CN102317847B - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells - Google Patents

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

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CN102317847B
CN102317847B CN200980156821.1A CN200980156821A CN102317847B CN 102317847 B CN102317847 B CN 102317847B CN 200980156821 A CN200980156821 A CN 200980156821A CN 102317847 B CN102317847 B CN 102317847B
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liquid crystal
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aligning agent
nmp
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CN102317847A (en
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后藤耕平
片山雅章
保坂和义
松本欣也
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

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Abstract

The invention provides the few and reduction of voltage retention is also little after the being exposed to backlight for a long time aligning agent for liquid crystal of a kind of film chip produced because of friction treatment.The feature of this aligning agent for liquid crystal is, containing have compound that group that formula [i] represents is incorporated into the structure of aromatic ring as (A) composition, be selected from the macromolecular compound of at least one of polyimide and polyimide precursor as (B) composition.In formula [i], X is the alkyl of hydrogen atom or carbon number 1 ~ 3.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells
Technical field
The present invention relates to the aligning agent for liquid crystal containing polyimide and/or polyimide precursor, liquid crystal orientation film and liquid crystal display cells.
Background technology
Liquid crystal display cells, as the display device realizing thin light, is widely used now.Usually in this liquid crystal display cells, for determining that the state of orientation of liquid crystal uses liquid crystal orientation film.In addition, except the vertical alignment-type liquid crystal display device etc. of a part, this liquid crystal orientation film of major part is by implementing certain orientation process to the surface of the polymkeric substance tunicle that electrode base board is formed and obtaining.
As the polymkeric substance used in liquid crystal orientation film, there will be a known polyimide, polyamide, polyamidoimide etc., these polymkeric substance of use or its precursor are dissolved in the aligning agent for liquid crystal in solvent usually.As the precursor of polyimide, usually use polyamic acid.
As the method for the polymkeric substance tunicle orientation making electrode base board is formed, now universal method as raw-material cloth in order to rayon cloth etc. this tunicle surface is applied to pressure wiping, namely implements the method for friction treatment.But in the operation of friction treatment, the part producing tunicle is sometimes peeled off, the surface of liquid crystal orientation film produces the problem of scar and so-called " film chip " with friction treatment.These are abnormal is one of the characteristic reduction and then the reason causing decrease in yield that make liquid crystal display cells.
For the film chip problem produced with friction treatment, the method (for example, see patent documentation 1) of the aligning agent for liquid crystal also containing particular thermal cross-linked compound while proposing at least a kind of polymkeric substance using and contain polyamic acid or polyimide or the method (for example, see patent documentation 2) of the aligning agent for liquid crystal of use similarly containing the compound containing epoxy radicals etc. improve the method for rub resistance by use hardening agent.
What is more, large picture and the liquid crystal TV set of high-resolution are by extensive practicality in recent years, and for the liquid crystal display cells in this purposes, requiring that it possesses under harsh environment for use can the resistance characteristics of Long-Time Service.Therefore, require that being used for this liquid crystal orientation film has reliability higher than ever, and for the electrical characteristics of liquid crystal orientation film, being also not only require that initial stage characteristic is good, also requiring such as being exposed to the excellent light of backlight for a long time.
Patent documentation 1 Japanese Patent Laid-Open 9-185065 publication
Patent documentation 2 Japanese Patent Laid-Open 9-146100 publication
Summary of the invention
The present invention completes in view of the foregoing.
That is, technical matters to be solved by this invention is to provide the few and reduction of voltage retention is also little after the being exposed to backlight for a long time aligning agent for liquid crystal of a kind of film chip produced because of friction treatment, and then provides that a kind of possess under harsh environment for use can the tolerance of Long-Time Service and the high liquid crystal display cells of reliability.
The present invention has following technology contents.
(1) aligning agent for liquid crystal, it is characterized in that, containing have compound that group that formula [i] represents is incorporated into the structure of aromatic ring as (A) composition, be selected from the macromolecular compound of at least one of polyimide and polyimide precursor as (B) composition
X is the alkyl of hydrogen atom or carbon number 1 ~ 3.
(2) aligning agent for liquid crystal as described in above-mentioned (1), wherein, the X in formula [i] is hydrogen atom.
(3) aligning agent for liquid crystal as described in above-mentioned (1) or (2), wherein, at least one of the compound that (A) composition represents for the compound that is selected from following formula [1] and represents and formula [2],
In formula, X 1, X 2and X 3be the alkyl of hydrogen atom or carbon number 1 ~ 3 independently of one another, Y 1, Y 2and Y 3respective is independently aromatic ring, and any hydrogen atom of this aromatic ring can be replaced by the alkoxy of the alkyl of hydroxyl, carbon number 1 ~ 3, halogen atom, carbon number 1 ~ 3 or vinyl, Z 1for singly-bound, all or part of can in conjunction with the saturated hydrocarbyl ,-NH-,-N (CH of the carbon number 1 ~ 10 of formation ring texture 3)-or the group that represents of formula [3], wherein all or part of can be able to be replaced by fluorine atoms in conjunction with any hydrogen atom of saturated hydrocarbyl of the carbon number 1 ~ 10 forming ring texture,
——P 1-Q 1-P 2—[3]
In formula, P 1and P 2be the alkyl of carbon number 1 ~ 5 independently of one another, Q 1for aromatic ring,
T 1be the integer of 2 ~ 4, t 2and t 3be the integer of 1 ~ 3 independently of one another, a and b is the integer of 1 ~ 3 independently of one another.
(4) aligning agent for liquid crystal as described in above-mentioned (3), wherein, the X in formula [1] 1and the X in formula [2] 2and X 3for hydrogen atom.
(5) aligning agent for liquid crystal as described in above-mentioned (3) or (4), wherein, the Y in formula [1] 1and the Y in formula [2] 2and Y 3be phenyl ring or pyridine ring independently of one another.
(6) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (5), wherein, (A) composition is at least one compound being selected from following compound,
(7) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (5), wherein (A) composition is at least one compound being selected from following compound,
(8) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (7), wherein, (B) composition is the macromolecular compound of at least one being selected from the polyamic acid being reacted by diamine component and tetracarboxylic dianhydride's composition and obtained and the polyimide obtained by this polyamic acid dehydration closed-loop.
(9) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (8), wherein, also containing organic solvent.
(10) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (9), wherein, the quality (concentration of solid constituent) after removing organic solvent is 1 ~ 20 quality %.
(11) liquid crystal orientation film, uses the aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (10) and obtains.
(12) liquid crystal display cells, possesses the liquid crystal orientation film described in above-mentioned (11).
Few and the reduction of voltage retention is also little after the being exposed to backlight for a long time liquid crystal orientation film of the film chip that aligning agent for liquid crystal of the present invention can obtain producing because of friction treatment.Therefore, the liquid crystal display cells reliability with the liquid crystal orientation film obtained by aligning agent for liquid crystal of the present invention is high, is applicable to the liquid crystal TV set etc. of large picture and high-resolution.
Embodiment
Aligning agent for liquid crystal of the present invention contain have group that formula [i] represents be incorporated into the compound (hereinafter also referred to " specific compound ") of the structure of aromatic ring as (A) composition, be selected from the macromolecular compound (hereinafter also referred to " particular polymers ") of at least one of polyimide and polyimide precursor as (B) composition
In formula [i], X is the alkyl of hydrogen atom or carbon number 1 ~ 3.Wherein, when X is hydrogen atom, can improve the tilt angle of liquid crystal under the state keeping homogeneous liquid crystal aligning, can accelerate the release of the electric charge put aside in liquid crystal display cells, be therefore preferred simultaneously.
Aligning agent for liquid crystal of the present invention is normally containing (A) composition and (B) composition and (A) composition and the solution state of (B) component dissolves in organic solvent.
< (A) composition >
Specific compound as (A) composition has the structure that group that above formula [i] represents is incorporated into aromatic ring, the group (-CH that formula [i] represents 2-OX base) structure that is directly incorporated into aromatic ring makes easily to carry out with the association reaction of polyimide and polyamic acid, makes the id reaction between specific compound also easily carry out simultaneously.Infer that this is the main cause having given play to effect of the present invention.
In specific compound, at least one compound being selected from compound that following formula [1] represents and the compound that formula [2] represents is preferred.
In formula, X 1, X 2and X 3be the alkyl of hydrogen atom or carbon number 1 ~ 3 independently of one another.Y 1, Y 2and Y 3respective is independently aromatic ring.Any hydrogen atom of this aromatic ring can be replaced by the alkoxy of the alkyl of hydroxyl, carbon number 1 ~ 3, halogen atom, carbon number 1 ~ 3 or vinyl, Z 1for singly-bound, all or part of can in conjunction with divalent the saturated hydrocarbyl ,-NH-,-N (CH of the carbon number 1 ~ 10 of formation ring texture 3the group that formula)-, [3] represents, wherein all or part of can be able to be replaced by fluorine atoms in conjunction with any hydrogen atom of the divalent saturated hydrocarbyl of the carbon number 1 ~ 10 of formation ring texture.T 1be the integer of 2 ~ 4, t 2and t 3be the integer of 1 ~ 3 independently of one another, a and b is the integer of 1 ~ 3 independently of one another.
——P 1-Q 1-P 2—[3]
In formula [3], P 1and P 2be the alkyl of carbon number 1 ~ 5 independently of one another, Q 1for aromatic ring.
-the CH of formula [1] and formula [2] 2-OX 1base ,-CH 2-OX 2base and-CH 2-OX 3base is directly incorporated into aromatic ring, therefore Y 1, Y 2and Y 3be aromatic ring independently of one another.
As object lesson, phenyl ring can be exemplified, naphthalene nucleus, tetrahydro naphthalene nucleus, Azulene ring, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring, compel the own ring of naphthalene cyclization (Off エ Na レ ン Ring), pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, cinnoline ring (チ ノ リ ン Ring), phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, acridine ring, oxazole ring etc.As the object lesson of preferred aromatic ring, phenyl ring, naphthalene nucleus, fluorenes ring, anthracene nucleus, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring, carbazole ring, pyridazine ring, pyrazine ring, benzimidazole ring, benzimidazole ring, indole ring, quinoxaline ring, acridine ring etc. can be exemplified.More preferably phenyl ring, naphthalene nucleus, pyridine ring, carbazole ring, most preferably phenyl ring, pyridine ring further.
In addition, the hydrogen atom of these aromatic rings can be replaced by the alkoxy of the alkyl of hydroxyl, carbon number 1 ~ 3, halogen atom, carbon number 1 ~ 3 or vinyl.
T in formula [2] 2and t 3be more preferably the integer of 1 or 2, a and b is more preferably 1 or 2.
X in formula [1] 1and the X in formula [2] 2and X 3independently of one another for being selected from hydrogen atom, CH 3, C 2h 5and C 3h 71 kind of group be advisable, carbon number is fewer, easier with the association reaction of polyimide and polyamic acid, or id reaction between this compound is easier.On the other hand, if carbon number becomes many, then-CH 2-OX 1base ,-CH 2-OX 2base and-CH 2-OX 3the reactivity of base can reduce, and the storage stability of the solution therefore containing this compound increases.Wherein, the X in formula [1] 1and the X in formula [2] 2and X 3during for hydrogen atom, can improve the tilt angle of liquid crystal under the state keeping homogeneous liquid crystal aligning, can accelerate the release of the electric charge put aside in liquid crystal display cells, be therefore preferred simultaneously.
Z in formula [2] 1for its all or part of can in conjunction with formed ring texture carbon number 1 ~ 10, preferably 1 ~ 5 divalent saturated hydrocarbyl time, its any hydrogen atom had can be replaced by fluorine atoms.
As Z 1example, the group of the carbon number 1 ~ 10 that the alkylidene of carbon number 1 ~ 10, the ester ring type alkyl of carbon number 3 ~ 10, alkylidene and ester ring type alkyl combine can be exemplified.In addition, the group that any hydrogen atom that also can exemplify above-mentioned group is replaced by fluorine atoms.
Q in formula [3] 1for aromatic ring, as its object lesson, phenyl ring can be exemplified, naphthalene nucleus, tetrahydro naphthalene nucleus, Azulene ring, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring, compel the own ring of naphthalene cyclization, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, acridine ring, oxazole ring etc.As the object lesson of preferred aromatic ring, phenyl ring, naphthalene nucleus, fluorenes ring, anthracene nucleus, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring, carbazole ring, pyridazine ring, pyrazine ring, benzimidazole ring, benzimidazole ring, indole ring, quinoxaline ring, acridine ring etc. can be exemplified.More preferably phenyl ring, naphthalene nucleus, pyridine ring, carbazole ring, fluorenes ring etc. further.
In the present invention, at least one compound of the formula of being selected from [1] and formula [2] can be used.
Object lesson as specific compound used in the present invention can exemplify the compound of [P1] ~ [P45], but is not limited thereto.
As the specific compound preferably compound that represents of [P15], [P17], [P19], [P29], [P31], [P41] of above-mentioned (A) composition, wherein the compound that represents of [P15], [P17], [P29], [P31], [P41] more preferably.
< (B) composition >
(B) composition is particular polymers, and particular polymers defines as above-mentioned.In the present invention, polyimide precursor refers to polyamic acid and/or poly amic acid ester.As particular polymers, preferably polyimide and polyamic acid.
In the present invention, the method for synthesis particular polymers is not particularly limited.
Particular polymers is usually reacted by diamine component and tetracarboxylic dianhydride's composition and is obtained.Usually, make to be selected from least a kind of tetrabasic carboxylic acid composition of tetracarboxylic dianhydride and derivant thereof and one or more diamine compounds and form diamine component and react, obtain the polyamic acid of the structural formula with the repetitive that formula [5] represents.For obtaining poly amic acid ester, the method that can to use the converting carboxylate groups of polyamic acid be ester.And then for obtaining polyimide, the method above-mentioned polyamic acid imidizate being obtained polyimide can be used.
In formula [5], R 1be 4 valency organic groups, R 2for divalent organic group, n is positive integer.
Suitably select as required as the tetrabasic carboxylic acid composition of raw material and diamine component.Said tetrabasic carboxylic acid and derivant thereof refer to tetrabasic carboxylic acid, tetracarboxylic acid acyl dihalo-and tetracarboxylic dianhydride herein.Wherein, the reactivity of tetracarboxylic dianhydride and diamine compound is high, thus preferably.
Above-mentioned R 1object lesson, the structure of following A-1 ~ A-46 can be exemplified.
In addition, R 2object lesson, the structure of B-1 ~ B-113 described later can be exemplified.
In above-mentioned B-112 and B-113, Q is-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-NH-any one.
As the manufacture method of particular polymers, such as, the diamine component of at least one making the tetrabasic carboxylic acid composition of at least one of the tetracarboxylic dianhydride represented containing formula [6] and contain the diamine compound that formula [7] represents can be exemplified at 1-METHYLPYRROLIDONE, N, N '-dimethyl acetamide, N, the method for polycondensation in the organic solvents such as N '-dimethyl formamide, gamma-butyrolacton.
In addition, the R in formula [6] 1identical with the definition in formula [5], its object lesson is above-mentioned A-1 ~ A-46.In addition, the R in formula [7] 2identical with the definition in formula [5], its object lesson is above-mentioned B-1 ~ B-113.
For obtaining tetracarboxylic dianhydride that particular polymers uses and derivant is not particularly limited.Tetracarboxylic dianhydride can one kind or two or morely combinationally use.Wherein, under the occasion paying attention to voltage retention performance, the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure that A-1 ~ A-25 and A-46 is so is preferably used.Particularly preferably use at least one being selected from A-1 ~ A-6, A-8, A-16, A-18 ~ A-24 and A-46.
In addition, when at least 10 ~ 100mol% of tetracarboxylic dianhydride's composition is the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, then effective on voltage retention performance.
On the other hand, under the occasion paying attention to liquid crystal aligning or reduction savings electric charge, the aromatic dianhydride that A-26 ~ A-45 is so is preferably used.Particularly preferably use at least one being selected from A-26, A-27, A-32, A-34 and A-39 ~ A-43.
In addition, when at least 20 ~ 100mol% of tetracarboxylic dianhydride's composition is aromatic dianhydride, then effective on liquid crystal aligning or reduction savings electric charge.
Have the occasion that the tetracarboxylic dianhydride of ester ring type structure or aliphatic structure and aromatic dianhydride combinationally use in tetracarboxylic dianhydride's composition under, its preferred ratio of components (mol%) is the former 10 ~ 80mol%, the latter 20 ~ 90mol%.
Particularly, in tetracarboxylic dianhydride, when using at least one of A-6, A-16, A-18, A-19 ~ A-22 and A-46, use the dissolubility of the particular polymers of this tetracarboxylic dianhydride to improve, dissolubility when making this polymkeric substance dehydration closed-loop and form soluble polyimide is good.
The diamines that formula [7] represents is not particularly limited, and only can use one in the present invention, also can use multiple.Wherein, for obtain diamine component that particular polymers uses part or all be the occasion of B-80 ~ B-101 etc. under, the tilt angle of liquid crystal can be improved.In addition, as the diamine component improving liquid crystal pretilt angle, the diamine compound that following formula represents can be exemplified.
In formula, A 4for the alkyl of carbon number 3 ~ 20 that can be replaced by fluorine atoms, A 3for Isosorbide-5-Nitrae-cyclohexylene or Isosorbide-5-Nitrae-phenylene, A 2for oxygen atom or-COO-* (associative key of band " * " and A 3in conjunction with), A 1for oxygen atom or-COO-* (associative key of band " * " and a 2in conjunction with).In addition, a 1be the integer of 0 or 1, a 2be the integer of 2 ~ 10, a 3it is the integer of 0 or 1.
Under particularly making the occasion of liquid crystal vertical-tropism, 5 ~ 100mol% of preferred diamine component, more preferably 10 ~ 80mol% use B-80 ~ B-101 etc.
When tetrabasic carboxylic acid composition and diamine component polyreaction, temperature of reaction can select the arbitrary temp of-20 DEG C ~ 150 DEG C, preferably in the scope of-5 DEG C ~ 100 DEG C.
The degree of polymerization of particular polymers is subject to the impact of raw materials ratio.Therefore, the total mole number forming the compound of tetrabasic carboxylic acid composition is preferably 0.8 ~ 1.2 with the ratio of the total mole number of the diamine compound forming diamine component, is more preferably 0.9 ~ 1.1.This mol ratio is more close to 1.0, and the degree of polymerization of the polymkeric substance of generation is larger.
As the method making polyamic acid imidizate, usually have by heating the hot-imide carried out, the catalysis imidizate using catalyzer to carry out, the catalysis imidizate method of carrying out imidization reaction at a lower temperature not easily causes the reduction of the molecular weight of the polyimide of gained thus preferred.
Catalysis imidizate by organic solvent, stir polyamic acid to carry out under the existence of base catalyst and acid anhydrides.Temperature of reaction is now-20 DEG C ~ 250 DEG C, is preferably 0 ~ 180 DEG C.Temperature of reaction height then imidizate carries out soon, but too high, and the molecular weight of polyimide can decline sometimes.The amount of base catalyst is 0.5 ~ 30 mole times, preferably 2 ~ 20 moles times of acid amides acidic group, and the amount of acid anhydrides is 1 ~ 50 mole times, preferably 3 ~ 30 moles times of acid amides acidic group.When the amount of base catalyst and acid anhydrides is few, reaction can not fully be carried out, and time too much, reaction is difficult to remove completely after terminating.As base catalyst, can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc., wherein pyridine also has the alkalescence of appropriateness while making reaction carry out, and is therefore preferred.In addition, as acid anhydrides, can exemplify acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc., wherein during use acetic anhydride, reaction terminates rear easily refining, is therefore preferred.As organic solvent, as long as dissolve polyamic acid, not circumscribed, its object lesson can exemplify N, N '-dimethyl formamide, N, N '-dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea (TMU), dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton etc.Catalysis imidizate and the acid imide rate that obtains controls by regulating catalytic amount and temperature of reaction, reaction time.
The polyimide generated is by obtaining reclaiming the precipitation of generation after above-mentioned reaction solution input Weak solvent.Now, Weak solvent used is not particularly limited, and can exemplify methyl alcohol, acetone, hexane, butyl cellosolve, heptane, MEK, methyl isobutyl ketone, ethanol, toluene, benzene, water etc.The polyimide dropping into Weak solvent postprecipitation after filtering, can form powder through normal temperature or heat drying under normal or reduced pressure.After being dissolved in by this polyimide powder in organic solvent, reppd operation repetition 2 ~ 10 times, can refine polyimide again.Precipitation reclaimer operation once not divisible impurity time, preferably carry out this refining step.
The molecular weight of specific polyimide used in the present invention is not particularly limited, and consider from the stability of characteristic when easy process and film forming, weight-average molecular weight is preferably 2000 ~ 200000, is more preferably 4000 ~ 50000.Molecular weight is tried to achieve by GPC (gel permeation chromatography).
< liquid crystal aligning process >
Aligning agent for liquid crystal of the present invention is obtained by mixing with as the particular polymers of (B) composition and other composition aftermentioned of using as required in organic solvent by the above-mentioned specific compound as (A) composition usually.Specific compound can use a kind, also can and with multiple.
As mixed method, the method for other composition aftermentioned of adding (A) composition at (B) component dissolves and use as required in the solution of organic solvent can be exemplified.As long as the solvent that organic solvent now used makes polyimide dissolve, be not particularly limited.Its object lesson exemplifies as follows.
N can be exemplified, N '-dimethyl formamide, N, N '-dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide, tetramethylurea (TMU), pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, cinene, ethyl pentyl group ketone, methyl nonyl ketone, MEK, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone etc.But two or more is used in combination for these solvents.
When making polyimide be dissolved in organic solvent, promote that the object that polyimide dissolves can heat for reaching.Heating-up temperature is too high, and the molecular weight of polyimide declines sometimes, therefore heating-up temperature preferably 30 ~ 100 DEG C, more preferably 50 ~ 90 DEG C.The concentration of polyimide solution is not particularly limited, and in solution, the concentration of polyimide is preferably 1 ~ 20 quality %, is more preferably 3 ~ 15 quality %, is particularly preferably 3 ~ 10 quality %.
Specific compound directly adds in the solution of polyamic acid and solvent-soluble polyimide also harmless, but preferably adds making with suitable solvent after concentration is the solution of 0.1 ~ 5 quality %, preferably 5 ~ 20 quality %.As this solvent, the solvent of aforesaid polyimide can be exemplified.
Other composition of < >
Aligning agent for liquid crystal of the present invention except particular polymers, specific compound, also can solvent containing thickness homogeneity during raising coating of liquid crystalline aligning agent as other composition and surface smoothness or material, adaptation between raising liquid crystal orientation film and substrate material etc.These compositions can add in the mixed process of particular polymers and specific compound, also can in the mixed solution adding particular polymers and specific compound afterwards to.
[improving the solvent of thickness homogeneity and surface smoothness]
As the object lesson of solvent improving thickness homogeneity and surface smoothness, following solvent can be exemplified.
Such as, isopropyl alcohol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, single acetic acid glycol ester, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, single propylene glycol acetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, diethylene glycol, single acetic acid binaryglycol ester, diethylene glycol dimethyl ether, single acetic acid dipropylene glycol ester monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, single acetic acid dipropylene glycol ester list ethylether, dipropylene glycol list propyl ether, single acetic acid dipropylene glycol ester list propyl ether, 3-methyl-3-methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, isopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, hexyl ether, normal hexane, n-pentane, normal octane, Anaesthetie Ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3-methoxy propyl ketone acid methyl esters, 3-ethoxy-c ketone acid Methylethyl ester, 3-methoxy propyl keto acid ethyl ester, 3-ethoxy-c ketone acid, 3-methoxy propyl ketone acid, 3-methoxy acetone propyl propionate, 3-methoxy acetone acid butyl ester, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, single propylene glycol acetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, propylene glycol-1-single ethylether-2-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the solvent etc. of low surface tension.
These solvents can use a kind, also can be multiple used in combination.Under the occasion using above-mentioned solvent, preferably account for 5 ~ 80 quality % of whole solvents contained in aligning agent for liquid crystal, more preferably account for 20 ~ 60 quality %.
[improving the material of thickness homogeneity and surface smoothness]
As the material improving thickness homogeneity and surface smoothness, fluorine system surfactant, silicon system surfactant, nonionic system surfactant etc. can be exemplified.
More specifically, エ Off ト Star プ EF301, EF303, EF352 (many Jims product Co., Ltd. (ト mono-ケ system プ ロ ダ クツ society) system), メ ガ Off ア Star Network F171, F173, R-30 (large Japanese ink Industrial Co., Ltd (large Japanese イ Application キ society) system), Off ロ ラ mono-De FC430, FC431 (Sumitomo 3M Co., Ltd. system), ア サ ヒ ガ mono-De AG710, サ mono-Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd's system) etc. can be exemplified.Relative to (B) composition 100 mass parts contained in aligning agent for liquid crystal, the usage ratio of these materials is preferably 0.01 ~ 2 mass parts, is more preferably 0.01 ~ 1 mass parts.
[improving the material of the adaptation between liquid crystal orientation film and substrate]
As the object lesson of the material of the adaptation improved between liquid crystal orientation film and substrate, the compound containing functional silanes shown below or the compound containing epoxy radicals can be exemplified.
Such as, 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTES of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) cyclohexane of 1,3-, N, N, N ', N ' ,-four glycidyl group-4, 4 '-diaminodiphenyl-methane etc.
When adding these compounds, relative to particular polymers composition 100 mass parts contained in aligning agent for liquid crystal, its content is preferably 0.1 ~ 30 mass parts, is more preferably 1 ~ 20 mass parts.Then cannot expect to improve the effect of adaptation less than 0.1 mass parts, more than 30 mass parts then sometimes the orientation of liquid crystal be deteriorated.
In aligning agent for liquid crystal of the present invention, except mentioned component, in the scope not damaging effect of the present invention, component of polymer beyond particular polymers can be added or change the material (dielectric or conductive materials etc.) of the electrical characteristics such as the specific inductive capacity of liquid crystal orientation film or electric conductivity, the bridging property material for the purpose of the hardness improving film when forming liquid crystal orientation film or density can also be added.
[changing the material of electrical characteristics]
Move, promote to use the concrete example of the material of the electric charge release of the liquid crystal cell of this liquid crystal orientation film as the electric charge promoted in liquid crystal orientation film, the amine (hereinafter also referred to " interpolation amine ") of M1 ~ M158 etc. can be exemplified.Adding amine directly adds in particular polymers harmless, but adds preferably form the solution of concentration 0.1 ~ 10 quality %, more preferably 1 ~ 7 quality % with suitable solvent after.As this solvent, the solvent of aforesaid polyimide can be exemplified.
The concentration of the solid constituent in aligning agent for liquid crystal of the present invention suitably can change according to the target film thickness of liquid crystal orientation film, from forming flawless film and the angle obtained as the suitable thickness of liquid crystal orientation film is considered, preferably 1 ~ 20 quality %, be more preferably 2 ~ 10 quality %.Said solid constituent refers to the quality except the composition after desolventizing from aligning agent for liquid crystal herein.
< liquid crystal orientation film liquid crystal display cells >
Aligning agent for liquid crystal of the present invention is being coated on substrate after burning till, the orientation process such as can carry out that friction treatment or illumination are penetrated, or is used as liquid crystal orientation film without orientation process in vertical orientated purposes etc.As long as the substrate that the substrate transparency is high, be not particularly limited, the plastic base etc. such as glass substrate or acrylic acid substrate, polycarbonate substrate can be used.Particularly, the substrate be formed for the ITO electrode etc. of liquid crystal drive considers it is preferred from the angle that technique simplifies.In addition, in reflection type liquid crystal display element, if only side substrate also can use the opaque materials such as silicon wafer, electrode now also can use the material of the reflected light such as aluminium.
The coating process of aligning agent for liquid crystal is not particularly limited, and the method be coated with is carried out in industrial usual employing by serigraphy, hectographic printing, flexible printing, ink-jet etc.As other coating process, there are dip coating, rolling method, seam to be coated with method, spin-coating method etc., these methods can be used according to object.
Burning till by using the heater means such as heating plate to make solvent evaporate at 50 ~ 300 DEG C, preferably 80 ~ 250 DEG C, form film and carry out after aligning agent for liquid crystal is coated substrate.The thickness of the film after burning till is blocked up then unfavorable in the energy consumption of liquid crystal display cells, cross thin then sometimes the reliability of liquid crystal display cells reduce, therefore preferably 5 ~ 300nm, is more preferably 10 ~ 100nm.When making liquid crystal horizontal alignment or tilted alignment, by friction or polarisation Ultraviolet radiation etc., the film after burning till is processed.
Liquid crystal display cells of the present invention is after being with the substrate of liquid crystal orientation film by said method by aligning agent for liquid crystal acquisition of the present invention, the element formed by known method manufacture liquid crystal cell.
An example of liquid crystal cell is manufactured if exemplify, following method can be illustrated: a pair substrate preparing to be formed with liquid crystal orientation film, the liquid crystal orientation film of a substrate scatters sept, makes liquid crystal aligning face become interior rear flank another baseplate-laminating, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with sept after, baseplate-laminating is carried out the method etc. sealed.The thickness of sept is now preferably 1 ~ 30 μm, is more preferably 2 ~ 10 μm.
Use aligning agent for liquid crystal of the present invention and obtained liquid crystal display cells excellent in reliability, be applicable to the LCD TV etc. of large picture and high-resolution.
Embodiment
Describe embodiment (synthesis example) and comparative example below so that the present invention will be described in more detail, but and be not interpreted as the present invention and be limited by this.
< synthesis example 1 ~ 14, embodiment 1 ~ 27 and comparative example 1 ~ 6>
Abbreviation used in these embodiments (synthesis example) and comparative example is as described below.In addition, the molecular weight determination of polyimide and the mensuration of acid imide rate are undertaken by following method.
< tetracarboxylic dianhydride >
A-1:4-dicarboxylic acid-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride
A-2:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
A-3: pyromellitic acid anhydride
A-4: dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
A-5:2,3,5-tricarboxylic cyclopentyl acetic acid-Isosorbide-5-Nitrae: 2,3-dianhydride
< diamines >
B-2:1,3-diamido-4-octadecane oxygen base benzene
B-4: p-phenylenediamine (PPD)
B-5:4-{4-(4-pentylcyclohexyl) phenoxy group }-1,3-diaminobenzene
B-8:4,4 '-diaminodiphenyl-methane
B-13:3,5-diaminobenzoic acid
B-14: m-phenylene diamine
B-15: the following formula B-15 diamine compound represented
B-16:1,3-diamido-5-{4-[trans-4-(trans-4-n-pentyl cyclohexyl) cyclohexyl] phenoxymethyl } benzene
(specific compound)
P15, P17, P29, P31 are identical with aforementioned with the implication of P41.
< amines >
C-1:3-aminomethyl pyridine
C-2:3-aminopropylimidazol
(organic solvent)
NMP:N-N-methyl-2-2-pyrrolidone N-
BCS: butyl cellosolve
GBL: gamma-butyrolacton
The molecular weight determination > of < polyimide
The chromatographic column (KD-803, KD-805) that normal temperature gel permeation chromatography (GPC) device (SSC-7200) that in synthesis example, the molecular weight of polyimide uses Xian Xiu science Co., Ltd. (セ Application シ ユ mono-science society) to make, Xiao De Ces Co., Ltd (Shodex society) make measures as follows.
Column temperature: 50 DEG C
Eluant: N, and N '-dimethyl formamide (as adjuvant, lithium bromide monohydrate (LiBrH 2o) 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) 30mmol/L, tetrahydrofuran (THF) 10ml/L)
Flow velocity: 1.0ml/ divides
Make the standard sample of calibration curve: (East ソ mono-society of TOSOH Co., Ltd) polyglycol (molecular weight about 12000,4000,1000) made of the TSK standard polyethylene oxide (molecular weight about 9000000,150000,100000,30000) made and polymer experiments company (Port リ マ mono-ラ ボ ラ ト リ mono-society).
The mensuration > of < acid imide rate
In synthesis example, the acid imide rate of polyimide measures as follows.The polyimide powder of 20mg is dropped in NMR coupon (the NMR coupon standard φ 5 that wasteland's science Co., Ltd. (wasteland's science society) makes), add the deuterated dimethylsulfoxide (DMSO-d of 0.53ml 6, 0.05%TMS melange), apply ultrasound wave make it to dissolve completely.The NMR analyzer (JNW-ECA500) that this solution NEC data Co., Ltd. (Japanese Electricity デ mono-タ system society) makes is measured the proton N MR of 500MHz.Not having the proton of vicissitudinous structure to be decided to be reference proton by coming from before and after imidizate, using the proton peak integrated value coming from the NH base of amic acid occurred near the peak integrated value of this proton and 9.5 ~ 10.0ppm, trying to achieve acid imide rate with following formula.
Acid imide rate (%)=(1-α x/y) × 100
In above formula, the peak integrated value that the proton peak integrated value that x is the NH base coming from amic acid, y are reference proton, relative to the number ratio of the reference proton of NH matrix of an amic acid when α is polyamic acid (acid imide rate is 0%).
(synthesis example 1)
Mixing A-4 (13.5g in NMP (80.1g), 54mmol), B-4 (5.4g, 50mmol) with B-5 (8.2g, 22mmol), after 3 hours, A-2 (3.3g, 17mmol) and NMP (41.8g) is added in 40 DEG C of reactions, in 40 DEG C of reactions 3 hours, obtain polyamic acid solution.Add after NMP is diluted to 6 quality % in this polyamic acid solution (104.2g), add the acetic anhydride (12.5g) as imidization catalyst and pyridine (9.7g), in 80 DEG C of reactions 3 hours.This reaction solution is dropped in methyl alcohol (1300ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (A).The acid imide rate of this polyimide is 55%, and number-average molecular weight is 19100, and weight-average molecular weight is 54300.
(synthesis example 2)
Mixing A-4 (127.6g in NMP (1096g), 510mmol), B-13 (51.8g, 340mmol) with B-5 (129.4g, 340mmol), after 5 hours, A-2 (33.0g, 168mmol) and NMP (272g) is added in 80 DEG C of reactions, in 40 DEG C of reactions 3 hours, obtain polyamic acid solution.Add after NMP is diluted to 6 quality % in this polyamic acid solution (510.2g), add the acetic anhydride (54.3g) as imidization catalyst and pyridine (42.2g), in 80 DEG C of reactions 3 hours.This reaction solution is dropped in methyl alcohol (6500ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (B).The acid imide rate of this polyimide is 57%, and number-average molecular weight is 22800, and weight-average molecular weight is 79200.
(synthesis example 3)
Mixing A-4 (127.6g in NMP (1096g), 510mmol), B-13 (51.8g, 340mmol) with B-5 (129.4g, 340mmol), after 5 hours, A-2 (33.0g, 168mmol) and NMP (272g) is added in 80 DEG C of reactions, in 40 DEG C of reactions 3 hours, obtain polyamic acid solution.Add after NMP is diluted to 6 quality % in this polyamic acid solution (101.2g), add the acetic anhydride (21.4g) as imidization catalyst and pyridine (16.0g), in 90 DEG C of reactions 3 hours.This reaction solution is dropped in methyl alcohol (650ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (C).The acid imide rate of this polyimide is 81%, and number-average molecular weight is 21400, and weight-average molecular weight is 65400.
(synthesis example 4)
Mixing A-4 (37.3g in NMP (203.5g), 148.8mmol), B-13 (21.1g, 138.9mmol) with B-16 (25.9g, 59.5mmol), after 5 hours, A-2 (9.5g, 48.3mmol) and NMP (171.4g) is added in 80 DEG C of reactions, in 40 DEG C of reactions 6 hours, obtain polyamic acid solution.Add after NMP is diluted to 6 quality % in this polyamic acid solution (125.6g), add the acetic anhydride (27.0g) as imidization catalyst and pyridine (20.9g), in 90 DEG C of reactions 3.5 hours.This reaction solution is dropped in methyl alcohol (1600ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (D).The acid imide rate of this polyimide is 80%, and number-average molecular weight is 21200, and weight-average molecular weight is 64500.
(synthesis example 5)
Mixing A-1 (30.3g, 100.0mmol), B-4 (9.7g, 90.0mmol) and B-2 (3.8g, 10.0mmol) in NMP (246.7g), in 50 DEG C of reactions 24 hours, obtain polyamic acid solution.Add after NMP is diluted to 6 quality % in this polyamic acid solution (120.8g), add the acetic anhydride (35.0g) as imidization catalyst and pyridine (16.2g), in 35 DEG C of reactions 3 hours.This reaction solution is dropped in methyl alcohol (1420ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (E).The acid imide rate of this polyimide is 83%, and number-average molecular weight is 12700, and weight-average molecular weight is 29200.
(synthesis example 6)
Mixing A-2 (11.8g in NMP (266.4g), 60.0mmol), A-3 (11.5g, 52.8mmol) and B-8 (23.8g, 120.0mmol), react 5 hours under room temperature, obtain polyamic acid solution (F).The number-average molecular weight of this polyamic acid is 11700, and weight-average molecular weight is 29400.
(synthesis example 7)
Mixing A-2 (39.2g, 200.0mmol) and B-4 (20.5g, 190.0mmol) in NMP (537.9g), react 5 hours, obtain polyamic acid solution (G) under room temperature.The number-average molecular weight of this polyamic acid is 13600, and weight-average molecular weight is 38400.
(synthesis example 8)
Mixing A-5 (22.2g, 99.0mmol) and B-8 (19.8g, 100.0mmol) in NMP (168.1g), in 40 DEG C of reactions 15 hours, obtain polyamic acid solution (H).The number-average molecular weight of this polyamic acid is 25500, and weight-average molecular weight is 92100.
(synthesis example 9)
Mixing A-5 (22.2g, 99.0mmol), B-8 (19.8g, 100.0mmol) in NMP (168.1g), in 40 DEG C of reactions 15 hours, obtain polyamic acid solution.Add after NMP is diluted to 4.5 quality % in this polyamic acid solution (50.0g), add acetic anhydride (6.0g), the pyridine (4.7g) as imidization catalyst, in 100 DEG C of reactions 3 hours.This reaction solution is dropped in methyl alcohol (620ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (I).The acid imide rate of this polyimide is 64%, and number-average molecular weight is 21200, and weight-average molecular weight is 75900.
(synthesis example 10)
Mixing A-5 (3.3g, 15mmol), B-4 (1.3g, 12mmol), B-12 (1.5g, 3mmol) in NMP (24.5g), in 40 DEG C of reactions 8 hours, obtain polyamic acid solution.Add after NMP is diluted to 6 quality % in this polyamic acid solution (20.0g), add acetic anhydride (2.5g), the pyridine (1.9g) as imidization catalyst, in 90 DEG C of reactions 3 hours.This reaction solution is dropped in methyl alcohol (330ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (J).The acid imide rate of this polyimide is 50%, and number-average molecular weight is 18100, and weight-average molecular weight is 52300.
(synthesis example 11)
Mixing A-5 (4.5g, 20mmol), B-14 (1.5g, 14mmol), B-5 (2.3g, 6mmol) in NMP (33.0g), in 40 DEG C of reactions 8 hours, obtain polyamic acid solution.Add after NMP is diluted to 6 quality % in this polyamic acid solution (30.0g), add acetic anhydride (3.7g), the pyridine (2.9g) as imidization catalyst, in 90 DEG C of reactions 3 hours.This reaction solution is dropped in methyl alcohol (370ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (K).The acid imide rate of this polyimide is 51%, and number-average molecular weight is 18600, and weight-average molecular weight is 72600.
(synthesis example 12)
Mixing A-4 (85.1g in NMP (556.3g), 340mmol), B-13 (39.6g, 260mmol), B-16 (60.9g, 140mmol), after 5 hours, A-2 (11.5g, 58mmol) and NMP (231.4g) is added in 80 DEG C of reactions, in 40 DEG C of reactions 3 hours, obtain polyamic acid solution.Add after NMP is diluted to 6 quality % in this polyamic acid solution (200.0g), add acetic anhydride (26.4g), the pyridine (13.7g) as imidization catalyst, in 100 DEG C of reactions 2.5 hours.This reaction solution is dropped in methyl alcohol (2500ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (L).The acid imide rate of this polyimide is 71%, and number-average molecular weight is 21300, and weight-average molecular weight is 54700.
(synthesis example 13)
Mixing A-4 (112.6g in NMP (793.5g), 450mmol), B-4 (19.5g, 180mmol), B-13 (18.3g, 120mmol), B-5 (114.2g, 300mmol), in 80 DEG C reaction 5 hours after, add A-2 (28.6g, 145mmol) with NMP (378.5g), in 40 DEG C of reactions 3 hours, obtain polyamic acid solution.Add after NMP is diluted to 6 quality % in this polyamic acid solution (300.0g), add acetic anhydride (31.3g), the pyridine (24.2g) as imidization catalyst, in 80 DEG C of reactions 4 hours.This reaction solution is dropped in methyl alcohol (3700ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (M).The acid imide rate of this polyimide is 52%, and number-average molecular weight is 19800, and weight-average molecular weight is 53800.
(synthesis example 14)
Mixing A-4 (138.2g in NMP (819g), 552mmol), B-13 (39.6g, 260mmol), B-5 (74.2g, 195mmol), after 5 hours, A-2 (18.1g, 92mmol) and NMP (346g) is added in 80 DEG C of reactions, in 40 DEG C of reactions 3 hours, obtain polyamic acid solution.Add after NMP is diluted to 6 quality % in this polyamic acid solution (500.0g), add acetic anhydride (68.1g), the pyridine (35.2g) as imidization catalyst, in 100 DEG C of reactions 2.5 hours.This reaction solution is dropped in methyl alcohol (6200ml), the sediment of isolated by filtration gained.This sediment methanol cleaning, in 100 DEG C of drying under reduced pressure, obtains polyimide powder (N).The acid imide rate of this polyimide is 68%, and number-average molecular weight is 22100, and weight-average molecular weight is 77200.
Prepare aligning agent for liquid crystal (1) ~ (27) as described below, evaluate the rub resistance of each aligning agent for liquid crystal.Its result gathers and is shown in table 1.
[evaluation of rub resistance]
The aligning agent for liquid crystal of the present invention of above-mentioned gained is spun on the glass substrate with transparency electrode, on the heating plate of 80 DEG C after dry 5 minutes, heats kiln roasting 30 minutes at the heated air circulation types of 220 DEG C, form the film of thickness 100nm.Under the condition of roller revolution 1000rpm, roller gait of march 50mm/ second, intrusion 0.4mm, use rayon cloth to rub this coated surface with the rubbing device of roller footpath 120mm, obtain the substrate being with liquid crystal orientation film.
Be set in 5 places on the liquid crystal orientation film surface of the immediate vicinity of the laser microscope random observation aforesaid substrate of 100 times by multiplying power, evaluate rub resistance according at the mean value of the amount as the scratch confirmed in the square scope of about 6.5mm of field of view and abrasive dust (attachment).The results are shown in aftermentioned table 1.And metewand is determined as following.
Metewand
A: scratch and abrasive dust are below 20
B: scratch and abrasive dust are 20 ~ 40
C: scratch and abrasive dust are 40 ~ 60
D: scratch and abrasive dust are more than 60
Embodiment 1
In polyimide powder (A) (5.2g) that synthesis example 1 obtains, add NMP (29.5g), stir in 80 DEG C and within 30 hours, make it to dissolve.10.0 quality %NMP solution (5.2g) (P15 is 0.52g), the NMP (3.4g) and BCS (43.3g) of P15 is added in this solution, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (1) thus.
Embodiment 2
In polyimide powder (B) (5.6g) that synthesis example 2 obtains, add NMP (27.3g), stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add 5.0 quality %NMP solution (5.6g) (C-1 is 0.28g), the NMP (8.1g) and BCS (46.6g) of C-1, stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (5.6g) (P15 is 0.56g) of P15, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (2) thus.
Embodiment 3
In polyimide powder (B) (5.6g) that synthesis example 2 obtains, add NMP (27.3g), stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add 5.0 quality %NMP solution (5.6g) (C-1 is 0.28g), the NMP (8.1g) and BCS (46.6g) of C-1, stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (3.9g) (P15 is 0.39g) of P15, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (3) thus.
Embodiment 4
In polyimide powder (B) (5.6g) that synthesis example 2 obtains, add NMP (27.3g), stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add 5.0 quality %NMP solution (5.6g) (C-1 is 0.28g), the NMP (8.1g) and BCS (46.6g) of C-1, stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (2.8g) (P15 is 0.28g) of P15, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (4) thus.
Embodiment 5
In polyimide powder (B) (5.6g) that synthesis example 2 obtains, add NMP (27.3g), stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add 5.0 quality %NMP solution (5.6g) (C-1 is 0.28g), the NMP (8.1g) and BCS (46.6g) of C-1, stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (1.7g) (P15 is 0.17g) of P15, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (5) thus.
Embodiment 6
In polyimide powder (C) (7.2g) that synthesis example 3 obtains, add NMP (35.2g), stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add 5.0 quality %NMP solution (7.2g) (C-1 is 0.36g), the NMP (10.4g) and BCS (60.0g) of C-1, stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (7.2g) (P15 is 0.72g) of P15, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (6) thus.
Embodiment 7
In polyimide powder (D) (5.2g) that synthesis example 4 obtains, add NMP (25.4g), stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add 5.0 quality %NMP solution (5.2g) (C-1 is 0.26g), the NMP (7.5g) and BCS (43.4g) of C-1, stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (5.2g) (P15 is 0.52g) of P15, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (7) thus.
Embodiment 8
Except being changed to except P31 by P15, and embodiment 7 is prepared in the same manner, obtains aligning agent for liquid crystal (8).
Embodiment 9
NMP (5.0g) and BCS (5.0g) is added, in stirred at ambient temperature 2 hours in polyamic acid (G) (15.0g) that obtain in synthesis example 7.In this solution, add the 10.0 quality %NMP solution (1.5g) (P15 is 0.15g) of P15, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (9) thus.
Embodiment 10
Except being changed to except P17 by P15, and embodiment 9 is prepared in the same manner, obtains aligning agent for liquid crystal (10).
Embodiment 11
Except being changed to except P29 by P15, and embodiment 9 is prepared in the same manner, obtains aligning agent for liquid crystal (11).
Embodiment 12
Except being changed to except P41 by P15, and embodiment 9 is prepared in the same manner, obtains aligning agent for liquid crystal (12).
Embodiment 13
Add GBL (45.0g) in polyimide powder (E) (5.0g) that obtain in synthesis example 5, stir in 50 DEG C and within 20 hours, make it to dissolve.In this solution, add GBL (33.3g), in stirred at ambient temperature 2 hours, obtain polyimide solution.Then, GBL (112.5g) and BCS (37.5g) is added in polyamic acid solution (F) (100.0g) that obtain in synthesis example (6), in stirred at ambient temperature 2 hours, obtain polyamic acid solution thus.Mix above-mentioned polyimide solution (20.0g) and polyamic acid solution (80.0g) again, in stirred at ambient temperature 20 hours, thus obtain the mixed solution of polyimide and polyamic acid.Finally, in this mixed solution, add the 10.0 quality %GBL solution (6.0g) (P15 is 0.6g) of P15, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (13) thus.
Embodiment 14
NMP (8.5g), the 10.0 quality %NMP solution (1.5g) (P17 is 0.15g) of P17, BCS (20.0g) is added in polyamic acid (H) (20.0g) that obtain in synthesis example 8, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (14) thus.
Embodiment 15
Add NMP (28.3g) in polyimide powder (I) (5.0g) that obtain in synthesis example 9, stir in 70 DEG C and within 30 hours, make it to dissolve.The 10.0 quality %NMP solution (2.5g) (P17 is 0.25g) of P17, NMP (11.7g), BCS (33.3g) is added in this solution, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (15) thus.
Embodiment 16
Add NMP (28.3g) in polyimide powder (J) (5.0g) that obtain in synthesis example 10, stir in 70 DEG C and within 30 hours, make it to dissolve.The 10.0 quality %NMP solution (2.5g) (P17 is 0.25g) of P17, NMP (11.7g), BCS (33.3g) is added in this solution, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (16) thus.
Embodiment 17
Add NMP (28.3g) in polyimide powder (K) (5.0g) that obtain in synthesis example 11, stir in 70 DEG C and within 30 hours, make it to dissolve.The 10.0 quality %NMP solution (2.5g) (P17 is 0.25g) of P17, NMP (11.7g), BCS (33.3g) is added in this solution, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (17) thus.
Embodiment 18
Add NMP (48.8g) in polyimide powder (L) (10.0g) that obtain in synthesis example 12, stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add the 5.0 quality %NMP solution (10.0g) (C-1 is 0.5g) of C-1, NMP (22.8g), BCS (75.0g), stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (5.0g) (P17 is 0.5g) of P17, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (18) thus.
Embodiment 19
Add NMP (48.8g) in polyimide powder (M) (10.0g) that obtain in synthesis example 13, stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add the 5.0 quality %NMP solution (10.0g) (C-2 is 0.5g) of C-2, NMP (22.8g), BCS (75.0g), stir 20 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (5.0g) (P17 is 0.5g) of P17, in stirred at ambient temperature 2 hours, obtain polyimide solution (0) thus.Then, add NMP (48.8g) in polyimide powder (N) (10.0g) that obtain in synthesis example 14, stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add the 5.0 quality %NMP solution (5.9g) (C-2 is 0.6g) of C-2, NMP (26.9g), BCS (75.0g), stir 20 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (5.0g) (P17 is 0.5g) of P17, in stirred at ambient temperature 2 hours, obtain polyimide solution (P) thus.Again above-mentioned polyimide solution (0) (30.0g) and polyimide solution (P) (30.0g) is mixed, stir 20 hours, obtain aligning agent for liquid crystal (19) thus.
Embodiment 20
Add NMP (9.8g) in polyimide powder (A) (2.0g) that obtain in synthesis example 1, stir in 80 DEG C and within 30 hours, make it to dissolve.The 10.0 quality %NMP solution (1.0g) (P17 is 0.1g) of P17, NMP (3.9g), BCS (16.7g) is added in this solution, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (20) thus.
Embodiment 21
Add NMP (9.8g) in polyimide powder (B) (2.0g) that obtain in synthesis example 2, stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add NMP (2.9g), BCS (16.7g), stir 2 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (2.0g) (P17 is 0.2g) of P17, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (21) thus.
Embodiment 22
Add NMP (9.8g) in polyimide powder (B) (2.0g) that obtain in synthesis example 2, stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add the 5.0 quality %NMP solution (2.0g) (C-1 is 0.1g) of C-1, NMP (1.5g), BCS (16.7g), stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (1.4g) (P17 is 0.14g) of P17, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (22) thus.
Embodiment 23
Add NMP (9.8g) in polyimide powder (B) (2.0g) that obtain in synthesis example 2, stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add NMP (2.9g), BCS (16.7g), stir 2 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (1.0g) (P17 is 0.1g) of P17, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (23) thus.
Embodiment 24
Add NMP (9.8g) in polyimide powder (B) (2.0g) that obtain in synthesis example 2, stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add the 5.0 quality %NMP solution (2.0g) (C-1 is 0.1g) of C-1, NMP (2.3g), BCS (16.7g), stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (0.6g) (P17 is 0.06g) of P17, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (24) thus.
Embodiment 25
Add NMP (9.8g) in polyimide powder (C) (2.0g) that obtain in synthesis example 3, stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add the 5.0 quality %NMP solution (2.0g) (C-1 is 0.1g) of C-1, NMP (1.9g), BCS (16.7g), stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (1.0g) (P17 is 0.1g) of P17, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (25) thus.
Embodiment 26
Add NMP (9.8g) in polyimide powder (D) (2.0g) that obtain in synthesis example 4, stir in 70 DEG C and within 30 hours, make it to dissolve.In this solution, add the 5.0 quality %NMP solution (2.0g) (C-1 is 0.1g) of C-1, NMP (1.9g), BCS (16.7g), stir 15 hours in 50 DEG C.In this solution, add the 10.0 quality %NMP solution (1.0g) (P17 is 0.1g) of P17, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (26) thus.
Embodiment 27
Add GBL (18.0g) in polyimide powder (E) (5.0g) that obtain in synthesis example 5, stir in 50 DEG C and within 20 hours, make it to dissolve.In this solution, add GBL (13.3g), in stirred at ambient temperature 2 hours, obtain polyimide solution.Then, GBL (112.5g) and BCS (37.5g) is added in polyamic acid solution (F) (100.0g) that obtain in synthesis example (6), in stirred at ambient temperature 2 hours, obtain polyamic acid solution thus.Mix above-mentioned polyimide solution (20.0g) and polyamic acid solution (80.0g) again, in stirred at ambient temperature 20 hours, thus obtain the mixed solution of polyimide, polyamic acid.Finally, in this mixed solution, add the 10.0 quality %GBL solution (6.0g) (P17 is 0.6g) of P17, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (27) thus.
Comparative example 1
Add NMP (32.2g) in polyimide powder (A) (6.6g) that obtain in synthesis example 1, stir in 80 DEG C and within 30 hours, make it to dissolve.In this solution, add NMP (16.1g) and BCS (55.0g), in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (28) thus.
Comparative example 2
Add NMP (22.5g) in polyimide powder (B) (4.6g) that obtain in synthesis example 2, stir in 70 DEG C and within 30 hours, make it to dissolve.5.0 quality %NMP solution (4.6g) (C-1 is 0.23g), the NMP (6.7g) and BCS (38.4g) of C-1 is added in this solution, stir 15 hours in 50 DEG C, obtain aligning agent for liquid crystal (29) thus.
Comparative example 3
Except the polyimide powder (C) obtained in use synthesis example 3, and comparative example 2 is prepared in the same manner, obtains aligning agent for liquid crystal (30).
Comparative example 4
Except the polyimide powder (D) obtained in use synthesis example 4, and comparative example 2 is prepared in the same manner, obtains aligning agent for liquid crystal (31).
Comparative example 5
Add γ-BL (18.0g) in polyimide powder (E) (2.0g) that obtain in synthesis example 5, stir in 50 DEG C and within 20 hours, make it to dissolve.In this solution, add GBL (8.3g) and BCS (5.0g), in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (32) thus.
Comparative example 6
Add NMP (5.0g) and BCS (5.0g) in polyimide powder (G) (15.0g) that obtain in synthesis example 7, in stirred at ambient temperature 2 hours, obtain aligning agent for liquid crystal (33) thus.
Table 1
Polyimide Polyamic acid Amines Specific compound Rub resistance
Embodiment 1 A P15 A
Embodiment 2 B C-1 P15 A
Embodiment 3 B C-1 P15 A
Embodiment 4 B C-1 P15 A
Embodiment 5 B C-1 P15 B
Embodiment 6 C C-1 P15 A
Embodiment 7 D C-1 P15 A
Embodiment 8 D C-1 P31 B
Embodiment 9 G P15 A
Embodiment 10 G P17 A
Embodiment 11 G P29 A
Embodiment 12 G P41 B
Embodiment 13 E F P15 A
Embodiment 14 H P17 A
Embodiment 15 I P17 A
Embodiment 16 J P17 A
Embodiment 17 K P17 A
Embodiment 18 L C-1 P17 A
Embodiment 19 M，N C-2 P17 A
Embodiment 20 A P17 A
Embodiment 21 B P17 A
Embodiment 22 B C-1 P17 A
Embodiment 23 B P17 A
Embodiment 24 B C-1 P17 B
Embodiment 25 C C-1 P17 A
Embodiment 26 D C-1 P17 A
Embodiment 27 E F P17 A
Comparative example 1 A D
Comparative example 2 B C-1 D
Comparative example 3 C C-1 D
Comparative example 4 D C-1 D
Comparative example 5 E D
Comparative example 6 G D
< embodiment 28 ~ 38 and comparative example 7,8>
The each liquid crystal treating agent alignment agent obtained in above-described embodiment and comparative example is spun on the glass substrate with ITO electrode, on the heating plate of 80 DEG C after dry 5 minutes, heat kiln roasting 1 hour at the heated air circulation types of 210 DEG C, form the liquid crystal orientation film of thickness 100nm.Prepare 2 pieces of substrates with this liquid crystal orientation film, printing and sealing agent from it after the sept of distribution 6 μm on 1 piece of liquid crystal aligning face wherein, makes sealant cures after laminating, makes negative crystal born of the same parents.By decompression injection method, in this negative crystal born of the same parents, inject liquid crystal MLC-6608 (Merck Japanese firm (メ Le Network ジ ヤ パ Application society) system), seal inlet, obtain nematic crystal structure cell.
With each liquid crystal cell of polarized light microscope observing, liquid crystal is vertical orientated equably, does not observe orientation defect.The voltage retention of (photostability) after voltage retention when the liquid crystal cell evaluating each liquid crystal cell makes and UV-vis irradiate, its result gathers and is shown in table 2.
Voltage retention > when < liquid crystal cell makes
The liquid crystal cell of above-mentioned making is applied to voltage 60 microsecond of 1V at the temperature of 80 DEG C, the voltage after measuring 16.67 milliseconds and after 50 milliseconds, calculating voltage can keep how many as voltage retention.Consequently 16.67 milliseconds time the voltage retention of voltage retention when being 97.0%, 50 milliseconds be 94.2%.
In addition, measure and use Dongyang technology Co., Ltd. (East Yang テ Network ニ カ society) the VHR-1 voltage retention determinator made, voltage: ± 1V, pulsewidth: 60 microseconds, between period of flaming (flame period): be set as 16.67 milliseconds or 50 milliseconds.
The postradiation voltage retention > of <UV-vis
Each liquid crystal cell after terminating is measured to above-mentioned voltage retention and is scaled 50J/cm in order to 365nm 2illumination penetrate after, carry out same mensuration.In addition, the desk-top UV solidification equipment (HCT3B28HEX-1) that UV-vis (high-pressure sodium lamp) irradiation Xian Laite company (セ Application ラ イ ト society) makes is carried out.Consequently, voltage retention when voltage retention when 16.67 milliseconds is 92.3%, 50 milliseconds is 88.9%.
Table 2
< embodiment 39 ~ 54 and comparative example 9 ~ 20>
Prepare each aligning agent for liquid crystal as described below.The composition of each aligning agent for liquid crystal of gained gathers and is shown in table 3.In addition, use each aligning agent for liquid crystal to make liquid crystal cell, evaluate respective tilt angle, rub resistance and RDC as described below.Result gathers and is shown in table 4.
In addition, the abbreviation used in these embodiments and comparative example is as described below.Its implication of the abbreviation be not particularly illustrated is identical with aforementioned.
(specific compound)
P13, P17, P46, P47, P31 are identical with aforementioned with the implication of P49.
(diamines)
B-1:2,4-diamino-N, N-diallyl aniline
B-3:4-(trans-4-pentylcyclohexyl) benzamido-2 ', 4 '-phenylenediamine
B-6:4-amino-benzylamine
B-7:3-amino-benzylamine
B-9:1,3-diamido-4-dodecyloxy benzene
B-10:1,3-diamido-4-tetradecyloxyaniline benzene
B-11:1,4-bis-(4-amino-benzene oxygen) pentane
B-12:4,4 '-diamino-diphenylamine
The making > of < liquid crystal cell
Liquid crystal treating agent alignment agent is spun on the glass substrate with transparency electrode, on the heating plate of 80 DEG C after dry 5 minutes, heats kiln roasting 10 minutes at the heated air circulation types of 210 DEG C, form the liquid crystal orientation film of thickness 70nm.Under the condition of roller revolution 1000rpm, roller gait of march 50mm/ second, intrusion 0.3mm, use rayon cloth to rub this coated surface with the rubbing device of roller footpath 120mm, obtain the substrate being with liquid crystal orientation film.Prepare the substrate of 2 pieces of band liquid crystal orientation films, printing and sealing agent from it after the sept of distribution 6 μm on 1 piece of liquid crystal aligning face wherein, relatively make sealant cures and the orthogonal mode of frictional direction is fitted after another block substrate with liquid crystal aligning face, make negative crystal born of the same parents.By decompression injection method, in this negative crystal born of the same parents, inject liquid crystal MLC-2003 (Merck Japanese firm (メ Le Network ジ ヤ パ Application society) system), seal inlet, obtain Twisted Nematic liquid crystal structure cell.
The mensuration > of < tilt angle
Obtained Twisted Nematic liquid crystal structure cell after 5 minutes, is carried out the mensuration of tilt angle in 105 DEG C of heating.Tilt angle crystal rotation method measures.
< puts aside the mensuration > of electric charge (RDC)
From 0V to 1.0V, DC voltage is applied with the interval of 0.1V to the Twisted Nematic liquid crystal structure cell that the method recorded in the making > with above-mentioned < liquid crystal cell makes at the temperature of 23 DEG C, measure the flicker amplitude level under each voltage, make calibration curve.After 5 minutes ground connection, apply 3.0V alternating voltage, 5.0V DC voltage 1 hour, then after only DC voltage has been just 0V, flicker amplitude level is measured immediately, by estimating RDC (evaluation method of this RDC is called flicker reference entry) according to the calibration curve made in advance.
Herein, RDC (before disconnection) has just applied 3.0V alternating voltage, the value of 5.0V DC voltage after 1 hour, and RDC (after 10 minutes) is the value that alternating voltage disconnects the savings electric charge after 10 minutes.
The evaluation > of < rub resistance
Aligning agent for liquid crystal of the present invention obtained above is spun on the glass substrate with transparency electrode, on the heating plate of 80 DEG C after dry 5 minutes, heats kiln roasting 10 minutes at the heated air circulation types of 210 DEG C, form the film of thickness 100nm.Under the condition of roller revolution 1000rpm, roller gait of march 50mm/ second, intrusion 0.5mm, use rayon cloth to rub this coated surface with the rubbing device of roller footpath 120mm, obtain the substrate being with liquid crystal orientation film.
Be set in 5 places on the liquid crystal orientation film surface of the immediate vicinity of the laser microscope random observation aforesaid substrate of 100 times by multiplying power, evaluate rub resistance according at the mean value of the amount as the scratch confirmed in the square scope of about 6.5mm of field of view and abrasive dust (attachment).And metewand is determined as following.
Metewand
Zero: scratch and abrasive dust are below 20
△: scratch and abrasive dust are 20 ~ 60
×: scratch and abrasive dust are more than 60
Embodiment 39
Be used as the A-1 of the 30.03g (100mmol) of tetracarboxylic dianhydride's composition, B-2 as B-4,3.77g (10mol) of the 9.73g (90mmol) of diamine component, in 40 DEG C of reactions 30 hours in the NMP of 247g, obtain polyamic acid solution.
This polyamic acid solution NMP of 50g is diluted to 5 % by weight, adds the acetic anhydride of the 17.6g as imidization catalyst, the pyridine of 8.2g, in 40 DEG C of reactions 3 hours, preparation soluble polyimide resin solution.This solution is dropped in the methyl alcohol of 0.6L, the sediment of isolated by filtration gained, drying, obtain the soluble polyimide (SPI-1) of white.Measure the molecular weight of this soluble polyimide, consequently number-average molecular weight is 13430, and weight-average molecular weight is 26952, and acid imide rate is 85%.
Make this polyimide powder of 1g be dissolved in the BCS of GBL, 4.8g of 11.8g, obtain homogeneous polyimide solution.In this solution of 10g, add the P17 of 0.03g, at room temperature stir 5 hours, make aligning agent for liquid crystal.
Embodiment 40
Be used as the A-3 of A-2,9.60g (44mmol) of the 9.80g (50mmol) of tetracarboxylic dianhydride's composition, B-8 as the 19.8g (100mmol) of diamine component, react 5 hours under room temperature in the NMP of 222g, obtain polyamic acid solution (PAA-1).The number-average molecular weight of this polyamic acid solution is 11153, and weight-average molecular weight is 29487.
In this polyamic acid solution of 8g, add the BCS of NMP, 7.5g of 10.5g, at room temperature stir 20 hours, obtain homogeneous aligning agent for liquid crystal.
By SPI-1 and PAA-1 mixing to make its mass ratio for 2: 8, in this solution of 10g, add the P17 of 0.03g, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Embodiment 41
By SPI-1 and PAA-1 mixing to make its mass ratio for 2: 8, in this solution of 10g, add the P19 of 0.03g, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Embodiment 42
By SPI-1 and PAA-1 mixing to make its mass ratio for 2: 8, in this solution of 10g, add the P13 of 0.03g, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Embodiment 43
By SPI-1 and PAA-1 mixing to make its mass ratio for 2: 8, in this solution of 10g, add the P49 of 0.03g, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Embodiment 44
By SPI-1 and PAA-1 mixing to make its mass ratio for 2: 8, in this solution of 10g, add the P48 of 0.03g, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Embodiment 45
By SPI-1 and PAA-1 mixing to make its mass ratio for 2: 8, in this solution of 10g, add the P46 of 0.03g, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Embodiment 46
By SPI-1 and PAA-1 mixing to make its mass ratio for 2: 8, in this solution of 10g, add the P47 of 0.03g, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Embodiment 47
Make the B-9 of B-4,5.85g (20mol) of A-1,8.56g (80mmol) of 30.03g (100mmol) in 50 DEG C of reactions 24 hours in the NMP of 252g, preparation polyamic acid solution.
This polyamic acid solution NMP of 50g is diluted to 5 quality %, then adds the pyridine of the 8.0g as imidization catalyst, the acetic anhydride of 17.2g, in 40 DEG C of reactions 3 hours.This solution is dropped in the methyl alcohol of 0.6L, the sediment of isolated by filtration gained, drying, obtain the polyimide powder (SPI-2) of white.The number-average molecular weight of the solvent-soluble polyimide of gained is 9111, and weight-average molecular weight is 18045, and acid imide rate is 83%.
By SPI-2 and PAA-1 mixing to make its mass ratio for 2: 8, in this solution of 10g, add the P17 of 0.03g, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Embodiment 48
Be used as the A-3 of A-2,1.63g (7.5mmol) of the 8.18g (42mmol) of tetracarboxylic dianhydride's composition, B-3 as B-1,6.11g (15mmol) of B-7,5.08g (25mmol) of the 1.22g (10mmol) of diamine component, react 24 hours under room temperature in the NMP of 88.96g, obtain polyamic acid solution.
The NMP adding 228.5g in this polyamic acid solution of 95.8g dilutes, and adds the acetic anhydride of 15.1g and the pyridine of 6.4g, within 3 hours, carries out imidizate in 50 DEG C of reactions.Drop in the methyl alcohol of 1259.1ml after about this reaction solution cool to room temperature, reclaim the solid of precipitation.Again with after this solid several of methanol wash, drying under reduced pressure at 100 DEG C of temperature, obtains the white powder of soluble polyimide (SPI-3).The number-average molecular weight of this polyimide is 18195, and weight-average molecular weight is 57063, and acid imide rate is 93%.In this polyimide powder of 1.2g, add the GBL of 10.8g, stir 24 hours at 50 DEG C of temperature.At the end of stirring, polyimide dissolves completely.After this solution of 12g is cooled to 23 DEG C, add the BCS of GBL, 6g of 2g, stir 20 hours at 50 DEG C of temperature.After stirring terminates, be cooled to 23 DEG C, obtain homogeneous aligning agent for liquid crystal.
In this solution of 10g, add the P17 of 0.03g, in stirred at ambient temperature 5 hours, obtain aligning agent for liquid crystal.
Embodiment 49
Be used as the A-3 of A-2,6.54g (30mmol) of the 13.53g (69mmol) of tetracarboxylic dianhydride's composition, B-9 as B-6,8.77g (30mmol) of B-1,3.67g (30mmol) of the 8.13g (40mmol) of diamine component, react 24 hours under room temperature in the NMP of 161.8g, obtain polyamic acid solution.
The NMP adding 62.65g in this polyamic acid solution of 34.81g dilutes, and adds the acetic anhydride of 5.15g and the pyridine of 2.19g, within 3 hours, carries out imidizate in 50 DEG C of reactions.
Drop in the methyl alcohol of 366.8ml after about this reaction solution cool to room temperature, reclaim the solid of precipitation.Again with after this solid several of methanol wash, drying under reduced pressure at 100 DEG C of temperature, obtains the white powder of polyimide (SPI-4).The number-average molecular weight of this polyimide is 12016, and weight-average molecular weight is 35126, and acid imide rate is 90%.
In this polyimide powder of 1.2g, add the GBL of 10.8g, stir 24 hours at 50 DEG C of temperature.At the end of stirring, polyimide dissolves completely.After this solution of 12g is cooled to 23 DEG C, add the BCS of GBL, 6g of 2g, stir 20 hours at 50 DEG C of temperature.After stirring terminates, be cooled to 23 DEG C, obtain homogeneous aligning agent for liquid crystal.
In this solution of 10g, add the P17 of 0.03g, in stirred at ambient temperature 5 hours, obtain aligning agent for liquid crystal.
Embodiment 50
Be used as the A-3 of A-2,6.54g (30mmol) of the 13.33g (68mmol) of tetracarboxylic dianhydride's composition, B-6 as B-1,7.64g (50mmol) of B-5,8.13g (40mmol) of the 3.81g (10mmol) of diamine component, react 24 hours under room temperature in the NMP of 151.7g, obtain polyamic acid solution.
The NMP adding 59.61g in this polyamic acid solution of 33.38g dilutes, then adds the acetic anhydride of 5.26g and the pyridine of 2.24g, within 3 hours, carries out imidizate in 50 DEG C of reactions.
Drop in the methyl alcohol of 351.7ml after about this reaction solution cool to room temperature, reclaim the solid of precipitation.Again with after this solid several of methanol wash, drying under reduced pressure at 100 DEG C of temperature, obtains the white powder of polyimide (SPI-5).The number-average molecular weight of this polyimide is 10111, and weight-average molecular weight is 33653, and acid imide rate is 90%.
In this polyimide powder of 1.2g, add the GBL of 10.8g, stir 24 hours at 50 DEG C of temperature.At the end of stirring, polyimide dissolves completely.After this solution of 12g is cooled to 23 DEG C, add the BCS of GBL, 6g of 2g, stir 20 hours at 50 DEG C of temperature.After stirring terminates, be cooled to 23 DEG C, obtain homogeneous aligning agent for liquid crystal.
In this solution of 10g, add the P17 of 0.03g, in stirred at ambient temperature 5 hours, obtain aligning agent for liquid crystal.
Embodiment 51
Be used as the A-3 of A-2,3.27g (15mmol) of the 6.86g (35mmol) of tetracarboxylic dianhydride's composition, B-3 as B-1,6.11g (15mmol) of B-7,3.04g (15mmol) of the 2.44g (20mmol) of diamine component, react 24 hours under room temperature in the NMP of 87.0g, obtain polyamic acid solution (PAA-2).The number-average molecular weight of this polyamic acid is 15539, and weight-average molecular weight is 47210.In this solution of 8g, add the BCS of NMP, 7.5g of 10.5g, at room temperature stir 20 hours, obtain homogeneous aligning agent for liquid crystal.
In this solution of 10g, add the P17 of 0.03g, in stirred at ambient temperature 5 hours, obtain aligning agent for liquid crystal.
Embodiment 52
By SPI-3 and PAA-4 mixing to make its mass ratio for 3: 7, in this solution of 10g, add the P17 of 0.03g, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Embodiment 53
Be used as the A-3 of the 4.05g (18mmol) of tetracarboxylic dianhydride's composition, B-2 as B-11,0.75g (2mmol) of the 5.15g (18mmol) of diamine component, react 16 hours under room temperature in the NMP of 73.07g, obtain the polyamic acid solution of 12 quality %.The number-average molecular weight of this polyamic acid is 12180, and weight-average molecular weight is 25160.The BCS of NMP, 50g of this polyamic acid solution 115g of 50g is diluted, obtains polyamic acid solution (PAA-3).
In this solution of 10g, add the P17 of 0.03g, in stirred at ambient temperature 5 hours, obtain aligning agent for liquid crystal.
Embodiment 54
Be used as the A-1 of A-2,3.00g (10mmol) of the 7.15g (37mmol) of tetracarboxylic dianhydride's composition, B-8 as B-12,1.98g (10mmol) of the 7.97g (40mmol) of diamine component, react 16 hours under room temperature in the NMP of 181g, obtain the polyamic acid solution of 10 quality %.The number-average molecular weight of this polyamic acid is 12180, and weight-average molecular weight is 30160.The BCS of NMP, 100g of this polyamic acid solution 230g of 100.0g is diluted, obtains polyamic acid solution (PAA-4).
By PAA-3 and PAA-4 mixing to make its mass ratio for 2: 8, in this solution of 10g, add the P17 of 0.03g, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Comparative example 9
Be used as the A-1 of the 30.03g (100mmol) of tetracarboxylic dianhydride's composition, B-2 as B-4,3.77g (10mol) of the 9.73g (90mmol) of diamine component, in 40 DEG C of reactions 3 hours in the NMP of 247g, preparation polyamic acid solution.
This polyamic acid solution NMP of 50g is diluted to 5 % by weight, then adds the acetic anhydride of the 17.6g as imidization catalyst, the pyridine of 8.2g, in 40 DEG C of reactions 3 hours, preparation soluble polyimide resin solution.This solution is dropped in the methyl alcohol of 0.6L, the sediment of isolated by filtration gained, drying, obtain the soluble polyimide (SPI-1) of white.Measure the molecular weight of this soluble polyimide, result is number-average molecular weight is 13430, and weight-average molecular weight is 26952, and acid imide rate is 85%.Make this polyimide powder of 1g be dissolved in the BCS of GBL, 4.8g of 11.8g, obtain homogeneous polyimide solution.
Comparative example 10
By SPI-1 and PAA-1 mixing to make its mass ratio for 2: 8, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Comparative example 11
By SPI-2 and PAA-1 mixing to make its mass ratio for 2: 8, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Comparative example 12
Be used as the A-3 of A-2,1.63g (7.5mmol) of the 8.18g (42mmol) of tetracarboxylic dianhydride's composition, B-3 as B-1,6.11g (15mmol) of B-7,5.08g (25mol) of the 1.22g (10mmol) of diamine component, react 24 hours under room temperature in the NMP of 88.96g, obtain polyamic acid solution.The NMP adding 228.5g in this polyamic acid solution of 95.8g dilutes, then adds the acetic anhydride of 15.1g and the pyridine of 6.4g, within 3 hours, carries out imidizate in 50 DEG C of reactions.Drop in the methyl alcohol of 1259.1ml after about this reaction solution cool to room temperature, reclaim the solid of precipitation.Again with after this solid several of methanol wash, drying under reduced pressure at 100 DEG C of temperature, obtains the white powder of soluble polyimide (SPI-3).The number-average molecular weight of this polyimide is 18195, and weight-average molecular weight is 57063, and acid imide rate is 93%.In this polyimide powder of 1.2g, add the GBL of 10.8g, stir 24 hours at 50 DEG C of temperature.At the end of stirring, polyimide dissolves completely.After this solution of 12g is cooled to 23 DEG C, add the BCS of GBL, 6g of 2g, stir 20 hours at 50 DEG C of temperature.After stirring terminates, be cooled to 23 DEG C, obtain homogeneous aligning agent for liquid crystal.
Comparative example 13
Be used as the A-3 of A-2,6.54g (30mmol) of the 13.53g (69mmol) of tetracarboxylic dianhydride's composition, B-9 as B-6,8.77g (30mmol) of B-1,3.67g (30mmol) of the 8.13g (40mmol) of diamine component, react 24 hours under room temperature in the NMP of 161.8g, obtain polyamic acid solution.
The NMP adding 62.65g in this polyamic acid solution of 34.81g dilutes, and adds the acetic anhydride of 5.15g and the pyridine of 2.19g, within 3 hours, carries out imidizate in 50 DEG C of reactions.
Drop in the methyl alcohol of 366.8ml after about this reaction solution cool to room temperature, reclaim the solid of precipitation.Again with after this solid several of methanol wash, drying under reduced pressure at 100 DEG C of temperature, obtains the white powder of polyimide (SPI-4).The number-average molecular weight of this polyimide is 12016, and weight-average molecular weight is 35126, and acid imide rate is 90%.
In this polyimide powder of 1.2g, add the GBL of 10.8g, stir 24 hours at 50 DEG C of temperature.At the end of stirring, polyimide dissolves completely.After this solution of 12g is cooled to 23 DEG C, add the BCS of GBL, 6g of 2g, stir 20 hours at 50 DEG C of temperature.After stirring terminates, be cooled to 23 DEG C, obtain homogeneous aligning agent for liquid crystal.
Comparative example 14
Be used as the A-3 of A-2,6.54g (30mmol) of the 13.33g (68mmol) of tetracarboxylic dianhydride's composition, B-6 as B-1,7.64g (50mmol) of B-5,8.13g (40mmol) of the 3.81g (10mmol) of diamine component, react 24 hours under room temperature in the NMP of 151.7g, obtain polyamic acid solution.The NMP adding 59.61g in this polyamic acid solution of 33.38g dilutes, then adds the acetic anhydride of 5.26g and the pyridine of 2.24g, within 3 hours, carries out imidizate in 50 DEG C of reactions.
Drop in the methyl alcohol of 351.7ml after about this reaction solution cool to room temperature, reclaim the solid of precipitation.Again with after this solid several of methanol wash, drying under reduced pressure at 100 DEG C of temperature, obtains the white powder of polyimide (SPI-5).The number-average molecular weight of this polyimide is 10111, and weight-average molecular weight is 33653, and acid imide rate is 90%.
In this polyimide powder of 1.2g, add the GBL of 10.8g, stir 24 hours at 50 DEG C of temperature.At the end of stirring, polyimide dissolves completely.After this solution of 12g is cooled to 23 DEG C, add the BCS of GBL, 6g of 2g, stir 20 hours at 50 DEG C of temperature.After stirring terminates, be cooled to 23 DEG C, obtain homogeneous aligning agent for liquid crystal.
Comparative example 15
Be used as the A-3 of A-2,3.27g (15mmol) of the 6.86g (35mmol) of tetracarboxylic dianhydride's composition, B-3 as B-1,6.11g (15mmol) of B-7,3.04g (15mmol) of the 2.44g (20mmol) of diamine component, react 24 hours under room temperature in the NMP of 87.0g, obtain polyamic acid solution (PAA-2).The number-average molecular weight of this polyamic acid is 15539, and weight-average molecular weight is 47210.In this solution of 8g, add the BCS of NMP, 7.5g of 10.5g, at room temperature stir 20 hours, obtain homogeneous aligning agent for liquid crystal.
Comparative example 16
By SPI-3 and PAA-4 mixing to make its mass ratio for 3: 7, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Comparative example 17
Be used as the A-3 of the 4.05g (18mmol) of tetracarboxylic dianhydride's composition, B-2 as B-11,0.75g (2mmol) of the 5.15g (18mmol) of diamine component, react 16 hours under room temperature in the NMP of 73.07g, obtain the polyamic acid solution of 12 quality %.The number-average molecular weight of this polyamic acid is 12180, and weight-average molecular weight is 25160.The BCS of NMP, 50g of this polyamic acid solution 115g of 50g is diluted, obtains polyamic acid solution (PAA-3).
Comparative example 18
Be used as the A-3 of A-2,9.60g (44mmol) of the 9.80g (50mmol) of tetracarboxylic dianhydride's composition, B-8 as the 19.8g (100mmol) of diamine component, react 5 hours under room temperature in the NMP of 222g, obtain polyamic acid solution (PAA-1).The number-average molecular weight of this polyamic acid solution is 11153, and weight-average molecular weight is 29487.In this polyamic acid solution of 8g, add the BCS of NMP, 7.5g of 10.5g, at room temperature stir 20 hours, obtain homogeneous aligning agent for liquid crystal.
In this solution of 10g, add the P17 of 0.03g, in stirred at ambient temperature 5 hours, obtain aligning agent for liquid crystal.
Comparative example 19
Be used as the A-1 of A-2,3.00g (10mmol) of the 7.15g (37mmol) of tetracarboxylic dianhydride's composition, B-8 as B-12,1.98g (10mmol) of the 7.97g (40mmol) of diamine component, react 16 hours under room temperature in the NMP of 181g, obtain the polyamic acid solution of 10 quality %.The number-average molecular weight of this polyamic acid is 12180, and weight-average molecular weight is 30160.The BCS of NMP, 100g of this polyamic acid solution 230g of 100.0g is diluted, obtains polyamic acid solution (PAA-4).
In this solution of 10g, add the P17 of 0.03g, in stirred at ambient temperature 5 hours, obtain aligning agent for liquid crystal.
Comparative example 20
By PAA-3 and PAA-4 mixing to make its mass ratio for 2: 8, at room temperature stir 5 hours, obtain aligning agent for liquid crystal.
Table 3
It is mixing ratio in polymkeric substance [] Specific compound Acid imide rate (%)
Embodiment 39 SPI-1 P17 85
Embodiment 40 SPI-1/PAA-1[2/8] P17
Embodiment 41 SPI-1/PAA-1[2/8] P19
Embodiment 42 SPI-1/PAA-1[2/8] P13
Embodiment 43 SPI-1/PAA-1[2/8] P49
Embodiment 44 SPI-1/PAA-1[2/8] P31
Embodiment 45 SPI-1/PAA-1[2/8] P46
Embodiment 46 SPI-1/PAA-1[2/8] P47
Embodiment 47 SPI-2/PAA-1[2/8] P17
Embodiment 48 SPI-3 P17 93
Embodiment 49 SPI-4 P17 90
Embodiment 50 SPI-5 P17 90
Embodiment 51 PAA-2 P17
Embodiment 52 SPI-3/SPI-4[3/7] P17
Embodiment 53 PAA-3 P17
Embodiment 54 PAA-3/PAA-4[2/8] P17
Comparative example 9 SPI-1 Nothing 85
Comparative example 10 SPI-1/PAA-1[2/8] Nothing
Comparative example 11 SPI-2/PAA-1[2/8] Nothing
Comparative example 12 SPI-3 Nothing 93
Comparative example 13 SPI-4 Nothing 90
Comparative example 14 SPI-5 Nothing 90
Comparative example 15 PAA-2 Nothing
Comparative example 16 SPI-3/SPI-4[3/7] Nothing
Comparative example 17 PAA-3 Nothing
Comparative example 18 PAA-1 P17
Comparative example 19 PAA-4 P17
Comparative example 20 PAA-3/PAA-4[2/8] Nothing
Table 4
Industrial utilizes possibility
The aligning agent for liquid crystal of the application of the invention, few and the reduction of voltage retention is also little after the being exposed to backlight for a long time liquid crystal orientation film of the film chip that can obtain producing because of friction treatment, the liquid crystal display cells reliability with gained liquid crystal orientation film is high, and can be used for large picture and the LCD of the liquid crystal TV set of high-resolution, monitor etc.
Quote the announcement of full content as instructions of the present invention of the instructions of No. 2008-334248, the Japanese patent application that on Dec 26th, 2008 files an application, claims and summary here.

Claims (7)

1. aligning agent for liquid crystal, it is characterized in that, containing be selected from the compound of at least one of the compound represented except the following formula [2] of 2-hydroxy-5-methyl base-isophthalic alcohol as (A) composition, be selected from the macromolecular compound of at least one of polyimide and polyimide precursor as (B) composition
In formula, X 2and X 3be the alkyl of hydrogen atom or carbon number 1 ~ 3 independently of one another, Y 2and Y 3respective is independently aromatic ring, and any hydrogen atom of this aromatic ring can be replaced by the alkoxy of the alkyl of hydroxyl, carbon number 1 ~ 3, halogen atom, carbon number 1 ~ 3 or vinyl, Z 1for singly-bound, all or part of can in conjunction with the saturated hydrocarbyl ,-NH-,-N (CH of the carbon number 1 ~ 10 of formation ring texture 3)-or the group that represents of formula [3], wherein all or part of can be able to be replaced by fluorine atoms in conjunction with any hydrogen atom of saturated hydrocarbyl of the carbon number 1 ~ 10 forming ring texture,
-P 1-Q 1-P 2[3]
In formula, P 1and P 2be the alkyl of carbon number 1 ~ 5 independently of one another, Q 1for aromatic ring,
T 2and t 3be the integer of 1 ~ 3 independently of one another, a and b is the integer of 1 ~ 3 independently of one another.
2. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, (A) composition is at least one compound being selected from following compound,
3. aligning agent for liquid crystal as claimed in claim 1 or 2, it is characterized in that, (B) composition is the macromolecular compound of at least one being selected from the polyamic acid being reacted by diamine component and tetracarboxylic dianhydride's composition and obtained and the polyimide obtained by this polyamic acid dehydration closed-loop.
4. aligning agent for liquid crystal as claimed in claim 3, is characterized in that, also containing organic solvent.
5. aligning agent for liquid crystal as claimed in claim 4, is characterized in that, the concentration of quality, i.e. solid constituent after removing organic solvent is 1 ~ 20 quality %.
6. liquid crystal orientation film, uses the aligning agent for liquid crystal according to any one of claim 1 ~ 5 and obtains.
7. liquid crystal display cells, possesses liquid crystal orientation film according to claim 6.
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