis of polyimides (PI-2)]

Using as bicyclic [3.3.0] octane -2 of the 2 of tetracarboxylic dianhydride, 4,6,8- tetracarboxylics：4,6：8- dianhydrides 24.9g (0.10 mole), the p-phenylenediamine 8.6g (0.08 mole) as diamines and 3,5- diaminobenzoic acid cholesteric Arrcostab 10.4g (0.02 mole), is dissolved in 176g NMP, carries out reacting for 6 hours at 60 DEG C, obtains containing the weight %'s of polyamic acid 20 Solution.Divide and take a small amount of gained polyamic acid solution, add NMP and the solution that polyamic acid concentration is 10 weight % is made, survey Solution viscosity obtained by fixed is 103mPas.

Then, the additional NMP in the polyamic acid solution of gained, is made the solution that polyamic acid concentration is 7 weight %, adds Add pyridine 11.9g and acetic anhydride 15.3g, 4 hours dehydration closed-loop reactions are carried out at 110 DEG C.After dehydration closed-loop reaction, using new NMP by system solvent carry out solvent displacement, be derived from the polyimides (PI- for being about 71% containing acid imide rate 2) 26 weight % solution.Divide and take a small amount of gained polyimide solution, it is 10 weights to add NMP and polyimides concentration is made % solution is measured, solution viscosity obtained by measure is 57mPas.Then, reaction solution is injected into excessive methanol In, precipitate reaction product.The sediment is cleaned with methanol, is dried 15 hours with 40 DEG C under reduced pressure, is derived from gathering Acid imide (PI-2).

[synthesis example 3：The synthesis of polyimides (PI-3)]

Using as the 2 of tetracarboxylic dianhydride, 3,5- tricarboxylic cyclopentyl acetic acid dianhydride 22.4g (0.1 mole), as diamines 3- (2,4- diamino phenoxy) cholestane 14.8g (0.03 mole), methacrylic acid 2- (2,4- diamino phenoxy) ethyl ester (compound represented by following formula (R-2)) 4.73g (0.02 mole) and 1- (4- aminophenyls) -2,3- dihydros -1,3,3- Trimethyl -1H- indenes -5- amine 13.3g (0.05 mole) are dissolved in 221g NMP, carry out reacting for 6 hours at 60 DEG C, are obtained Solution containing the weight % of polyamic acid 20.A small amount of gained polyamic acid solution point is taken, adds NMP and that polyamic acid is made is dense Spend for 10 weight % solution, solution viscosity obtained by measure is 92mPas.

Then, the additional NMP in the polyamic acid solution of gained, is made the solution that polyamic acid concentration is 7 weight %, adds Add pyridine 7.9g and acetic anhydride 10.2g, 4 hours dehydration closed-loop reactions are carried out at 110 DEG C.After dehydration closed-loop reaction, using new NMP by system solvent carry out solvent displacement, be derived from the polyimides (PI- for being about 48% containing acid imide rate 3) 25 weight % solution.Divide and take a small amount of gained polyimide solution, it is 10 weights to add NMP and polyimides concentration is made % solution is measured, solution viscosity obtained by measure is 47mPas.Then, reaction solution is injected into excessive methanol In, precipitate reaction product.The sediment is cleaned with methanol, is dried 15 hours with 40 DEG C under reduced pressure, is derived from gathering Acid imide (PI-3).

[changing 7]

[synthesis example 4：The synthesis of polyamic acid (PA-1)]

Using as the 1 of tetracarboxylic dianhydride, 2,3,4- cyclobutane tetracarboxylic dianhydride 200g (1.0 moles), 2 as diamines, 2 '-dimethyl -4,4 '-benzidine 210g (1.0 moles), it is dissolved in the mixed of 370g NMP and 3,300g gamma-butyrolacton In bonding solvent, carry out reacting for 3 hours at 40 DEG C, it is 10 weight %, solution viscosity 160mPas to obtain solid component concentration Polyamic acid solution.Then, the polyamic acid solution is injected into excessive methanol, precipitates reaction product. The sediment is cleaned with methanol, is dried 15 hours with 40 DEG C under reduced pressure, is derived from polyamic acid (PA-1).

[synthesis example 5：The synthesis of polyamic acid (PA-2)]

Using as the 2 of tetracarboxylic dianhydride, 3,5- tricarboxylic cyclopentyl acetic acid dianhydride 7.0g (0.031 mole), as diamines Following formula (R-1) represented by compound (r1) 13g (relative to 2,3,5- 1 mole of tricarboxylic cyclopentyl acetic acid dianhydrides, quite In 1 mole), it is dissolved in 80g NMP, carries out reacting for 4 hours at 60 DEG C, is derived from containing polyamic acid (PA-3) 20 Weight % solution.The solution viscosity of the polyamic acid solution is 2,000mPas.In addition, compound (r1) is according to Japan The records of open patent 2011-100099 publications synthesizes.Then, the polyamic acid solution is injected into excessive first In alcohol, precipitate reaction product.The sediment is cleaned with methanol, is dried 15 hours, is derived from 40 DEG C under reduced pressure Polyamic acid (PA-2).

[changing 8]

[synthesis example 6：The synthesis of polyamic acid (PA-3)]

In the 50ml four-hole boiling flasks with agitating device and nitrogen ingress pipe, add as double (the 4- ammonia of 1,3- of diamines Base phenethyl) urea (1,3-bis (4-aminophenethyl) urea, BAPU) 0.60g (2.0mmol) and p-phenylenediamine (p- Phenylene diamine, p-PDA) 1.95g (18.0mmol), adds N, N, 2- trimethylpropanamide 30g, one side delivery of nitrogen Gas is while stirring and making its dissolving.While the diamine solution is stirred, while 1,2,3,4- rings of the addition as tetracarboxylic dianhydride Butane tetracarboxylic acid dianhydride 3.70g (18.9mmol), and then add N, N, 2- in a manner of solid component concentration turns into 12 weight % Trimethylpropanamide, in a nitrogen environment, it is stirred at room temperature 4 hours and obtains polyamic acid (PA-3) solution.

[synthesis example 7：The synthesis of polyamic acid (PA-4)]

Using as the 1 of tetracarboxylic dianhydride, 2,3,4- cyclobutane tetracarboxylic dianhydride 19.61g (0.1mol) and as diamines 4,4 '-diamino-diphenyl amine (4,4 '-DADPA) 18.73g (0.094mol), in N, N, 2- trimethylpropanamides 345.1g Mixing, carries out reacting for 5 hours at room temperature.Polymerisation is easily and evenly carried out, obtains polyamic acid (PA-4).

[synthesis example 8：The synthesis of polyamic acid (PA-5)]

Using as 2, the 4- diamino-Ns of diamines, N- diallyl anilines 14.64g (0.072mol), as monoamine just Lauryl amine 2.96g (0.016mol) and 1,2,3, the 4- cyclobutane tetracarboxylic dianhydride 15.69g as tetracarboxylic dianhydride (0.08mol), in N, N, 2- trimethylpropanamides 300g, carry out reacting for 4 hours at room temperature, obtain polyamic acid (PA-5) Solution.

[synthesis example 9：The synthesis of polyamic acid (PA-6)]

Using double [2- (4- aminophenyls) ethyl] adipic acid 10.36g as diamines and the equal benzene as tetracarboxylic dianhydride Tetracarboxylic acid dianhydride 19.63g, in N, N, 2- trimethylpropanamides 170g, carry out reacting for 4 hours at room temperature, obtain polyamide The solution of sour (PA-6).

[synthesis example 10：The synthesis of polyamic acid (PA-7)]

Using the change represented by as double [2- (4- aminophenyls) ethyl] adipic acid 11.88g of diamines, following formula (R-3) Compound 6.8g and 1 as tetracarboxylic dianhydride, 2,3,4- cyclobutane tetracarboxylic dianhydride 11.27g, in N, N, 2- trimethyl propionyl In amine 170g, carry out reacting for 4 hours at room temperature, obtain the solution of polyamic acid (PA-7).

[changing 9]

[synthesis example 11：The synthesis of polysiloxane (APS-1)]

In the reaction vessel for possessing mixer, thermometer, addition funnel and the cooling tube that flows back, 2- (3,4- epoxies are put into Butylcyclohexyl) ethyl trimethoxy silane (2- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, ECETS) 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, are mixed at room temperature.Then, from addition funnel In spend 30 minutes deionized water 100g be added dropwise after, stir under reflux on one side, while carrying out reaction in 6 hours at 80 DEG C.Reaction After end, organic layer is taken out, using 0.2 weight % aqueous ammonium nitrate solutions, is cleaned untill the water after cleaning turns into neutral, then Distillation removes solvent and water under reduced pressure, and reactive polysiloxane is thus obtained in the form of sticky transparency liquid (EPS-1).The reactive polysiloxane is carried out¹H-NMR(Nuclear Magnetic Resonance Spectroscopy, NMR spectrum) analysis, as a result near chemical shift (δ)=3.2ppm, the acquisition such as theoretical strength Peak value based on epoxy radicals, confirm not producing the side reaction of epoxy radicals in reaction.The weight of the reactive polysiloxane of gained It is 3,500 to measure average molecular weight Mw, and epoxide equivalent is 180g/ moles.

Then, in 200mL three-necked flask, reactive polysiloxane (EPS-1) 10.0g is put into, as solvent Methyl iso-butyl ketone (MIBK) 30.28g, the 4- dodecyl p-methoxybenzoic acid 3.98g as reactive compounds and as catalyst UCAT18X (trade name, general sieve in Sanya (San-Apro) (stock) manufacture) 0.10g, stirred at 100 DEG C while carrying out 48 Hour reaction.After reaction terminates, the solution for adding ethyl acetate in the reactive mixture and obtaining is washed 3 times, uses sulfuric acid After magnesium dries organic layer, distillation removes solvent, is derived from liquid crystal aligning polysiloxane (APS-1) 9.0g.Gained Polymer weight average molecular weight Mw be 9,900.

Resistance to precipitation property experiment

[embodiment 1]

By polymer (PI-1) 0.5g obtained in synthesis example 1 and METHYLPYRROLIDONE 4.5g mixed dissolutions.Xiang Qi The middle solvent (following be the second solvent) added respectively described in table 1 below, untill polymer precipitation, sentence by visual observation Break to be separated out in the stage of solution gonorrhoea, polymer.The evaluation of resistance to precipitation property experiment is to carry out as follows：By non-polymer The situation of precipitation is evaluated as " good ", and the situation that the second solvent for adding more than 5g is separated out is evaluated as "available", small by adding Be evaluated as in the situation that 5g the second solvent separates out " can not ".Its result is N, N, and 2- trimethylpropanamides are resistance to precipitation " good ".

[2~embodiment of embodiment 8]

In addition to the species of used second solvent is changed to as described in table 1 below respectively, using with it is described The identical method of embodiment 1 is tested to implement resistance to precipitation property.Its result is shown in table 1 below in the lump.

[table 1]

The preparation and evaluation of aligning agent for liquid crystal

[embodiment 9A]

By as the parts by weight of polyimides (PI-1) 100 obtained in the synthesis example 1 of polymer (A), it is dissolved in comprising N, The mixed solvent of N, 2- trimethylpropanamide (p1) and butyl cellosolve (butyl cellosolve, BC) (solvent group turns into p1: BC=50: 50 (weight ratios)) in, the solution that solid component concentration is 6.5 weight % is made.Use the filter that aperture is 1 μm The solution is filtered, thus prepares aligning agent for liquid crystal (S-1).In addition, aligning agent for liquid crystal (S-1) is mainly for the manufacture of vertical orientated Type liquid crystal display cells.

To above-mentioned prepared aligning agent for liquid crystal (S-1), after being filtered using 1.0 μm of filter, taken using liquid crystal To film printing machine (Japan's description printing (stock) manufacture), the saturating of the glass substrate with the transparency electrode comprising ito film is coated on Prescribed electrode face.Then, (prebake conditions) 1 minute are heated in 80 DEG C of heating plate and after removing solvent, in 160 DEG C of heating plate Heating (rear baking) 10 minutes, forming average film thickness isFilm, find out the viscosity of film whether there is.It is 20 using multiplying power Times microscope observe the film, find out that printing is uneven and the presence or absence of pin hole.Evaluation is to carry out as follows：Will be inviscid And do not observe that printing is uneven and the situation of pin hole is evaluated as printing well (zero) substantially, there will be viscosity or observe It is bad (×) that printing inequality and at least situation of any one of pin hole are evaluated as printing.Its result is the aligning agent for liquid crystal (160 DEG C) of printing be " good ".

To above-mentioned prepared aligning agent for liquid crystal (S-1), heating-up temperature during rear baking is changed to 220 DEG C by 160 DEG C, In addition, " evaluated by with described in a manner of the identical of evaluation 1 " of printing.Its result is, the aligning agent for liquid crystal (220 DEG C) of printing is " good ".

[embodiment 10A~embodiment 15A and comparative example 1A]

Except by the species and composition of used polymer (A) and solvent be changed to respectively as described in table 2 below with Outside, using with the embodiment 9A identicals method come prepare respectively aligning agent for liquid crystal (S-2)~aligning agent for liquid crystal (S-7) and Aligning agent for liquid crystal (SR-1).In addition, the evaluation of printing is carried out in a manner of with the embodiment 9A identicals.It the results are shown in In table 2 below.In addition, in table 2, the allotment of polymer (A) is than representing relative to the total of polymer contained in aligning agent for liquid crystal Measure the containing ratio (weight %) of 100 weight % each polymer.In addition, aligning agent for liquid crystal (S-1)~aligning agent for liquid crystal (S-3) is main It is used to manufacturing vertical alignment-type liquid crystal display device, aligning agent for liquid crystal (S-4) is mainly used in manufacturing using optical alignment method vertical Straight alignment-type liquid crystal display device, aligning agent for liquid crystal (S-5)~aligning agent for liquid crystal (S-6), aligning agent for liquid crystal (SR-1) are mainly used It is mainly used in TN type liquid crystal display cells in manufacture IPS types or FFS type liquid crystal display cells, aligning agent for liquid crystal (S-7).

[table 2]

In addition, the mark of the solvent composition in table 2 is respectively following meanings.

a：N, N, 2- trimethylpropanamide

b：Butyl cellosolve

c：Diacetone alcohol

d：METHYLPYRROLIDONE

As shown in table 2, for the aligning agent for liquid crystal of embodiment under 160 DEG C, 220 DEG C of baking temperature, printing is good. On the other hand, for the aligning agent for liquid crystal of comparative example under 160 DEG C of baking temperature, film is bad with viscosity, printing.Therefore can To say, the aligning agent for liquid crystal of embodiment can be such that polyimides or polyamic acid etc. fully dissolves, and can be by comparing low temperature Heat to form liquid crystal orientation film.

[embodiment 16A~embodiment 20A]

Except the species and composition of used polymer (A) and solvent are changed to as described in Table 3 below respectively In addition, aligning agent for liquid crystal (S-8)~aligning agent for liquid crystal (S-12) is prepared respectively using with the embodiment 9A identicals method. In addition, the evaluation of printing is carried out in a manner of with the embodiment 9A identicals.It the results are shown in Table 3 below.In addition, table In 3, the allotment of polymer (A) is than representing total amount 100 weight of each polymer phase for polymer contained in aligning agent for liquid crystal Measure % containing ratio (weight %).In addition, aligning agent for liquid crystal (S-9) is mainly for the manufacture of vertical alignment-type liquid crystal display device, Aligning agent for liquid crystal (S-8), aligning agent for liquid crystal (S-10), aligning agent for liquid crystal (S-11) are mainly for the manufacture of IPS types or FFS type liquid crystal Display element, aligning agent for liquid crystal (S-12) are mainly used in manufacturing IPS types or FFS type liquid crystal display cells using optical alignment method.

[table 3]

In addition, the mark of the solvent composition in table 3 is respectively following meanings.In addition, refer to the identical mark of table 2 With the identical compound of table 2.

e：Diethylene glycol diethyl ether

f：DIBK

i：Gamma-butyrolacton

As shown in table 3, embodiment 16A~embodiment 20A aligning agent for liquid crystal is under 160 DEG C, 220 DEG C of baking temperature, Printing is good.

[embodiment 9B]

Form using with the embodiment 9A identicals solvent, separately prepared in a manner of solution viscosity turns into 6mPas Polymer solution, filtered using 0.2 μm of filter to prepare aligning agent for liquid crystal (S-1a).Aligning agent for liquid crystal (S-1a) carries Supply the evaluation of ink-jet application.

The printing of the embodiment 9A is observed using AFM (atomic force microscope, AFM) Property evaluation 2 (220 DEG C) evaluation in gained film, measure center average roughness (Ra).Evaluation is to enter as follows OK：Situations of the Ra less than 10nm is evaluated as concave-convex surface " good ", more than 10nm, the situation less than 15nm are evaluated as "available", more than 15nm situation is evaluated as " bad ".If in addition, generally using the favorable solubility to polymer solvent, The surface tension that film then be present rises, the tendency of even levelling (concave-convex surface) decline of film.On the other hand, just obtain good For the viewpoint of good film, aligning agent for liquid crystal is preferably that surface tension is low and to the favorable solubility of polymer.In the embodiment, Concave-convex surface is the result of " good ".

Glass substrate with the transparency electrode comprising ITO is heated 1 minute in 200 DEG C of heating plate, then, carried out Ultraviolet/ozone clean, the contact angle for the water for making transparency electrode face is set to less than 10 ° persons and is used as substrate at once.Use ink-jet Coating machine (sesame Pu electromechanics (Shibaura Mechatronics) (stock) manufacture), by above-mentioned prepared aligning agent for liquid crystal (S- 1a) it is coated on the transparency electrode face of the glass substrate with transparency electrode.Application conditions now are set to：With 2,500 Secondary/(nozzle minute), spray volume 250mg/10 seconds carry out 2 coatings for coming and going and (amounting to 4 times).After coating, 1 point is stood Clock, then heated at 80 DEG C, be consequently formed the film that average film thickness is 0.1 μm.For the film of gained, in interference bar Line measurement lamp (sodium vapor lamp) irradiation under visually to be observed, will not see inequality and repel the situation of both be evaluated as ink-jet painting Cloth " good ", it will be seen that the situation of at least one of uneven and repulsion is evaluated as ink-jet application " bad ", as a result, the liquid The ink-jet application of brilliant alignment agent is " good ".

[embodiment 10B~embodiment 20B and comparative example 1B]

For aligning agent for liquid crystal (S-2)~aligning agent for liquid crystal (S-12) and aligning agent for liquid crystal (SR-1), with the implementation Example 9B identicals mode carries out the evaluation of concave-convex surface.It the results are shown in table 4 below.

[comparative example 2B]

Except used solvent to be dissolved in the mixing for including NMP, propylene carbonate (PC) and butyl cellosolve (BC) Beyond aspect in solvent (solvent group turns into NMP: PC: BC=40: 30: 30 (weight ratios)), with identical with the embodiment 9A Mode prepare aligning agent for liquid crystal (SR-2).In addition, the concave-convex surface of film is carried out in a manner of with the embodiment 9B identicals The evaluation of property.It the results are shown in table 4 below.

[table 4]

As shown in table 4, the evaluation of the concave-convex surface of the aligning agent for liquid crystal of embodiment is " good " or "available".The opposing party Face, not comprising compound (p1) as in the comparative example 2B of solvent composition, concave-convex surface is the evaluation of " bad ".According to the above Experimental result understand, the aligning agent for liquid crystal of embodiment has the dissolubility of polymer (resistance to precipitation) and the even levelling of film concurrently (concave-convex surface), in addition, even low temperature calcination, printing are also good.On the other hand, the aligning agent for liquid crystal of comparative example is low Printing under temperature calcining is bad, or the even levelling of film is bad.

[embodiment 21：Phase retardation film]

(1) preparation of aligning agent for liquid crystal

The parts by weight of polymer (PA-7) 100 obtained in synthesis example 10 are dissolved in comprising N, N, 2- trimethylpropanamides (DMIB) and in the mixed solvent (DMIB: BC=60: 40 (weight ratio)) of butyl cellosolve (BC), solid component concentration, which is made, is 5 weight % solution.The solution is filtered using the filter that aperture is 0.2 μm, thus prepares aligning agent for liquid crystal.

(2) manufacture of phase retardation film

In the one side of the TAC film as substrate, above-mentioned prepared aligning agent for liquid crystal is coated with using rod coater, is being dried Toasted 2 minutes using 120 DEG C in case and form film of the thickness as 100nm.Then, for the film coated surface, using Hg-Xe lamps and Glan-Taylor prism (Glan-Taylor prism), the polarisation that the open-wire line comprising 254nm is vertically irradiated from substrate normal is ultraviolet Line 500mJ/cm².Then, using the filter that aperture is 0.2 μm by polymerizable liquid crystal (RMS03-013C, Merck ＆ Co., Inc. manufacture) After filtering, using rod coater, the polymerizable liquid crystal is coated on the film after light irradiation and forms the painting of polymerizable liquid crystal Film.After temperature is adjusted to toast 1 minute in 50 DEG C of baking oven, using Hg-Xe lamps, coated surface is irradiated from vertical direction The ultraviolet 1,000mJ/cm of the non-polarized of open-wire line comprising 365nm², polymerizable liquid crystal is hardened and forms liquid crystal layer, thus Manufacture phase retardation film.

(3) evaluation of liquid crystal aligning

For the phase retardation film of manufacture in (2), pass through the mesh under Nicol crossed (crossed nicols) Regard and petrographic microscope (multiplying power is 2.5 times) observes the presence or absence of abnormal area, thus evaluate liquid crystal aligning (light orientation Property).Evaluation is to carry out as follows：Orientation is good when will be visual and does not observe abnormal area under petrographic microscope Situation is evaluated as liquid crystal aligning " good "；Abnormal area is not observed when will be visual, but in polarized light microscope observing to exception The situation in region is evaluated as liquid crystal aligning "available"；It will observe that the situation of abnormal area is commented under visual and petrographic microscope Valency is liquid crystal aligning " bad ".Its result is that the phase retardation film is be evaluated as liquid crystal aligning " good ".

(4) adhesion

Using the phase retardation film of manufacture in (2), the film and the adhesion of substrate formed by aligning agent for liquid crystal is entered Row evaluation.First, using the separator at equal intervals with guiding element, using cutter (cutter knife) from the liquid of phase retardation film The face incision otch of crystal layer side, form the grid pattern of 10 × 10.The depth of each otch is set to reach from liquid crystal layer surface Untill the half of substrate thickness.Then, to make cellophane tape in a manner of covering the entire surface of the grid pattern After (cellophane tape) contiguity, the cellophane tape is peeled off.Pass through visually being peeled off to observe under Nicol crossed The notch of grid pattern afterwards, and evaluate adhesion.Evaluation is to carry out as follows：It will be passed along the part of tangent line The cross section of sub-pattern is unconfirmed to be evaluated as adhesion " good " to situation about peeling off；By relative to overall of grid pattern Number, adhesion "available" is evaluated as in situation of the number less than 15% of the grid of the partially observable stripping；Will be relative to lattice The overall number of sub-pattern, the situation for being more than 15% in the number of the grid of the partially observable stripping are evaluated as adhesion " bad ".Its result is that the phase retardation film is adhesion " good ".

Claims

1. a kind of aligning agent for liquid crystal, it contains：

Selected from least one of group being made up of polyamic acid, polyimides, poly amic acid ester and polysiloxane Polymer (A)；And

The solvent of the compound (p1) represented by following formula (1) is included, and the content of the compound (p1) is the solvent Total amount the weight % of 5 weight %~50；

In formula (1), R¹~R⁴It is separately the alkyl or the C- in the alkyl of straight-chain or the carbon number 1~6 of branch-like There is the base selected from least one of-O- ,-COO- and-OCO- between C keys.

2. aligning agent for liquid crystal according to claim 1, its include be selected from by being reacted tetracarboxylic dianhydride and diamines and At least one of group that polyamic acid, polyimides and the poly amic acid ester of acquisition are formed is used as the polymer (A), The tetracarboxylic dianhydride is included selected from bicyclic [3.3.0] by 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, 2,4,6,8- tetracarboxylics Octane -2:4,6:8- dianhydrides, 1,2,3,4- cyclobutane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acids 2:3, 5:6- dianhydrides, 1,3,3a, 4,5,9b- hexahydros -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphtho- [1,2-c] furans -1,3- Diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphtho- [1,2-c] furans - At least one of group that 1,3- diketone, 1,2,4,5- cyclopentanetetracarboxylics dianhydride and pyromellitic acid anhydride are formed.

3. a kind of liquid crystal orientation film, it is formed using aligning agent for liquid crystal as claimed in claim 1 or 2.

4. a kind of liquid crystal display cells, it includes liquid crystal orientation film as claimed in claim 3.

5. a kind of phase retardation film, it includes liquid crystal orientation film as claimed in claim 3.

6. a kind of liquid crystal orientation film, it is by the way that aligning agent for liquid crystal as claimed in claim 1 or 2 is coated on substrate to be formed Film, light irradiation is carried out to the film to make.

7. a kind of manufacture method of liquid crystal orientation film, it includes：Aligning agent for liquid crystal as claimed in claim 1 or 2 is formed at Step on substrate；And the step of light irradiation is to assign liquid crystal aligning ability is carried out to film.

8. a kind of manufacture method of aligning agent for liquid crystal, it includes：

Synthesis is selected from by polyamic acid, polyimides in the organic solvent comprising the compound (p1) represented by following formula (1) And the step of at least one of group for being formed of poly amic acid ester polymer；And

Manufacture aligning agent for liquid crystal the step of, the aligning agent for liquid crystal contain by it is described synthesis and obtain polymer and comprising The solvent of compound (p1) represented by following formula (1), and the content of the compound (p1) is the 5 of the total amount of the solvent The weight % of weight %~50；

9. a kind of manufacture method of phase retardation film, it includes：

The step of aligning agent for liquid crystal as claimed in claim 1 or 2 is coated on substrate and forms film；

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

The step of polymerizable liquid crystal being coated with the film after the light irradiation and making its hardening.