CN102329626B - Liquid crystal aligning agent, method for forming liquid crystal alignment film, liquid crystal display device, and related compounds - Google Patents

Liquid crystal aligning agent, method for forming liquid crystal alignment film, liquid crystal display device, and related compounds Download PDF

Info

Publication number
CN102329626B
CN102329626B CN201110187805.8A CN201110187805A CN102329626B CN 102329626 B CN102329626 B CN 102329626B CN 201110187805 A CN201110187805 A CN 201110187805A CN 102329626 B CN102329626 B CN 102329626B
Authority
CN
China
Prior art keywords
liquid crystal
aligning agent
display device
crystal aligning
crystal display
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201110187805.8A
Other languages
Chinese (zh)
Other versions
CN102329626A (en
Inventor
安田博幸
永尾隆
坂本昌巳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Chiba University NUC
Original Assignee
JSR Corp
Chiba University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JSR Corp, Chiba University NUC filed Critical JSR Corp
Publication of CN102329626A publication Critical patent/CN102329626A/en
Application granted granted Critical
Publication of CN102329626B publication Critical patent/CN102329626B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

The present invention relates to a liquid crystal aligning agent, a method for forming a liquid crystal alignment film, a liquid crystal display device, and related compounds. The present invention provides the liquid crystal aligning agent of the liquid crystal alignment film which can form an orientation control force given to liquid crystal molecules through a light orientation method, and when the liquid crystal aligning agent is used for a vertical alignment type liquid crystal display device, a good balance between the vertical alignment control force and a coating property can be achieved. On the other hand, when the liquid crystal aligning agent is used for a TN type, STN type or a transverse electric field type liquid crystal display device, the orientation control force is also good. The liquid crystal aligning agent contains radioactive ray sensitive polymer with a specific structure represented by the structure shown as following formula (1'-1).

Description

The formation method of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device and compound
Technical field
The present invention relates to a kind of liquid crystal aligning agent, the formation method of liquid crystal orientation film, liquid crystal display device and compound.More specifically, the liquid crystal aligning agent of the excellent liquid crystal orientation film of a kind of orientation control force that can form liquid crystal molecule and the excellent liquid crystal display device of display quality is related to.
Background technology
All the time, there will be a known the substrate of the band transparency electrode by having liquid crystal orientation film, the nematic liquid crystal will with positive dielectric anisotropy forms sandwich structure, and makes the major axis of liquid crystal molecule between substrate, reverse 0 ~ 360 ° and the liquid crystal display device (see patent documentation 1 and 2) such as TN (twisted-nematic) type that formed and STN (supertwist to row) type continuously as required.
In this liquid crystal display device, in order to make liquid crystal molecule relative to real estate with prescribed direction orientation, need to arrange liquid crystal orientation film on the surface of the substrate.This liquid crystal orientation film is formed by the method (rubbing manipulation) using the cloth material such as artificial silk to rub to the organic membrane surface that substrate surface is formed in a direction usually.But, when forming liquid crystal orientation film by friction treatment, owing to easily producing dust or electrostatic in operation, therefore, having dust and being attached on alignment layer surface, thus cause the bad problem of display occurs.Particularly when having the substrate of TFT (thin film transistor) element, also having the electrostatic because producing and causing the circuit of TFT element to damage, causing the problem of the reason of decrease in yield.In addition, from now in the liquid crystal display device of more and more high-precision refinement, along with the densification of pixel, inevitably produce concavo-convex on the surface of the substrate, therefore carry out uniform friction treatment and become more and more difficult.
Therefore, as other method controlling liquid crystal molecular orientation in liquid crystal display device, propose the radioactive rays photosensitive film such as polyvinyl cinnamate, polyimide, azobenzene derivatives formed on the surface of the substrate being irradiated to polarization or non-polarized light, thus give the optical alignment method of liquid crystal aligning ability.According to the method, electrostatic or dust can not be produced, and uniform liquid crystal aligning (see patent documentation 3 ~ 13) can be realized.
On the other hand, as the operating method with above-mentioned different liquid crystal display device, also there will be a known VA (vertical orientated) the type liquid crystal display device of the liquid crystal molecule vertical orientation mode on substrate making to have negative dielectric anisotropic.In this operating method, when applying voltage between substrate, thus during the direction making liquid crystal molecule tend to substrate-parallel, need liquid crystal molecule is tilted from substrate normal direction to the direction of in real estate.As the method realizing this situation, such as, proposing the method that projection is set on the surface of the substrate, the method that striped is set on the transparent electrodes, by using friction orientation film, liquid crystal molecule having been tilted a little from substrate normal direction to the direction of in real estate the method etc. of (pre-tilt).
Known aforementioned optical alignment method can also effectively be used as in the liquid crystal display device of vertical orientating type, controls the method in liquid crystal molecules tilt direction.That is, by using the liquid crystal orientation film of the vertical orientated property of being given tropism control ability and tilt angle expression power by optical alignment method, the vergence direction (see patent documentation 11 ~ 12 and 14 ~ 16) of liquid crystal molecule when can control equably to apply voltage.
But, when being applicable to the liquid crystal orientation film of TN type, STN type or vertical alignment-type liquid crystal display device by optical alignment method formation, not yet know the liquid crystal aligning agent can stablized and show the liquid crystal aligning control being enough to applicable industrial degree so far.Particularly when the liquid crystal display device for vertical orientating type, should show and have to that there is upright and outspoken liquid crystal structure with the liquid crystal aligning control in the vertical direction of real estate, the polymkeric substance that forms liquid crystal orientation film, therefore have the coating of the liquid crystal aligning agent containing this polymkeric substance or the impaired problem of printing, and not yet know the vertical alignment-type liquid crystal aligning agent with good liquid crystal aligning and good coating so far.
But in recent years, proposed and only on the side of a pair substrate of subtend configuration, formed electrode, and with the direction of substrate-parallel on produce the liquid crystal display device (see patent documentation 17) of the lateral electric field type (IPS mode) of electric field.The liquid crystal display device of this lateral electric field type only on the side of a pair substrate of subtend configuration, forms electrode, and with the direction of substrate-parallel on produce the liquid crystal display device of Electric Field Mode, it with on two substrates, form electrode, and the liquid crystal display device producing the in the past vertical Electric Field Mode of electric field is in a direction perpendicular to the substrate compared, known its has wide viewing angle characteristic, and can carry out the display of high-quality.The liquid crystal display device of lateral electric field type, due to liquid crystal molecule only with the direction of substrate-parallel on carry out electric field response, therefore the problem of the variations in refractive index in long axis of liquid crystal molecule direction can not be produced, even and if when changing visual angle, the contrast gradient of viewer's visual confirmation and the deep or light change of Show Color also little, therefore regardless of visual angle, the display of high-quality can both be carried out.
But, when being applicable to the liquid crystal orientation film of the liquid crystal display device of this lateral electric field type by optical alignment method formation, pointing out that the orientation control force of liquid crystal molecule is not enough, therefore having needed to improve.
Prior art
[patent documentation]
[patent documentation 1] Japanese Laid-Open Patent Publication 56-91277 publication
[patent documentation 2] Japanese Unexamined Patent Publication 1-120528 publication
[patent documentation 3] Japanese Unexamined Patent Publication 6-287453 publication
[patent documentation 4] Japanese Unexamined Patent Publication 10-251646 publication
[patent documentation 5] Japanese Unexamined Patent Publication 11-2815 publication
[patent documentation 6] Japanese Unexamined Patent Publication 11-152475 publication
[patent documentation 7] Japanese Unexamined Patent Publication 2000-144136 publication
[patent documentation 8] Japanese Unexamined Patent Publication 2000-319510 publication
[patent documentation 9] Japanese Unexamined Patent Publication 2000-281724 publication
[patent documentation 10] Japanese Unexamined Patent Publication 9-297313 publication
[patent documentation 11] Japanese Unexamined Patent Publication 2003-307736 publication
[patent documentation 12] Japanese Unexamined Patent Publication 2004-163646 publication
[patent documentation 13] Japanese Unexamined Patent Publication 2002-250924 publication
[patent documentation 14] Japanese Unexamined Patent Publication 2004-83810 publication
[patent documentation 15] Japanese Unexamined Patent Publication 9-211468 publication
[patent documentation 16] Japanese Unexamined Patent Publication 2003-114437 publication
[patent documentation 17] United States Patent (USP) No. 5928733 specification sheets
[patent documentation 18] Japanese Laid-Open Patent Publication 63-291922 publication
[patent documentation 19] Japanese Unexamined Patent Publication 2010-097188 publication
[non-patent literature]
[non-patent literature 1] " ゾ Le-ゲ Le forensic science ", (strain) ア グ ネ Cheng Wind society issues, 1988,154-161 page
Summary of the invention
The present invention carries out in view of the foregoing, its objective is that providing a kind of can form the orientation control force can being given liquid crystal molecule by optical alignment method, and when the liquid crystal display device for vertical orientating type, the balance of vertical orientated control and coating is excellent, on the other hand, when the liquid crystal display device for TN type, STN type or lateral electric field type, the liquid crystal aligning agent of the liquid crystal orientation film that orientation control force is also excellent.
It is excellent that another object of the present invention is to provide a kind of liquid crystal aligning control, and the liquid crystal display device that display quality is also excellent.
Other object of the present invention and advantage, learned by following explanation.
First, above object and advantages of the present invention are reached by a kind of liquid crystal aligning agent, it contains the radiation-sensitive polymkeric substance had by least one structure selected in the group of following formula (1 ') ~ (3 ') Structure composing represented separately
(in formula (1 ') ~ (3 '), R 1for hydrogen atom, fluorine atom, carbonatoms be 1 ~ 30 alkyl or carbonatoms be the fluoro-alkyl of 1 ~ 30, or there is 1 valency group of steroid skeleton, R 2for cyclohexylidene or phenylene, R 3for phenylene or following formula (R 3-1) group represented by,
(formula (R 3-1) in, X 1for +-COO-or +-OCO-or Sauerstoffatom (wherein, the connecting key with "+" is connected with phenylene), d is 0 or 1, and when d is 0, e is the integer of 0 ~ 12, and when d is 1, e is the integer of 1 ~ 12.)
The alkylidene group that X is singly-bound, Sauerstoffatom, sulphur atom, methylene radical, carbonatoms are 2 or 3 ,-CH=CH-,-NH-, *-COO-or *-OCO-is (wherein, with connecting key and the R of " * " 2connect), Z 1and Z 2in one be carbonyl, another one is methylene radical or Sauerstoffatom, and a is the integer of 0 ~ 3, b be 0 or 1, c be the integer of 0 ~ 3, and when a is 2 or 3, multiple R of existence 2and X, separately can be identical, also can be different.)
The second, above object and advantages of the present invention are reached by a kind of liquid crystal display device with the liquid crystal orientation film formed by above-mentioned liquid crystal aligning agent.
Liquid crystal aligning agent of the present invention, a kind of orientation control force giving liquid crystal molecule by optical alignment method can be formed, and when the liquid crystal display device for vertical orientating type, the vertical orientated control of liquid crystal molecule and the balance of coating excellent, on the other hand, when the liquid crystal display device for TN type, STN type or lateral electric field type, the liquid crystal orientation film that the orientation control force of liquid crystal molecule is also excellent.
There is the liquid crystal display device of the present invention of this liquid crystal orientation film formed by liquid crystal aligning agent of the present invention, the display of high-quality can be carried out, and low price, therefore, it is possible to be effective to various display unit.
Embodiment
Liquid crystal aligning agent of the present invention contains the radiation-sensitive polymkeric substance of at least one group selected in the group having and be made up of the group that above-mentioned formula (1 ') ~ (3 ') is represented separately.
As the skeleton of above-mentioned radiation-sensitive polymkeric substance, such as polyamic acid, polyimide, poly amic acid ester, organopolysiloxane, polyester, polymeric amide, cellulose and its derivates, polyacetal, polystyrene and derivative thereof, poly-(vinylbenzene-phenyl maleimide) and derivative thereof, poly-(methyl) acrylate etc. can be enumerated, wherein preferred organopolysiloxane.That is, as the radiation-sensitive polymkeric substance contained by liquid crystal aligning agent of the present invention, preferably there is the radiation-sensitive organopolysiloxane of at least one group selected in the group be made up of the group that above-mentioned formula (1 ') ~ (3 ') is represented separately.
< radiation-sensitive organopolysiloxane >
The radiation-sensitive organopolysiloxane preferably contained in liquid crystal aligning agent of the present invention, has at least one group selected in the group be made up of the group that above-mentioned formula (1 ') ~ (3 ') is represented separately.
As R in above-mentioned formula (1 ') ~ (3 ') 1carbonatoms be the alkyl of 1 ~ 30, such as methyl, ethyl, propyl group, butyl, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl etc. can be enumerated;
Be the fluoro-alkyl of 1 ~ 30 as carbonatoms, such as trifluoromethyl, pentafluoroethyl group, nine fluorine butyl, ten trifluoro hexyls, 15 fluorine heptyl, 17 fluorine octyl groups, 19 fluorine nonyls etc. can be enumerated;
As the 1 valency group with steroid skeleton, such as 3-cholestane base, 3-cholesteryl etc. can be enumerated.As abovementioned alkyl and fluoro-alkyl, be preferably straight chain.
As this R 1for hydrogen atom, fluorine atom, carbonatoms be 1 ~ 5 alkyl or carbonatoms be the fluoro-alkyl of 1 ~ 5 time, liquid crystal aligning agent of the present invention can be preferred for the liquid crystal display device of TN type, STN type or lateral electric field type,
And work as R 1for carbonatoms be 2 ~ 30 alkyl or carbonatoms be the fluoro-alkyl of 2 ~ 30, or when having 1 valency group of steroid skeleton, liquid crystal aligning agent of the present invention can be preferred for the liquid crystal display device of vertical orientating type.
R 2phenylene and cyclohexylidene, be respectively preferably Isosorbide-5-Nitrae-phenylene and Isosorbide-5-Nitrae-cyclohexylidene.
R 3phenylene be preferably Isosorbide-5-Nitrae-phenylene, and work as R 3for above-mentioned formula (R 3-1), during group represented by, wherein contained phenylene is preferably Isosorbide-5-Nitrae-phenylene.Formula (R 3-1) e in, when d is 0, it is preferably the integer of 0 ~ 4, and when d is 1, it is preferably the integer of 1 ~ 4.
As X, be preferably singly-bound or *-COO-is (wherein, with connecting key and the R of " * " 2connect).
As the object lesson of the group that the radiation-sensitive organopolysiloxane contained in liquid crystal aligning agent of the present invention has, as the group represented by above-mentioned formula (1 '), the group that such as following formula (1 '-1) ~ (1 '-36) are represented separately can be enumerated;
As the group represented by above-mentioned formula (2 '), the group that such as following formula (2 '-1) ~ (2 '-12) are represented separately can be enumerated;
As the group represented by above-mentioned formula (3 '), the group that such as following formula (3 '-1) ~ (3 '-6) are represented separately can be enumerated.
In the examples described above, n is the integer of 0 ~ 20, and group C nh 2n+1-can be replaced by one or more fluorine atom.
Containing of at least one group selected in the group be made up of the group that above-mentioned formula (1 ') ~ (3 ') is represented separately in the radiation-sensitive organopolysiloxane contained in liquid crystal aligning agent of the present invention is proportional, be preferably 0.2 ~ 6 mmole/gram polymkeric substance, and be more preferably 0.3 ~ 5 mmole/gram polymkeric substance.
The radiation-sensitive organopolysiloxane contained in liquid crystal aligning agent of the present invention, except at least one group selected in the group that the group represented separately by above-mentioned formula (1 ') ~ (3 ') is formed, preferably further there is epoxide group.At this moment, the epoxy equivalent (weight) of radiation-sensitive organopolysiloxane, is preferably more than 150 grams/mol, is more preferably 200 ~ 10000 grams/mol, and more preferably 200 ~ 2000 grams/mol.By using the radiation-sensitive organopolysiloxane of this epoxy equivalent (weight), liquid crystal aligning agent of the present invention can not damage the storage stability of liquid crystal aligning agent, and it is more excellent to form liquid crystal aligning, the liquid crystal orientation film that image retention characteristic is also excellent, therefore preferably.
By the weight-average molecular weight of gel permeation chromatography to the polystyrene conversion that the radiation-sensitive organopolysiloxane contained in liquid crystal aligning agent of the present invention measures, be preferably 1000 ~ 200000, be more preferably 2000 ~ 100000, and be particularly preferably 3000 ~ 30000.
The synthesis > of < radiation-sensitive organopolysiloxane
The radiation-sensitive organopolysiloxane preferably contained in liquid crystal aligning agent of the present invention, as long as mentioned above, just can use the material synthesizing gained by any method.As the synthetic method of the radiation-sensitive organopolysiloxane contained in liquid crystal aligning agent of the present invention, such as, can adopt:
To there is the hydrolysable silanes compound of at least one group selected in the group that is made up of the group that above-mentioned formula (1 ') ~ (3 ') is separately represented or the mixture of this hydrolysable silanes compound and other hydrolysable silanes compound is hydrolyzed and the method for condensation;
At least one (hereinafter referred to as " specific carboxylic acid ") selected in the group that the organopolysiloxane making to have epoxy group(ing) and the compound represented separately by following formula (1) ~ (3) are formed carries out the method etc. of reacting,
(the R in formula (1) ~ (3) 1, R 2, R 3, X, Z 1, Z 2, a, b and c, respectively with above-mentioned formula (1 ') ~ (3 ') in synonym.)。
Wherein, the viewpoint such as ease that is ease from the synthesis of starting compound, reaction is considered, a method after preferably adopting.
Below, the preferred method of the radiation-sensitive organopolysiloxane contained in involutory one-tenth liquid crystal aligning agent of the present invention, the reaction method of the organopolysiloxane and specific carboxylic acid with epoxy group(ing) is described.
[there is the organopolysiloxane of epoxy group(ing)]
There is the epoxy group(ing) in the organopolysiloxane of epoxy group(ing), preferably as ethylene oxide skeleton or 1,2-epoxy group(ing) loop chain alkane skeleton, in the group (there is the group of epoxy group(ing)) being directly connected with Siliciumatom or being connected with Siliciumatom by the alkylidene group that wherein can be interrupted by Sauerstoffatom the epoxy group(ing) that comprises and being present in organopolysiloxane.As the group with this epoxy group(ing), such as following formula (EP-1) or the group represented by (EP-2) can be enumerated.
(in formula (EP-1) and (EP-2), " * " represents connecting key.)
There is the epoxy equivalent (weight) of the organopolysiloxane of epoxy group(ing), be preferably 100 ~ 10000 grams/mol, and be more preferably 150 ~ 1000 grams/mol.
By the weight-average molecular weight of gel permeation chromatography to the polystyrene conversion that the organopolysiloxane with epoxy group(ing) measures, be preferably 500 ~ 100000, be more preferably 1000 ~ 10000, and be particularly preferably 1000 ~ 5000.
This organopolysiloxane with epoxy group(ing), such as can by preferably under the existence of suitable organic solvent, water and catalyzer, make to have the silane compound of epoxy group(ing) or there is the silane compound of epoxy group(ing) and the mixture of other silane compound, being hydrolyzed and condensation and synthesizing.
As the above-mentioned silane compound with epoxy group(ing), such as 3-glycydoxy Trimethoxy silane can be enumerated, 3-glycydoxy triethoxyl silane, 3-glycydoxy methyl dimethoxysilane, 3-glycydoxy methyldiethoxysilane, 3-glycydoxy dimethyl methoxy silane, 3-glycydoxy dimethylethoxysilane, 2-(3, 4-expoxycyclohexyl) ethyl trimethoxy silane, 2-(3, 4-expoxycyclohexyl) ethyl triethoxysilane etc.
As other silane compound above-mentioned, such as tetrachloro silicane can be enumerated, tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane, trichlorosilane, Trimethoxy silane, triethoxyl silane, three positive propoxy silane, three isopropoxy silane, three n-butoxy silane, three sec-butoxy silane, fluorine trichlorosilane, fluorine Trimethoxy silane, fluorine triethoxyl silane, fluorine three positive propoxy silane, fluorine three isopropoxy silane, fluorine three n-butoxy silane, fluorine three sec-butoxy silane, METHYL TRICHLORO SILANE, methyltrimethoxy silane, Union carbide A-162, methyl three positive propoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three sec-butoxy silane, 2-(trifluoromethyl) ethyl trichlorosilane, 2-(trifluoromethyl) ethyl trimethoxy silane, 2-(trifluoromethyl) ethyl triethoxysilane, 2-(trifluoromethyl) ethyl three positive propoxy silane, 2-(trifluoromethyl) ethyl three isopropoxy silane, 2-(trifluoromethyl) ethyl three n-butoxy silane, 2-(trifluoromethyl) ethyl three sec-butoxy silane, 2-(perfluor n-hexyl) ethyl trichlorosilane, 2-(perfluor n-hexyl) ethyl trimethoxy silane, 2-(perfluor n-hexyl) ethyl triethoxysilane, 2-(perfluor n-hexyl) ethyl three positive propoxy silane, 2-(perfluor n-hexyl) ethyl three isopropoxy silane, 2-(perfluor n-hexyl) ethyl three n-butoxy silane, 2-(perfluor n-hexyl) ethyl three sec-butoxy silane, 2-(n-perfluoro-octyl) ethyl trichlorosilane, 2-(n-perfluoro-octyl) ethyl trimethoxy silane, 2-(n-perfluoro-octyl) ethyl triethoxysilane, 2-(n-perfluoro-octyl) ethyl three positive propoxy silane, 2-(n-perfluoro-octyl) ethyl three isopropoxy silane, 2-(n-perfluoro-octyl) ethyl three n-butoxy silane, 2-(n-perfluoro-octyl) ethyl three sec-butoxy silane, hydroxymethyl trichlorosilane, hydroxymethyl Trimethoxy silane, hydroxyethyl Trimethoxy silane, hydroxymethyl three positive propoxy silane, hydroxymethyl three isopropoxy silane, hydroxymethyl three n-butoxy silane, hydroxymethyl three sec-butoxy silane, 3-(methyl) acryloxypropyl trichlorosilane, 3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl triethoxyl silane, 3-(methyl) acryloxypropyl three positive propoxy silane, 3-(methyl) acryloxypropyl three isopropoxy silane, 3-(methyl) acryloxypropyl three n-butoxy silane, 3-(methyl) acryloxypropyl three sec-butoxy silane, 3-mercaptopropyi trichlorosilane, 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi three positive propoxy silane, 3-mercaptopropyi three isopropoxy silane, 3-mercaptopropyi three n-butoxy silane, 3-mercaptopropyi three sec-butoxy silane, mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three positive propoxy silane, vinyl silane triisopropoxide, vinyl three n-butoxy silane, vinyl three sec-butoxy silane, allyltrichlorosilane, allyltrimethoxysilanis, allyltriethoxysilane, allyl group three positive propoxy silane, allyl group three isopropoxy silane, allyl group three n-butoxy silane, allyl group three sec-butoxy silane, phenyl-trichloro-silicane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl three positive propoxy silane, phenyl three isopropoxy silane, phenyl three n-butoxy silane, phenyl three sec-butoxy silane, dimethyl dichlorosilane (DMCS), methyl dimethoxysilane, methyldiethoxysilane, methyl two positive propoxy silane, methyl diisopropoxy silane, methyl two n-butoxy silane, methyl two sec-butoxy silane, dimethyldichlorosilane(DMCS), dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl two positive propoxy silane, dimethyl diisopropoxy silane, dimethyl two n-butoxy silane, dimethyl two sec-butoxy silane, (methyl) [2-(n-perfluoro-octyl) ethyl] dichlorosilane, (methyl) [2-(n-perfluoro-octyl) ethyl] dimethoxysilane, (methyl) [2-(n-perfluoro-octyl) ethyl] diethoxy silane, (methyl) [2-(n-perfluoro-octyl) ethyl] two positive propoxy silane, (methyl) [2-(n-perfluoro-octyl) ethyl] diisopropoxy silane, (methyl) [2-(n-perfluoro-octyl) ethyl] two n-butoxy silane, (methyl) [2-(n-perfluoro-octyl) ethyl] two sec-butoxy silane, (methyl) (3-mercaptopropyi) dichlorosilane, (methyl) (3-mercaptopropyi) dimethoxysilane, (methyl) (3-mercaptopropyi) diethoxy silane, (methyl) (3-mercaptopropyi) two positive propoxy silane, (methyl) (3-mercaptopropyi) diisopropoxy silane, (methyl) (3-mercaptopropyi) two n-butoxy silane, (methyl) (3-mercaptopropyi) two sec-butoxy silane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxy silane, (methyl) (vinyl) two positive propoxy silane, (methyl) (vinyl) diisopropoxy silane, (methyl) (vinyl) two n-butoxy silane, (methyl) (vinyl) two sec-butoxy silane, divinyldichlorosilane, divinyl dimethoxysilane, divinyl diethoxy silane, divinyl two positive propoxy silane, divinyl diisopropoxy silane, divinyl two n-butoxy silane, divinyl two sec-butoxy silane, diphenyl dichlorosilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenylbenzene two positive propoxy silane, phenylbenzene diisopropoxy silane, phenylbenzene two n-butoxy silane, phenylbenzene two sec-butoxy silane, chlorodimethylsilane, methoxyl group dimethylsilane, oxyethyl group dimethylsilane, trimethylchlorosilane, bromotrimethylsilane, Iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, positive propoxy trimethyl silane, IPOTMS isopropyloxy trimethylsilane, n-butoxy trimethyl silane, sec-butoxy trimethyl silane, tert.-butoxy trimethyl silane, (chlorine) (vinyl) dimethylsilane, (methoxyl group) (vinyl) dimethylsilane, (oxyethyl group) (vinyl) dimethylsilane, (chlorine) (methyl) diphenyl silane, (methoxyl group) (methyl) diphenyl silane, (oxyethyl group) (methyl) diphenyl silane etc. has the silane compound of a Siliciumatom, in addition, can also enumerate trade(brand)name, such as KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (more than, SHIN-ETSU HANTOTAI's chemical industry (strain) is made), グ ラ ス レ ジ Application (Showa electrician (strain) system), SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (more than, eastern レ ダ ウ コ mono-ニ Application グ (strain) system), FZ3711, FZ3722 (more than, Japanese ユ ニ カ mono-(strain) system), DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (more than, チ Star ソ (strain) makes), methyl silicate MS51, methyl silicate MS56 (more than, Mitsubishi Chemical's (strain) makes), tetraethyl silicate 28, ethyl silicate 40, tetraethyl silicate 48 (more than, コ Le コ mono-ト (strain) makes), the partial condensate of GR100, GR650, GR908, GR950 (more than, Showa electrician (strain) make) etc., and more than one that can use wherein.
As other silane compound, wherein, preferred use is by tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, 3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, select in the group that dimethyldimethoxysil,ne and dimethyldiethoxysilane are formed more than one.
When having the organopolysiloxane of epoxy group(ing) in synthesis the present invention, have the silane compound of epoxy group(ing) and the usage ratio of other silane compound, preferably modulation is set as making the epoxy equivalent (weight) of the organopolysiloxane of gained reach above-mentioned preferable range.
As the organic solvent that can use when synthesizing and there is the organopolysiloxane of epoxy group(ing), such as hydrocarbon, ketone, ester, ether, alcohol etc. can be enumerated.
As above-mentioned hydrocarbon, such as toluene, dimethylbenzene etc. can be enumerated;
As above-mentioned ketone, such as methylethylketone, mibk, MAK, diethyl ketone, pimelinketone etc. can be enumerated;
As above-mentioned ester, such as ethyl acetate, n-butyl acetate, Isoamyl Acetate FCC, propylene glycol methyl ether acetate, acetic acid 3-methoxybutyl, ethyl lactate etc. can be enumerated;
As above-mentioned ether, such as glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), diox etc. can be enumerated;
As above-mentioned alcohol, such as 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether etc. can be enumerated.Wherein, preferred non-water-soluble material.
These organic solvents can be used alone or be use mixing two or more.
The usage quantity of organic solvent, relative to 100 weight part silane compounds total (refer to the total of the silane compound with epoxy group(ing) and optional other silane compound used, lower with.), be preferably 10 ~ 10000 weight parts, and be more preferably 50 ~ 1000 weight parts.
Synthesis has the water usage quantity during organopolysiloxane of epoxy group(ing), relative to the total 1 mole of silane compound, is preferably 0.5 ~ 100 mole, and is more preferably 1 ~ 30 mole.
As above-mentioned catalyzer, such as acid, alkali metal compound, organic bases, titanium compound, zirconium compounds etc. can be enumerated.
As above-mentioned alkali metal compound, such as sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate etc. can be enumerated.
As above-mentioned organic bases, organic primary amine or the secondary amine such as such as ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles can be enumerated; The trimethylamines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo undecylene; Organic quaternary amines etc. such as tetramethyl-ammonium oxyhydroxide.In these organic basess, the trimethylamines such as preferred triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; Organic quaternary amines such as tetramethyl-ammonium oxyhydroxide.
As the catalyzer synthesized when there is the organopolysiloxane of epoxy group(ing), be preferably alkali metal compound or organic bases.By using alkali metal compound or organic bases as catalyzer, can not produce the side reactions such as the open loop of epoxy group(ing), and can obtain the organopolysiloxane of target with height hydrolysis and condensation rates, therefore production stability is excellent, is preferred.In addition, containing the liquid crystal aligning agent of the present invention with the organopolysiloxane of epoxy group(ing) and the reactant of cinnamic acid derivative using alkali metal compound or organic bases to synthesize as catalyzer, because storage stability is extremely excellent, therefore highly beneficial.Its reason can be speculated as, as non-patent literature 1 (" science of sol-gel method ", (strain) ア グ ネ Cheng Wind society issues, 1988,154 ~ 161 pages) pointed by, when using alkali metal compound or organic bases as catalyzer in hydrolysis, condensation reaction, whether define the three-dimensional structure such as random structure or cagelike structure, and silanol base can be obtained containing proportional few organopolysiloxane.And can infer, because silanol base is containing proportional few, therefore, it is possible to suppress silanol groups condensation reaction each other, in addition, when liquid crystal aligning agent of the present invention contains other polymkeric substance described later, the condensation reaction of silanol groups and other polymkeric substance can also be suppressed, therefore obtain the result that storage stability is excellent.
As catalyzer, be particularly preferably organic bases.The usage quantity of organic bases, different and different according to the reaction conditions such as kind, temperature of organic bases, it should suitably set, such as, relative to the total 1 mole of silane compound, preferably 0.01 ~ 3 mole, and be more preferably 0.05 ~ 1 mole.
Synthesize hydrolysis when there is the organopolysiloxane of epoxy group(ing) and condensation reaction, preferably by there is the silane compound of epoxy group(ing) and other silane compound as required dissolves in organic solvent, this solution is mixed with organic bases, water, and is undertaken heating by suitable heating units such as such as oil baths and implement.
When hydrolysis and condensation reaction, it is desirable to make Heating temperature be preferably less than 130 DEG C, and be more preferably 40 DEG C ~ 100 DEG C, and preferably heat 0.5 ~ 12 hour, more preferably heat 1 ~ 8 hour.Add and hanker, can liquid be uniformly mixed, also can not stir, or under mixed solution can also being placed in reflux state.
After reaction terminates, preferably wash the organic solvent layer separated from reaction mixture with water.When carrying out this washing, use the water containing a small amount of salt, such as the aqueous ammonium nitrate solution etc. of about 0.2 % by weight washs, and it is preferred for becoming easily this one side making washing operation.Wash, until the water layer after washing is in neutral, after the desiccant dryness organic solvent layer then using anhydrous calciumsulphate, molecular sieve etc. suitable as required, except desolventizing, the organopolysiloxane with epoxy group(ing) as object can be obtained thus.
In the present invention, commercial goods can be used as the organopolysiloxane with epoxy group(ing).As this commercially available product, such as DMS-E01, DMS-E12, DMS-E21, EMS-32 (above is チ Star ソ (strain) system) etc. can be enumerated.
[specific carboxylic acid]
As the object lesson of specific carboxylic acid, the connecting key that can be set forth in the group of illustrating hereinbefore as separately represented group of above-mentioned formula (1 ') ~ (3 ') connects the carboxylic acid that hydrogen atom is formed.
[synthesis of radiation-sensitive organopolysiloxane]
The radiation-sensitive organopolysiloxane preferably contained in liquid crystal aligning agent of the present invention, can by making preferably there is the organopolysiloxane of epoxy group(ing) and specific carboxylic acid as above, preferably reaction and obtaining easily under the existence of catalyzer and organic solvent.
Herein, specific carboxylic acid, it adds up to the epoxy group(ing) 1 mole had relative to organopolysiloxane, preferably with 0.01 ~ 5 mole, is more preferably 0.05 ~ 2 mole, and more preferably the ratio of 0.1 ~ 0.8 mole uses.
In the present invention, in the scope not damaging effect of the present invention, can a part for specific carboxylic acid be replaced with the compound represented by following formula (4) and use,
R I-R II-COOH (4)
(in formula (4), R ifor carbonatoms be 8 ~ 20 alkyl or alkoxyl group or carbonatoms be 1 ~ 21 fluoro-alkyl or fluoroalkyl, R iIfor singly-bound, Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene).
At this moment, the synthesis of radiation-sensitive organopolysiloxane, by making the organopolysiloxane with epoxy group(ing), can carry out with the mixture reaction of the compound represented by specific carboxylic acid and formula (4).
As the preference of the compound represented by above-mentioned formula (4), such as following formula (4-1) or the compound represented by (4-2) can be enumerated,
C fF 2f+1-C gH 2g-COOH (4-1)
(in above-mentioned formula, f is the integer of 1 ~ 3, and g is the integer of 3 ~ 18, and h is the integer of 1 ~ 20, and i is the integer of 0 ~ 18.)
Wherein, the compound of preferred following formula (4-2-1) ~ (4-2-3) represented by any one
Due to the compound represented by above-mentioned formula (4), that specific carboxylic acid together reacts with the organopolysiloxane with epoxy group(ing), and form the compound liquid crystal orientation film of gained being given to the position of tilt angle expression power, therefore, it is possible to preferably use when liquid crystal aligning agent of the present invention is used for vertical alignment-type liquid crystal display device.In this manual, the compound represented by above-mentioned formula (4) is hereinafter referred to as " other carboxylic acid ".
In the present invention, when at least one selected in the group that the compound represented by specific carboxylic acid is formed and other carboxylic acid together use, the total usage ratio of specific carboxylic acid and other carboxylic acid, relative to the epoxy group(ing) 1 mole that organopolysiloxane has, be preferably 0.001 ~ 1.5 mole, be more preferably 0.01 ~ 1 mole, and more preferably 0.05 ~ 0.9 mole.At this moment, other carboxylic acid, relative to the total with specific carboxylic acid preferably with less than 50 % by mole, the scope being more preferably less than 25 % by mole uses.If the usage ratio of other carboxylic acid is more than 50 % by mole, then when liquid crystal display device is ON, there is the situation producing and occur abnormal area defect.
As above-mentioned catalyzer, organic bases can be used or as promoting the so-called curing catalyst of epoxy compounds and anhydride reaction and known compound.
As above-mentioned organic bases, can enumerate such as:
Organic primary amine or the secondary amine such as ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles;
The trimethylamines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo undecylene;
Organic quaternary amines etc. such as tetramethyl-ammonium oxyhydroxide.
In these organic basess, the trimethylamines such as preferred triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; Organic quaternary amines such as tetramethyl-ammonium oxyhydroxide.
As above-mentioned curing catalyst, can enumerate such as:
The tertiary amines such as benzyldimethylamine, 2,4,6-tri-(dimethylaminomethyl) phenol, cyclohexyldimethylamine, trolamine;
Glyoxal ethyline, 2-n-heptyl imidazoles, 2-n-undecane base imidazoles, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyano ethyl)-glyoxal ethyline, 1-(2-cyano ethyl)-2-n-undecane base imidazoles, 1-(2-cyano ethyl)-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis-(hydroxymethyl) imidazoles, 1-(2-cyano ethyl)-2-phenyl-4,5-bis-[(2 '-cyanoethoxy) methyl] imidazoles, 1-(2-cyano ethyl)-2-n-undecane base imidazoles trimellitate, 1-(2-cyano ethyl)-2-phenylimidazole trimellitate, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole trimellitate, 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')] ethyl-s-triazine, 2,4-diamino-6-(2 '-n-undecane base imidazolyl) ethyl-s-triazine, 2,4-diamino-6-[2 '-ethyl-4 '-methylimidazolyl-(1 ')] ethyl-s-triazine, the isocyanuric acid adduct of glyoxal ethyline, the isocyanuric acid adduct of 2-phenylimidazole, the imidazolium compoundss such as the isocyanuric acid adduct of 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')] ethyl-s-triazine,
The organo phosphorous compoundss such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;
The quaternary alkylphosphonium salt such as benzyltriphenyl phosphonium phosphonium chloride, four normal-butyl phosphonium bromides, first base three phenyl phosphonium bromide, second base three phenyl phosphonium bromide, normal-butyl three phenyl phosphonium bromide, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, second base triphenyl phosphonium acetate, four positive fourth base Phosphonium, o, o-diethyl phosphorothioate, four positive fourth base Phosphonium benzotriazole salt, four positive fourth base Phosphonium a tetrafluoro borates, four positive fourth base Phosphonium tetraphenyl borate salts, tetraphenylphosphoniphenolate tetraphenyl borate salts;
The diazabicyclo alkenes such as 1,8-diazabicyclo [5.4.0] undecylene-7, its organic acid salt;
The organometallic compounds such as zinc octoate, stannous octoate, aluminium acetylacetic ester complex compound;
The quaternary ammonium salts such as the positive fourth ammonium of tetraethyl-ammonium bromide, bromination four, tetraethylammonium chloride, the positive fourth ammonium of chlorination four;
The boron compound such as boron trifluoride, triphenyl borate;
The metal halide such as zinc chloride, tin chloride;
The high-melting-point decentralized potentiality curing catalysts such as amine add-on type promotor such as the affixture of diamines diamide or amine and epoxy resin;
By the microcapsule-type potentiality curing catalyst on the curing catalyst surfaces such as the aforementioned imidazolium compounds of polymer overmold, organo phosphorous compounds, quaternary alkylphosphonium salt;
Amine salt type potentiality curing catalyst;
The potentiality curing catalysts etc. such as the hot cationic polymerization type potentiality curing catalyst of lewis acid, Bronsted hydrochlorate contour temperature decomposition type.
Wherein, the quaternary ammonium salt that preferred tetraethylammonium bromide, bromination tetra-n-butyl ammonium, etamon chloride, chlorination tetra-n-butyl ammonium are such.
Catalyzer, relative to organopolysiloxane 100 weight part with epoxy group(ing), preferably with below 100 weight parts, be more preferably 0.01 ~ 100 weight part, and more preferably the ratio of 0.1 ~ 20 weight part uses.
There is the organopolysiloxane of epoxy group(ing) and the reaction of specific carboxylic acid, can carry out in presence of organic solvent as required.As this organic solvent, such as hydrocarbon, ether, ester, ketone, acid amides, alcohol etc. can be enumerated.Wherein, ether, ester and ketone, it is preferred for easily refining from the viewpoint of the solvability of raw material and resultant and resultant.Solvent is preferably more than 0.1 % by weight with solid component concentration (weight of the composition in reaction soln beyond solvent accounts for the ratio of total solution weight), and the ratio being more preferably 5 ~ 50 % by weight uses.
Temperature of reaction, is preferably 0 ~ 200 DEG C, and is more preferably 50 ~ 150 DEG C.Reaction times is preferably 0.1 ~ 50 hour, and is more preferably 0.5 ~ 20 hour.
The synthesis of radiation-sensitive organopolysiloxane as above, be the open loop addition of the epoxy group(ing) that the organopolysiloxane by having epoxy group(ing) has, and import the method for at least one group selected in the group be made up of the group that above-mentioned formula (1 ') ~ (3 ') is represented separately.This simple synthetic method, and the method being extremely suitable in the Drug delivery rate that can improve at least one group selected in the group be made up of the group that above-mentioned formula (1 ') ~ (3 ') is represented separately.
Other composition of < >
Liquid crystal aligning agent of the present invention, containing radiation-sensitive polymkeric substance as above, and preferred radiation-sensitive organopolysiloxane.
Liquid crystal aligning agent of the present invention, except radiation-sensitive polymkeric substance as above, and preferably beyond radiation-sensitive organopolysiloxane, only otherwise damage effect of the present invention, can also contain other composition further.As other composition this, polymkeric substance beyond such as radiation-sensitive polymkeric substance can be enumerated (hereinafter referred to as " other polymkeric substance ".), solidifying agent, curing catalysts, curing catalyst, have in molecule at least one epoxy group(ing) compound (but, except being equivalent to the material of above-mentioned radiation-sensitive organopolysiloxane.Hereinafter referred to as " epoxy compounds ".), functional silanes compound (but, except being equivalent to the material of above-mentioned radiation-sensitive organopolysiloxane.), tensio-active agent etc.
[other polymkeric substance]
Other polymkeric substance above-mentioned, can be used in the electrical characteristic improving the solution properties of liquid crystal aligning agent of the present invention and the liquid crystal orientation film of gained further.Other polymkeric substance this, be the polymkeric substance of any one without respective represented group of above-mentioned formula (1 ') ~ (3 '), it is preferably such as polyamic acid, polyimide; Organopolysiloxane beyond above-mentioned radiation-sensitive organopolysiloxane is (hereinafter referred to as " other organopolysiloxane ".); Poly amic acid ester, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc., and more than one that can use wherein.
As other polymkeric substance in the present invention, preferably use at least one polymkeric substance selected in the group be made up of polyamic acid and polyimide or other organopolysiloxane.
{ polyamic acid }
Above-mentioned polyamic acid, can react by making tetracarboxylic dianhydride and diamine compound and obtain.
As the tetracarboxylic dianhydride for the synthesis of polyamic acid of the present invention, such as aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc. can be enumerated.As its object lesson, as aliphatics tetracarboxylic dianhydride, such as butane tetracarboxylic acid dianhydride etc. can be enumerated;
As ester ring type tetracarboxylic dianhydride, such as 1 can be enumerated, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl group norbornane-2: 3, 5: 6-dianhydride, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2: 4, 6: 8-dianhydride, 4, 9-dioxa three ring [5.3.1.02, 6] undecane-3, 5, 8, 10-tetraketone etc.,
As aromatic tetracarboxylic acid's dianhydride, such as pyromellitic acid dianhydride etc. can be enumerated,
In addition, tetracarboxylic dianhydride described in Japanese Unexamined Patent Publication 2010-097188 publication (patent documentation 19) can also be used.
As the tetracarboxylic dianhydride for the synthesis of foregoing polyamides acid, wherein preferably comprise ester ring type tetracarboxylic dianhydride, preferably comprise by 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 1 further, 2, the at least one selected in the group that 3,4-tetramethylene tetracarboxylic dianhydride is formed, and particularly preferably comprise 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride.
As the tetracarboxylic dianhydride for the synthesis of foregoing polyamides acid, relative to whole tetracarboxylic dianhydride, preferably comprise more than 10 % by mole by 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 1,2, the at least one selected in the group that 3,4-tetramethylene tetracarboxylic dianhydride is formed, more preferably comprises more than 20 % by mole, and most preferably only by 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 1,2, the at least one selected in the group that 3,4-tetramethylene tetracarboxylic dianhydride is formed is formed.
As the diamines for the synthesis of polyamic acid, such as aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc. can be enumerated.As its object lesson, as aliphatie diamine, such as 1,1-MXDP, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine etc. can be enumerated;
As ester ring type diamines, such as Isosorbide-5-Nitrae-diamino-cyclohexane, 4 can be enumerated, 4 '-methylene radical two (hexahydroaniline), 1,3-bis-(amino methyl) hexanaphthene etc.;
As aromatic diamine, such as Ursol D can be enumerated, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 2,7 diamin of luorene, 4,4 '-diaminodiphenyl oxide, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(to benzene diisopropylidene) two (aniline), 4,4 '-(isophthalic diisopropylidene) two (aniline), Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-two (4-aminophenyl) p-diaminodiphenyl, N, N '-two (4-aminophenyl)-N, N '-dimethyl p-diaminodiphenyl, Isosorbide-5-Nitrae-two (4-aminophenyl) piperazine, 3,5-diaminobenzoic acid, cholestane oxygen base-3,5-diaminobenzene, cholestene oxygen base-3,5-diaminobenzene, cholestane oxygen base-2,4-diaminobenzene, cholestene oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, 3,6-bis-(4-aminobenzoic acyl-oxygen base) cholestane, 3,6-bis-(4-amino-benzene oxygen) cholestane, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethylbenzoyl oxygen base) cyclohexyl-3,5-diaminobenzoic acid ester, 1,1-bis-(4-((aminophenyl) methyl) phenyl)-4-butyl cyclohexane, 1,1-bis-(4-((aminophenyl) methyl) phenyl)-4-heptylcyclohexane, 1,1-bis-(4-((amino-benzene oxygen) methyl) phenyl)-4-heptylcyclohexane, 1,1-bis-(4-((aminophenyl) methyl) phenyl)-4-(4-heptyl cyclohexyl) hexanaphthene and the compound etc. represented by following formula (D-1),
(in formula (D-1), X ifor carbonatoms be 1 ~ 3 alkyl, *-O-, *-COO-or *(connecting key wherein, with " * " is connected with diamino-phenyl-OCO-.), m be 0 or 1, n be the integer of 0 ~ 2, p is the integer of 1 ~ 20.)
As diamino organo-siloxane, such as 1,3-bis-(3-aminopropyl)-tetramethyl-bicyclohexane etc. can be enumerated,
In addition, diamines described in Japanese Unexamined Patent Publication 2010-097188 publication (patent documentation 19) can also be used.
X in above-mentioned formula (D-1) i, be preferably carbonatoms be 1 ~ 3 alkyl, *-O-or *(connecting key wherein, with " * " is connected with diamino-phenyl-COO-.)。As group C ph 2p+1the object lesson of-Ji, can enumerate such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.Two amino in diamino-phenyl, relative to other group, are preferably placed at 2,4-position and 3,5-position.
As the object lesson of the compound represented by above-mentioned formula (D-1), such as dodecyloxy-2 can be enumerated, 4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxyaniline-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, the compound etc. that following formula (D-1-1) ~ (D-1-4) is represented separately.
In above-mentioned formula (D-1), be 0 when preferred m with n is different.
These diamines can be used alone, or are used in combination of two or more.
Be provided in the tetracarboxylic dianhydride of polyamic acid building-up reactions and the usage ratio of diamines, be preferably relative to amino 1 equivalent contained in diamine compound, the anhydride group of tetracarboxylic dianhydride is the ratio of 0.2 ~ 2 equivalent, and is more preferably the ratio of 0.3 ~ 1.2 equivalent.
The building-up reactions of polyamic acid, preferably in organic solvent, and preferably at-20 ~ 150 DEG C, under being more preferably the temperature condition of 0 ~ 100 DEG C, preferably carries out 0.5 ~ 24 hour, and is more preferably 2 ~ 10 hours.Herein, as organic solvent, as long as the polyamic acid of synthesis can be dissolved, just be not particularly limited, it can enumerate such as METHYLPYRROLIDONE, N, the non-proton class polar solvent such as N-N,N-DIMETHYLACETAMIDE, DMF, N, N-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA;
The phenol solvents etc. such as meta-cresol, xylenol, phenol, halogenated phenol.The usage quantity (a) of organic solvent, preferably makes the total amount (b) of tetracarboxylic dianhydride and diamine compound be 0.1 ~ 50 % by weight relative to the total amount (a+b) of reaction soln, and is more preferably the amount of 5 ~ 30 % by weight.
As mentioned above, the reaction soln that dissolving polyamic acid is formed can be obtained.This reaction soln directly can supply the modulation of liquid crystal aligning agent, also polyamic acid contained in reaction soln can be separated the modulation of rear supply liquid crystal aligning agent, or after isolated polyamic acid can also being refined, resupply the modulation of liquid crystal aligning agent.
When polyamic acid dehydration closed-loop forms polyimide, above-mentioned reaction soln directly can supply dehydration closed-loop reaction, also polyamic acid contained in reaction soln can be separated the reaction of rear supply dehydration closed-loop, or resupply dehydration closed-loop reaction after isolated polyamic acid can also being refined.
The separation of polyamic acid, can obtain precipitate by being injected in a large amount of poor solvents by above-mentioned reaction soln, and the method etc. of the organic solvent method of this precipitate drying under reduced pressure or the decompression of use vaporizer distillated in reaction soln is carried out.In addition, can by this polyamic acid be dissolved in organic solvent again, and the method then making it separate out with poor solvent or polyamic acid is dissolved in organic solvent again, and wash the solution of gained, then carry out the method etc. that one or many uses vaporizer decompression to distillate the operation of organic solvent in this solution and carry out refining polyamic acid.
{ polyimide }
Above-mentioned polyimide, can be synthesized by the amido acid structure dehydration closed-loop making the polyamic acid of as above gained have.At this moment, can by whole amido acid structure dehydration closed-loop complete imidization, or also only a part of dehydration closed-loop in amido acid structure can be formed amido acid structure and imide structure and the part imide compound of depositing.
The dehydration closed-loop of polyamic acid, the method of polyamic acid can be heated or polyamic acid dissolves in organic solvent by (ii) by (i), and add dewatering agent and dehydration closed-loop catalyzer in this solution, and the method heated as required etc. and carrying out.
Above-mentioned (i) heats the temperature of reaction in the method for polyamic acid, is preferably 50 ~ 200 DEG C, and is more preferably 60 ~ 170 DEG C.When temperature of reaction is less than 50 DEG C, dehydration closed-loop reaction cannot fully be carried out, and when temperature of reaction is more than 200 DEG C, the molecular weight of the polyimide of gained can decline.In reaction times in the method for heating polyamic acid, be preferably 0.5 ~ 48 hour, and be more preferably 2 ~ 20 hours.
On the other hand, add in the solution of the polyamic acid of above-mentioned (ii) in the method for dewatering agent and dehydration closed-loop catalyzer, as dewatering agent, the acid anhydrides such as such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride can be enumerated.The usage quantity of dewatering agent, relative to polyamic acid structure unit 1 mole, is preferably 0.01 ~ 20 mole.In addition, as dehydration closed-loop catalyzer, the tertiary amines such as such as pyridine, collidine, lutidine, triethylamine can be enumerated.But be not limited thereto.The usage quantity of dehydration closed-loop catalyzer, relative to the dewatering agent 1 mole used, is preferably 0.01 ~ 10 mole.As organic solvent used in dehydration closed-loop reaction, can enumerate and organic solvent that the organic solvent of illustrating as solvent used in polyamic acid synthesis is same.The temperature of reaction of dehydration closed-loop reaction, be preferably 0 ~ 180 DEG C, and be more preferably 10 ~ 150 DEG C, the reaction times is preferably 0.5 ~ 20 hour, and is more preferably 1 ~ 8 hour.
In aforesaid method (i), the polyimide of gained, directly can supply the modulation of liquid crystal aligning agent, or resupply the modulation of liquid crystal aligning agent after the polyimide of gained can being refined.On the other hand, in method (ii), the reaction soln containing polyimide can be obtained.This reaction soln directly can supply the modulation of liquid crystal aligning agent, also the modulation of liquid crystal aligning agent can be resupplied after remove dewatering agent and dehydration closed-loop catalyzer from reaction soln, and after polyimide can being separated, resupply the modulation of liquid crystal aligning agent, or resupply the modulation of liquid crystal aligning agent after isolated polyimide can also being refined.From reaction soln, remove dewatering agent and dehydration closed-loop catalyzer, the methods such as such as solvent exchange can be used.The separation of polyimide, refining, can by carrying out as being separated of polyamic acid, operation that process for purification is identical with above-mentioned.
{ other organopolysiloxane }
Other organopolysiloxane in the present invention is the organopolysiloxane beyond above-mentioned radiation-sensitive organopolysiloxane.Other organopolysiloxane this, such as can by preferably in suitable organic solvent, under the existence of water and catalyzer, the at least one silane compound (hereinafter also referred to as " raw silicon hydride compounds ") selected in the group be made up of organoalkoxysilane and silane halide compound is hydrolyzed and condensation and synthesizing.
As raw silicon hydride compounds used herein, such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane, four tert-butoxy silane, tetrachloro silicane can be enumerated, methyltrimethoxy silane, Union carbide A-162, methyl three positive propoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three sec-butoxy silane, methyl three tert-butoxy silane, methyl triple phenoxyl silane, METHYL TRICHLORO SILANE, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three positive propoxy silane, ethyl three isopropoxy silane, ethyl three n-butoxy silane, ethyl three sec-butoxy silane, ethyl three tert-butoxy silane, ethyl trichlorosilane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl-trichloro-silicane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyldichlorosilane(DMCS), trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane etc., and more than one preferably using wherein, and particularly preferably use at least one selected in the group be made up of tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylmethoxysilane and trimethylethoxysilane.
Other organopolysiloxane in the present invention, except using above-mentioned raw materials silane compound, can also synthesize equally with the above-mentioned synthetic method with the organopolysiloxane of epoxy group(ing).
By the weight-average molecular weight of gel permeation chromatography to the polystyrene conversion that other organopolysiloxane measures, be preferably 1000 ~ 100000, and be more preferably 5000 ~ 50000.
{ usage ratio of other polymkeric substance }
When liquid crystal aligning agent of the present invention contains aforementioned radiation-sensitive polymkeric substance and other polymkeric substance, as the usage ratio of other polymkeric substance, relative to radiation-sensitive polymkeric substance 100 weight part, be preferably below 10000 weight parts.The preferred usage ratio of other polymkeric substance is different and different according to the kind of the polymkeric substance contained in liquid crystal aligning agent of the present invention.
When liquid crystal aligning agent of the present invention contain radiation-sensitive organopolysiloxane and select in the group that is made up of polyamic acid and polyimide at least one polymkeric substance time, both preferred usage ratios are, relative to radiation-sensitive organopolysiloxane 100 weight part, the total amount of polyamic acid and polyimide is 100 ~ 5000 weight parts, and more preferably 200 ~ 2000 weight parts.
On the other hand, when liquid crystal aligning agent of the present invention contains radiation-sensitive organopolysiloxane and other organopolysiloxane, both preferred usage ratios are, relative to radiation-sensitive organopolysiloxane 100 weight part, the amount of other organopolysiloxane is 100 ~ 2000 weight parts.
When liquid crystal aligning agent of the present invention contains radiation-sensitive polymkeric substance and other polymkeric substance, as the kind of other polymkeric substance, at least one polymkeric substance selected in the group be preferably made up of polyamic acid and polyimide or other organopolysiloxane or its both.
[solidifying agent and curing catalysts]
In order to make radiation-sensitive polymkeric substance, the crosslinking reaction of preferred radiation-sensitive organopolysiloxane is more firm, above-mentioned solidifying agent and curing catalysts can be contained in liquid crystal aligning agent of the present invention, and the curing reaction in order to promote solidifying agent to control, can above-mentioned curing catalyst be contained in liquid crystal aligning agent of the present invention.
As above-mentioned solidifying agent, the solidified nature compound that is generally used for having epoxy group(ing) can be used or containing the solidifying agent of solidification of solidification compound of compound with epoxy group(ing), it can enumerate such as polyamine, polybasic acid anhydride, polycarboxylic acid etc.
As above-mentioned polybasic acid anhydride, acid anhydride and other polybasic acid anhydride of such as cyclohexanetricarboxylic acid can be enumerated.
As the object lesson of cyclohexanetricarboxylic acid's acid anhydride, such as hexanaphthene-1 can be enumerated, 3, 4-tricarboxylic acid-3, 4-acid anhydride, hexanaphthene-1, 3, 5-tricarboxylic acid-3, 5-acid anhydride, hexanaphthene-1, 2, 3-tricarboxylic acid-2, 3-acid anhydride etc., as other polybasic acid anhydride, such as 4-methyl nadic anhydride can be enumerated, interior methyne dicarboxylic acid anhydride, dodecenyl succinic anhydride, Succinic anhydried, maleic anhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, compound represented by following formula (CA-1) and in the synthesis of polyamic acid normally used tetracarboxylic dianhydride,
(in formula (CA-1), q is the integer of 1 ~ 20.)
In addition, α-terpinene, alloocimene etc. can also be enumerated there is the ester ring type compound of conjugated double bond and the Diels-Alder reaction resultant of maleic anhydride and their hydride etc.
As above-mentioned curing catalysts, such as antimony hexafluoride compound, phosphorus hexafluoride compound, aluminium triacetoacetate etc. can be enumerated.These catalyzer, can the cationoid polymerisation of epoxy group(ing) that produces by heating of catalysis.
As above-mentioned curing catalyst, can enumerate such as:
Imidazolium compounds;
Quaternary phosphonium compound;
Quaternary ammonium compound;
1,8-diazabicyclo [5.4.0] undecylene-7 or the such diazabicyclo alkene of its organic acid salt;
The organometallic compound that zinc octoate, stannous octoate, aluminium acetylacetic ester complex compound are such;
The boron compound that boron trifluoride, triphenyl borate are such;
The metal halide that zinc chloride, tin chloride are such;
The high-melting-point decentralized potentiality curing catalysts such as the amine add-on type promotor that the affixture of diamines diamide, amine and epoxy resin is such;
By the microcapsule-type potentiality curing catalyst on the surfaces such as polymer overmold quaternary alkylphosphonium salt;
Amine salt type potentiality curing catalyst;
The hot cationic polymerization type potentiality curing catalyst etc. of the high-temperature decomposition type that lewis acid, Bronsted hydrochlorate are such.
[epoxy compounds]
From the viewpoint of improving the liquid crystal orientation film of formation further relative to the cementability of substrate surface, above-mentioned epoxy compounds can be contained in liquid crystal aligning agent of the present invention.
As this epoxy compounds, such as ethylene glycol diglycidylether can be enumerated, 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 diglycidylether, 1, 3, 5, 6-four glycidyl group-2, 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, 3-bis-(N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-aminomethyl cyclohexane etc. are as preferred substance.
When liquid crystal aligning agent of the present invention contains epoxy compounds, it relative to total 100 weight part of above-mentioned radiation-sensitive polymkeric substance with optional other polymkeric substance used containing proportional, be preferably below 40 weight parts, and be more preferably 0.1 ~ 30 weight part.
In addition, when liquid crystal aligning agent of the present invention contains epoxy compounds, in order to effectively produce its crosslinking reaction, can be used together the alkaline catalystss such as 1 benzyl 2 methyl imidazole.
[functional silanes compound]
In order to the cementability of the liquid crystal orientation film and substrate that improve gained, above-mentioned functional silanes compound can be used.As functional silanes compound, such as 3-TSL 8330 can be enumerated, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-uride base propyl trimethoxy silicane, 3-acyl 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 ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, N-bis-(oxygen base ethylidene)-3-TSL 8330, N-bis-(oxygen base ethylidene)-APTES, 3-glycidoxypropyltrimewasxysilane, 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane etc., and can use as tetracarboxylic dianhydride described in patent documentation 18 (Japanese Laid-Open Patent Publication 63-291922 publication) and the reactant etc. with amino silane compound.
When liquid crystal aligning agent of the present invention contains functional silanes compound, as it containing proportional, relative to total 100 weight part of above-mentioned radiation-sensitive polymkeric substance with optional other polymkeric substance used, be preferably below 50 weight parts, and be more preferably below 20 weight parts.
[tensio-active agent]
As above-mentioned tensio-active agent, such as nonionogenic tenside, anion surfactant, cats product, amphoterics, polysiloxane surfactant, polyoxyalkylene surfactants, fluorochemical surfactant etc. can be enumerated.
When liquid crystal aligning agent of the present invention contains tensio-active agent, it is containing proportional, relative to entirety 100 weight part of this liquid crystal aligning agent, is preferably below 10 weight parts, and is more preferably below 1 weight part.
< liquid crystal aligning agent >
Liquid crystal aligning agent of the present invention, as mentioned above, containing radiation-sensitive polymkeric substance as neccessary composition, in addition, as required containing other composition, and preferably modulates as each component dissolves molten liquid composition in organic solvent.
As can be used in the organic solvent modulating liquid crystal aligning agent of the present invention, being preferably and dissolving radiation-sensitive polymkeric substance and optional other composition used, and the solvent that can not react with them.
Can be preferred for the organic solvent of liquid crystal aligning agent of the present invention, the kind of the polymkeric substance contained by liquid crystal aligning agent of the present invention is different and different.
As when containing at least one polymkeric substance selected in radiation-sensitive organopolysiloxane and the group that is made up of polyamic acid and polyimide when liquid crystal aligning agent of the present invention, and except containing at least one polymkeric substance selected in radiation-sensitive organopolysiloxane and the group that is made up of polyamic acid and polyimide, also containing preferred organic solvent during other organopolysiloxane, the organic solvent of illustrating as solvent used in polyamic acid synthesis can be enumerated.These organic solvents can be used alone or are used in combination of two or more.
On the other hand, as when liquid crystal aligning agent of the present invention only contains the radiation-sensitive organopolysiloxane as polymkeric substance, or containing radiation-sensitive organopolysiloxane and other organopolysiloxane, but not containing the preferred organic solvent during at least one polymkeric substance selected in the group be made up of polyamic acid and polyimide, such as 1-oxyethyl group-2-propyl alcohol can be enumerated, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether (ethylene glycol butyl ether), ethylene glycol monopentyl ether, ethylene glycol ether, Diethylene Glycol, methylcellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetic ester, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl group Trivalin SF, diethylene glycol monobutyl ether, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, acetic acid 3-methoxybutyl, methyl amyl acetate, acetic acid 2-ethyl butyl ester, acetic acid 2-ethylhexyl, jasmal, n-hexyl acetate, hexalin acetate, octyl acetate, pentyl acetate, Isoamyl Acetate FCC etc.Wherein, preferred n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate etc.
Can be used in the preferred solvent of modulating liquid crystal aligning agent of the present invention, according to the kind with or without other polymkeric substance of use and this polymkeric substance, one or more of above-mentioned organic solvent can be combinationally used and obtain, and in following preferred solid component concentration, the each composition contained in liquid crystal aligning agent can not be separated out, and make the surface tension of liquid crystal aligning agent be the scope of 25mN/m ~ 40mN/m.
The solid component concentration of liquid crystal aligning agent of the present invention, the weight of all the components beyond that is desolventizing in liquid crystal aligning agent accounts for the ratio of liquid crystal aligning agent gross weight, considers that viscosity, volatility etc. are selected, and is preferably 1 ~ 10 % by weight.By liquid crystal aligning agent of the present invention coating on the surface of the substrate, form the film forming liquid crystal orientation film, and when solid component concentration less than 1 % by weight time, there is thickness due to this film too small and be difficult to the situation of the good liquid crystal orientation film of acquisition.On the other hand, when solid component concentration is more than 10 % by weight, have film thickness excessive and be difficult to obtain good liquid crystal orientation film, and the viscosity of liquid crystal aligning agent increases and causes the situation of coating characteristics deficiency.The scope of particularly preferred solid component concentration is different according to the method adopted during coating of liquid crystalline alignment agent on substrate.Such as, when adopting spin-coating method, 1.5 ~ 4.5 % by weight are particularly preferably.When adopting print process, solid component concentration is particularly preferably the scope of 3 ~ 9 % by weight, and makes soltion viscosity be the scope of 12 ~ 50mPas thus.When adopting ink jet method, solid component concentration is particularly preferably the scope of 1 ~ 5 % by weight, and makes soltion viscosity be the scope of 3 ~ 15mPas thus.
Modulate temperature during liquid crystal aligning agent of the present invention, be preferably 0 DEG C ~ 200 DEG C, and be more preferably 0 DEG C ~ 40 DEG C.
The formation method > of < liquid crystal orientation film
Liquid crystal aligning agent of the present invention, can be preferred for being formed by optical alignment method the liquid crystal display device that can be used for TN type, STN type, lateral electric field type (IPS type) or VA type.Liquid crystal aligning agent of the present invention, when the liquid crystal display device for TN type, STN type or lateral electric field type, particularly when the liquid crystal display device for lateral electric field type, can play effect of the present invention, therefore preferably to greatest extent.
In order to use liquid crystal aligning agent of the present invention to form liquid crystal orientation film, can adopt and form film through being coated with liquid crystal aligning agent of the present invention on substrate, and this film being irradiated to the method for the operation of radioactive rays.
Herein, when liquid crystal aligning agent of the present invention being used for the liquid crystal display device of TN type, STN type or VA type, first, two panels is provided with the substrate of the nesa coating forming pattern as a pair, its each transparent conductive film forming surface is coated with liquid crystal aligning agent of the present invention, forms film.On the other hand, when liquid crystal aligning agent of the present invention is used for the liquid crystal display device of lateral electric field type, one side will have the substrate that nesa coating or metal film pattern turn to the electrode of comb teeth-shaped and the subtend substrate that electrode is not set as a pair, and in the forming surface of comb-like electrode and in the one side of subtend substrate, be coated with liquid crystal aligning agent of the present invention respectively, form film.
In either case, as aforesaid substrate, the transparency carrier etc. such as formed by the plastic basis material such as glass, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate that float glass, soda-lime glass are such can be used.As above-mentioned nesa coating, can use such as by In 2o 3-SnO 2the ito film formed, by SnO 2nESA (registered trademark) film etc. formed.As above-mentioned metallic membrane, the film such as formed by metals such as chromium can be used.The formation pattern of nesa coating and metallic membrane, can being adopted the method for such as carrying out photoengraving after forming patternless nesa coating, the method being formed pattern by sputtering method etc., using the method etc. with the mask of desired pattern when forming nesa coating.
To on substrate during coating of liquid crystalline alignment agent, in order to make the cementability of substrate or conducting film or electrode and film more good, functional silanes compound, titanic acid ester etc. can be coated with in advance on substrate and electrode.
The method of coating of liquid crystalline alignment agent on substrate, preferably can be undertaken by suitable coating processes such as adherography, spin-coating method, rolling method, ink jet printing methods, then, by preheating (prebake) coated face, and then burn till (curing afterwards) and form film.The condition of prebake, such as, for carry out at 40 ~ 120 DEG C 0.1 ~ 5 minute, after the condition of curing, be preferably at 120 ~ 300 DEG C, more preferably at 150 ~ 250 DEG C, preferably carry out 5 ~ 200 minutes, more preferably carry out 10 ~ 100 minutes.After cure after film thickness be preferably 0.001 ~ 1 μm, and be more preferably 0.005 ~ 0.5 μm.
By irradiating the radioactive rays of rectilinearly polarized light or partial polarization to thus formed film or giving liquid crystal aligning ability without the radioactive rays of polarization.Herein, as radioactive rays, the ultraviolet and visible rays that such as comprise 150 ~ 800nm wavelength light can be used, and preferably comprise the ultraviolet of 300 ~ 400nm wavelength light.Radioactive rays used be rectilinearly polarized light or partial polarization light time, can to irradiate from the direction vertical with real estate, and in order to give tilt angle, also can irradiate from the direction tilted, in addition, also they combinations can be carried out.When irradiating the radioactive rays of non-polarized light, the direction of irradiation is necessary for vergence direction.
As the light source used, such as Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon gas resonance lamp, xenon lamp, excimer laser etc. can be used.The ultraviolet in aforementioned optimal wavelength region, can by obtaining said light source and method also such as such as spectral filter, diffraction grating etc. etc.
As the irradiation dose of radioactive rays, be preferably 1J/m 2above and less than 10000J/m 2, and be more preferably 10 ~ 3000J/m 2.In addition, when giving liquid crystal aligning ability by optical alignment method for the film formed by known liquid crystal aligning agent, 10000J/m is needed 2above radiation exposure amount.And when using liquid crystal aligning agent of the present invention, even if radiation exposure amount during optical alignment method is 3000J/m 2below, be 1000J/m further 2below, also can give good liquid crystal aligning ability, and the productivity contributing to liquid crystal display device improves and the decline of manufacturing cost.
The manufacture method > of < liquid crystal display device
Use the liquid crystal display device that liquid crystal aligning agent of the present invention is formed, such as, can manufacture as follows.
First, prepare a pair substrate forming liquid crystal orientation film as mentioned above, be manufactured on the liquid crystal cell clamping the structure of liquid crystal between this pair substrate.In order to manufacture liquid crystal cell, such as following two kinds of methods can be enumerated.
First method is in the past known method.First, two plate bases are oppositely disposed across gap (box gap), make respective liquid crystal orientation film relative, and use sealing agent the peripheral part of this two plate base to be fit together, inject filling liquid crystal in the box gap divided by substrate surface and sealing agent after, close filling orifice, can liquid crystal cell be manufactured thus.
As second method, it is the method being called ODF (under liquid crystal drop) mode.Wherein, predetermined portion on one piece of substrate in two plate bases forming liquid crystal orientation film, coating such as ultra-violet solidified sealing material, drip liquid crystal again on liquid crystal aligning face, then to fit another block substrate, make liquid crystal orientation film relative, then to substrate whole irradiation ultraviolet radiation, make sealant cures, can liquid crystal cell be manufactured thus.
No matter adopt which kind of method, be next all wish liquid crystal cell to be heated to the temperature that liquid crystal used is isotropic phase, then slowly cool to room temperature, remove flow orientation during filling liquid crystal thus.
Then, by polarization plates of fitting on the outer surface of liquid crystal cell, liquid crystal display device of the present invention can be obtained thus.Herein, by suitably adjusting the polarization direction angulation of rectilinearly polarized light radioactive rays and the angle of each substrate and polarization plates that are formed and irradiate in two plate bases of liquid crystal orientation film, desired liquid crystal display device can be obtained.
As aforementioned seal agent, can enumerate and such as contain as the alumina balls of separator and the epoxy resin etc. of solidifying agent.
As foregoing liquid crystal, such as nematic liquid crystal and smectic liquid crystal etc. can be enumerated.Be preferably formed the liquid crystal with positive dielectric anisotropy of nematic liquid crystal, it can use such as biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc.In addition, use can also be added further such as cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonates in foregoing liquid crystal; The chiral agent of selling is carried out as trade(brand)name " C-15 ", " CB-15 " (more than, メ ルク society system); To oxygen base α-tolylene-to Ferroelectric liquid Crystals etc. such as amino-2-methyl butyl laurates in the last of the ten Heavenly stems.
As the polarization plates used outside liquid crystal cell; can enumerate and clamp polarizing coating with rhodia protective membrane and the polarization plates etc. that self formed of the polarization plates formed or H film; this polarizing coating is the simultaneously stability iodine gained making polyvinyl alcohol stretch orientation, is referred to as " H film ".
The liquid crystal display device of the present invention of manufacture like this, because the orientation control force of liquid crystal molecule is excellent, therefore display characteristic is excellent.
Embodiment
Below, by embodiment, the present invention is specifically described, but the present invention is not restricted to these embodiments.
Weight-average molecular weight Mw in following synthesis example, is respectively the polystyrene conversion value measured by the gel permeation chromatography of following condition.
Post: East ソ mono-(strain) makes, TSKgel GRCXLII
Solvent: tetrahydrofuran (THF)
Temperature: 40 DEG C
Pressure: 68kgf/cm 2
In addition, in following synthesis example, as required according to following synthetic route, repeat the synthesis of starting compound and polymkeric substance, thus guarantee the necessary amount in embodiment afterwards.
< has the synthesis example > of the organopolysiloxane of epoxy group(ing)
Synthesis example ES1
In the reaction vessel with stirrer, thermometer, dropping funnel and reflux condensing tube, add 100.0g 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, 500g mibk and 10.0g triethylamine, and at room temperature mix.
Then, by dropping funnel through 30 minutes instillation 100g deionized waters, then mix under reflux, and react 6 hours at 80 DEG C.After reaction terminates, take out organic layer, use the aqueous ammonium nitrate solution of 0.2 % by weight to be washed the water to washing in neutral, then under reduced pressure distillate solvent and water, obtain the organopolysiloxane (ES-1) with epoxy group(ing) as clear viscous liquid.
The organopolysiloxane that this has epoxy group(ing) is carried out 1h-NMR analyzes, and result can obtain the peak based on epoxy group(ing) the same with theoretical strength near chemical shift (δ)=3.2ppm, can confirm the side reaction not producing epoxy group(ing) in the reaction thus.
This has the viscosity of the organopolysiloxane (ES-1) of epoxy group(ing), Mw and epoxy equivalent (weight) and is shown in table 1.
Synthesis example ES2 ~ 3
Except make the raw material that adds as shown in table 1 except, and synthesis example 1 is similarly, obtains the organopolysiloxane (ES-2) with epoxy group(ing) as clear viscous liquid and (ES-3) respectively.
These have the Mw of the organopolysiloxane of epoxy group(ing) and epoxy equivalent (weight) is shown in table 1.
In addition, in Table 1, the abbreviation of raw silicon hydride compounds is respectively following implication.
ECETS:2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane
MTMS: methyltrimethoxy silane
PTMS: phenyltrimethoxysila,e
Table 1. has the synthesis of the organopolysiloxane of epoxy group(ing)
The synthesis example > of the specific carboxylic acid of <
According to following synthetic route 1, modulate compound (3-1), (3-2) and (3-3) respectively.
synthetic route 1
Wherein, in said synthesis route 1, the resultant when R is hydrogen atom is compound (3-1), and the resultant when R is fluorine atom is compound (3-2), and the resultant when R is cyclohexyl is compound (3-3).
Following synthetic operation carries out in inert atmosphere.
Synthesis example (3)-1
In the 3L there-necked flask with prolong and dropping funnel, add 40 % by weight ethanolic solns (being equivalent to 0.88 mole of benzyltrimethylammon.um oxyhydroxide) of 0.39 mole of indenes and tetramethyl-ammonium oxyhydroxide, be heated to 40 DEG C.Drip 50 % by weight aqueous solution (being equivalent to 0.59 mole of acetaldehyde acid) of oxoethanoic acid wherein, stir 1 hour at 50 DEG C, react.After reaction terminates, in reaction mixture, add 700mL pure water and 1L toluene, and add 1N sulfuric acid further, by the pH regulator of water layer to being about 2.Then, be warming up to 70 DEG C and after abundant stirring, take out organic layer, wash.Use the mixed aqueous solution (pH is about 8) formed by 1N aqueous ammonium chloride solution and 1N ammoniacal liquor, several times operation is extracted to this organic layer.Merge the water layer of gained, and add 1,2-ethylene dichloride, add 1N hydrochloric acid further, after making the pH of aqueous phase be about 2, vibrate.Take out organic layer, distillate solvent, and by toluene, recrystallization is carried out to the solid of gained, obtain 26.9g compound (3-1).
Synthesis example (3)-2 and (3)-3
Except in above-mentioned synthesis example (3)-1,0.39 mole of 5-fluorine indenes (synthesis example (3)-2) and 5-cyclohexyl indenes (synthesis example (3)-3) is used to replace beyond indenes respectively, implement equally with synthesis example (3)-1, obtain 33g compound (3-2) and 29g compound (3-3) respectively.
The comparison synthesis example > of < carboxylic acid
Synthesis example R-1
According to following synthetic route 2, synthesis ratio comparatively uses carboxylic acid (R-1).
synthetic route 2
In the there-necked flask of 200mL, add 11.21g4-hydroxy-benzalacetophenone, 8.35g ethyl bromoacetate, 13.8g salt of wormwood and 100mL N,N-DIMETHYLACETAMIDE, stir 7 hours at 120 DEG C, react.After reaction terminates, reaction soln is cooled to room temperature, then adds 100mL ethyl acetate.After organic layer is washed, under reduced pressure except desolventizing, and the mixing solutions formed by second alcohol and water (ethanol: water=4: 1 (volumetric ratio)) carries out recrystallization to the solid of gained, obtains the compound (R-1a) of 11.4g as intermediate.
Then, in the 500mL there-necked flask with prolong, add 6.2g above-claimed cpd (R-1a), 2g sodium hydroxide, 200mL ethanol and 50mL water, stir 3 hours under reflux, react.After reaction terminates, reaction mixture, then adds dilute hydrochloric acid and makes it be after acidity, add 500mL ethyl acetate, carry out separatory extraction.After the organic layer of gained is washed, under reduced pressure except desolventizing, obtain 4.1g compound (R-1).
The synthesis example > of < radiation-sensitive organopolysiloxane
Synthesis example S-1
In the there-necked flask of 100mL, add compound (3-1) and the 0.10g UCAT 18X (trade(brand)name of gained in the organopolysiloxane (ES-1) with epoxy group(ing) of gained in the above-mentioned synthesis example ES-1 of 9.3g, 26g mibk, the above-mentioned synthesis example (3)-1 of 4.30g, the quaternary ammonium salt that サ Application ア プ ロ (strain) makes), stir 12 hours at 80 DEG C, react.After reaction terminates, in reaction mixture, add methyl alcohol, reclaim the throw out generated, be dissolved in ethyl acetate, and three times are washed to the solution of gained, then heat up in a steamer desolventizing, obtain the radiation-sensitive organopolysiloxane (S-1) of 9g as white powder.The weight-average molecular weight Mw of radiation-sensitive organopolysiloxane (S-1) is 5500.
Synthesis example S-2 and S-3
Except in above-mentioned synthesis example S-1, make to have the organopolysiloxane of epoxy group(ing) and the kind of carboxylic acid (compound represented by above-mentioned formula (3)) and usage quantity respectively, outside as described in Table 2, same with synthesis example S-1, obtain radiation-sensitive organopolysiloxane (S-2) and (S-3) respectively.The weight-average molecular weight Mw of these radiation-sensitive organopolysiloxane is combined and is shown in table 2.
The comparison synthesis example > of < radiation-sensitive organopolysiloxane
Synthesis example RS-1
Except in above-mentioned synthesis example S-1, the compound (R-1) of gained in the above-mentioned synthesis example R-1 of 3.52g is used to replace compound (3-1) outward, same with synthesis example S-1, obtain radiation-sensitive organopolysiloxane (RS-1).The weight-average molecular weight Mw of radiation-sensitive organopolysiloxane (RS-1) is shown in table 2.
The synthesis of table 2. radiation-sensitive organopolysiloxane
The synthesis example > of other polymkeric substance of <
[synthesis example of polyamic acid]
Synthesis example PA-1
By 19.61g (0.1 mole) tetramethylene tetracarboxylic dianhydride and 21.23g (0.1 mole) 4,4 '-diamino-2,2 '-dimethyl diphenyl, is dissolved in 367.6g METHYLPYRROLIDONE, at room temperature carries out reaction in 6 hours.Then, reaction mixture is injected in very excessive methyl alcohol, resultant of reaction is precipitated.Reclaim throw out, by methanol wash, and under reduced pressure, at 40 DEG C, drying 15 hours, obtains 35g polyamic acid (PA-1).
Synthesis example PA-2
By 22.4g (0.1 mole) 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 14.23g (0.1 mole) hexanaphthene two (methylamine), be dissolved in 329.3g METHYLPYRROLIDONE, at 60 DEG C, carry out reaction in 6 hours.Then, reaction mixture is injected in very excessive methyl alcohol, resultant of reaction is precipitated.Use methanol wash throw out, and under reduced pressure, drying 15 hours, obtains 32g polyamic acid (PA-2) at 40 DEG C.
The part of this polyamic acid (PA-2) is supplied in aftermentioned embodiment the modulation of liquid crystal aligning agent, remainder is supplied to the synthesis of following polyimide.
[synthesis of polyimide]
Synthesis example PI-1
Get the polyamic acid (PA-2) of gained in the above-mentioned synthesis example PA-2 of 17.5g, add 232.5g METHYLPYRROLIDONE, 3.8g pyridine and 4.9g diacetyl oxide wherein, at 120 DEG C, carry out 4 hours imidization reaction.The reaction mixture of gained is injected in very excessive methyl alcohol, resultant of reaction is precipitated.Use methanol wash throw out, and drying under reduced pressure 15 hours, obtain 15g polyimide (PI-1).
Embodiment 1
The modulation > of < liquid crystal aligning agent
Using the radiation-sensitive organopolysiloxane (S-1) of gained in 100 weight part above-described embodiment S-1 and the 1000 weight parts polyamic acid (PA-1) as gained in the above-mentioned synthesis example PA-1 of other polymkeric substance, be dissolved in the mixed solvent (METHYLPYRROLIDONE: ethylene glycol butyl ether=50: 50 (weight ratios)) formed by METHYLPYRROLIDONE and ethylene glycol butyl ether, form the solution that solid component concentration is 3.0 % by weight.Use aperture is this solution of metre filter of 1 μm, modulation liquid crystal aligning agent.
The manufacture > of < liquid crystal display device
Spin coater is used to be coated on respectively by the liquid crystal aligning agent of above-mentioned modulation on the electrode forming surface of the glass substrate with the chromium metal electrode being patterned into comb teeth-shaped, and do not arrange in the one side of subtend glass substrate of electrode, and on the hot plate of 80 DEG C prebake 1 minute, then carried out in casing in the baking oven of nitrogen replacement, cure 1 hour after at 200 DEG C, form the film that thickness is 0.1 μm.Then, use Hg-Xe lamp and Glan-Taylor prism, from the normal direction of substrate, respectively 600J/m is irradiated to this film coated surface 2comprise the polarized UV rays that wavelength is 313nm bright line, obtain the substrate a pair with liquid crystal orientation film.
Pass through silk screen printing, the substrate in above-mentioned a pair substrate with chromium metal electrode is formed the periphery in the face of liquid crystal orientation film, it is after the epoxy resin binder of the alumina balls of 5.5 μm that coating adds diameter, by the liquid crystal orientation film of a pair substrate in the face of to, carry out pressing, making the direction of each substrate when irradiation ultraviolet radiation is each other reverse direction, and heats 1 hour at 150 DEG C, makes tackiness agent thermofixation.Then, filled the liquid crystal MLC-7028 of メ ルク society in the gap of substrate by liquid crystal injecting port after, with epoxy adhesive encapsulated liquid crystals inlet.In addition, in order to eliminate flow orientation during Liquid crystal pour, room temperature is slowly cooled at its 150 DEG C after heating.Then, polarization plates of fitting in the two sides, outside of substrate, makes its direction of polarized light orthogonal, and orthogonal with the projecting direction of ultraviolet optical axis on real estate of liquid crystal orientation film, manufactures the liquid crystal display device of lateral electric field type thus.
The evaluation > of < liquid crystal display device
By the following method this liquid crystal display device is evaluated.Evaluation result is shown in table 3.
(1) evaluation of liquid crystal aligning
By observation by light microscope abnormal area with or without light and shade change when liquid crystal display device switch (apply remove) the 5V voltage to above-mentioned manufacture, and when not observing abnormal area, liquid crystal aligning is evaluated as " well ", when observing abnormal area, liquid crystal aligning is evaluated as " bad ".
(2) evaluation of voltage retention
To the liquid crystal display device of above-mentioned manufacture, apply the voltage of 5V with the application time of 60 microseconds, the interval of 167 milliseconds at 60 DEG C after, measure from applying to remove the voltage retention after 167 milliseconds.Determinator uses (strain) Dongyang テ Network ニ カ system, VHR-1.
Embodiment 2 ~ 8 and comparative example 1
Except in above-described embodiment 1, the kind of change radiation-sensitive organopolysiloxane as described in Table 3 and the kind of other polymkeric substance are with outside amount respectively, and embodiment 1 modulates liquid crystal aligning agent equally, and manufacture liquid crystal display device evaluation.Evaluation result is shown in table 3.
In addition, in comparative example 1, polarized ultraviolet irradiation dose when manufacturing liquid crystal display device is 1000J/m 2.
The modulation of table 3. liquid crystal aligning agent and evaluation

Claims (11)

1. a liquid crystal aligning agent, is characterized in that containing radiation-sensitive polymkeric substance, and this radiation-sensitive polymkeric substance has the structure represented by following formula (3 '),
In formula (3 '), R 1for hydrogen atom, fluorine atom, or there is 1 valency group of steroid skeleton, R 2for cyclohexylidene or phenylene, R 3for phenylene or following formula (R 3-1) group represented by,
Formula (R 3-1) in, X 1for +-COO-or +-OCO-or Sauerstoffatom, wherein, the connecting key with "+" is connected with phenylene, and d is 0 or 1, and when d is 0, e is the integer of 0 ~ 12, and when d is 1, e is the integer of 1 ~ 12,
The alkylidene group that X is singly-bound, Sauerstoffatom, sulphur atom, methylene radical, carbonatoms are 2 or 3 ,-CH=CH-,-NH-, *-COO-or *-OCO-, wherein, with connecting key and the R of " * " 2connect, a is the integer of 0 ~ 3, b be 0 or 1, c be the integer of 0 ~ 3, wherein, when a is 2 or 3, multiple R of existence 2separately can be identical with X, also can be different,
Wherein, the structure in described radiation-sensitive polymkeric substance represented by above-mentioned formula (3 ') containing proportional be 0.2 ~ 6 mmole/gram polymkeric substance.
2. liquid crystal aligning agent as claimed in claim 1, wherein, above-mentioned radiation-sensitive polymkeric substance is the radiation-sensitive organopolysiloxane of the structure had represented by formula (3 ').
3. liquid crystal aligning agent as claimed in claim 2, wherein, above-mentioned radiation-sensitive organopolysiloxane is the resultant of reaction with the organopolysiloxane of epoxy group(ing) and the compound represented by following formula (3),
R in formula (3) 1, R 2, R 3, X, a, b and c, with above-mentioned formula (3 ') in synonym.
4. the liquid crystal aligning agent as described in any one of claims 1 to 3, it is further containing at least one polymkeric substance selected in the group be made up of polyamic acid and polyimide, and wherein, this polymkeric substance is not containing the structure represented by formula (3 ').
5. the liquid crystal aligning agent as described in any one of claims 1 to 3, it is further containing organopolysiloxane, and wherein, this organopolysiloxane is not containing the structure represented by formula (3 ').
6. a formation method for liquid crystal orientation film, is characterized in that liquid crystal aligning agent through being coated with on substrate described in any one of Claims 1 to 5 and forms film, and irradiates the operation of radioactive rays to this film.
7. a liquid crystal display device, is characterized in that having the liquid crystal orientation film formed by the liquid crystal aligning agent described in any one of Claims 1 to 5.
8. liquid crystal display device as claimed in claim 7, the R wherein in formula (3 ') described in claim 1 1for hydrogen atom, fluorine atom, carbonatoms be 1 ~ 5 alkyl or carbonatoms be the fluoro-alkyl of 1 ~ 5, and liquid crystal display device is the liquid crystal display device of TN type, STN type or lateral electric field type.
9. liquid crystal display device as claimed in claim 8, wherein liquid crystal display device is the liquid crystal display device of lateral electric field type.
10. liquid crystal display device as claimed in claim 7, the radicals R wherein in formula (3 ') described in claim 1 1for having 1 valency group of steroid skeleton, and liquid crystal display device is the liquid crystal display device of vertical orientating type.
Compound represented by 11. following formula (3),
In formula (3), R 1for hydrogen atom, fluorine atom, or there is 1 valency group of steroid skeleton, R 2for cyclohexylidene or phenylene, R 3for phenylene or following formula (R 3-1) group represented by,
Formula (R 3-1) in, X 1for +-COO-or +-OCO-or Sauerstoffatom, wherein, the connecting key with "+" is connected with phenylene, and d is 0 or 1, and when d is 0, e is the integer of 0 ~ 12, and when d is 1, e is the integer of 1 ~ 12,
The alkylidene group that X is singly-bound, Sauerstoffatom, sulphur atom, methylene radical, carbonatoms are 2 or 3 ,-CH=CH-,-NH-, *-COO-or *-OCO-, wherein, with connecting key and the R of " * " 2connect, a is the integer of 0 ~ 3, b be 0 or 1, c be the integer of 0 ~ 3, and when a is 2 or 3, multiple R of existence 2separately can be identical with X, also can be different.
CN201110187805.8A 2010-06-30 2011-06-29 Liquid crystal aligning agent, method for forming liquid crystal alignment film, liquid crystal display device, and related compounds Expired - Fee Related CN102329626B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010149082A JP5642435B2 (en) 2010-06-30 2010-06-30 Liquid crystal aligning agent and liquid crystal display element
JP2010-149082 2010-06-30

Publications (2)

Publication Number Publication Date
CN102329626A CN102329626A (en) 2012-01-25
CN102329626B true CN102329626B (en) 2015-01-14

Family

ID=45481597

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110187805.8A Expired - Fee Related CN102329626B (en) 2010-06-30 2011-06-29 Liquid crystal aligning agent, method for forming liquid crystal alignment film, liquid crystal display device, and related compounds

Country Status (4)

Country Link
JP (1) JP5642435B2 (en)
KR (1) KR101654018B1 (en)
CN (1) CN102329626B (en)
TW (1) TWI502029B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6492982B2 (en) * 2014-08-29 2019-04-03 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0539901A1 (en) * 1991-10-29 1993-05-05 Japan Synthetic Rubber Co., Ltd. Process for producing thermoplastic resin
CN1312847A (en) * 1998-08-10 2001-09-12 美国3M公司 Tristable liquid crystal display device
CN101261403A (en) * 2007-03-06 2008-09-10 Jsr株式会社 Liquid crystal oriented agent and liquid crystal display element
CN101735825A (en) * 2008-11-17 2010-06-16 Jsr株式会社 Liquid crystal aligning agent, polyorganosiloxane, liquid crystal aligning film, forming method thereof and liquid crystal display element

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2018A (en) * 1841-03-26 Joseph francis
JPS5691277A (en) 1979-12-25 1981-07-24 Citizen Watch Co Ltd Liquiddcrystal display panel
JPS63291922A (en) 1987-05-26 1988-11-29 Japan Synthetic Rubber Co Ltd Production of curable polymer
JPH01120528A (en) 1987-11-04 1989-05-12 Alps Electric Co Ltd Liquid crystal element
SG64893A1 (en) 1993-02-17 1999-08-17 Rolic Ag Orientating layers for liquid crystals
JP2872628B2 (en) 1996-02-05 1999-03-17 スタンレー電気株式会社 Manufacturing method of liquid crystal display element
JP3893659B2 (en) 1996-03-05 2007-03-14 日産化学工業株式会社 Liquid crystal alignment treatment method
EP0806698B1 (en) 1996-05-08 2005-01-12 Hitachi, Ltd. In-plane switching-mode active-matrix liquid crystal display
JP4126731B2 (en) 1997-03-13 2008-07-30 Ｊｓｒ株式会社 Liquid crystal alignment agent
KR100261119B1 (en) 1997-04-18 2000-08-01 김순택 Optical alignment polymer
JP4134362B2 (en) 1997-11-19 2008-08-20 Ｊｓｒ株式会社 Liquid crystal alignment agent
JP4099522B2 (en) 1998-11-12 2008-06-11 Ｊｓｒ株式会社 Liquid crystal alignment agent
JP4094764B2 (en) 1999-03-30 2008-06-04 Ｊｓｒ株式会社 Liquid crystal alignment agent
JP2000319510A (en) 1999-05-14 2000-11-21 Jsr Corp Liquid crystal alignment agent and liquid crystal alignment treatment
JP3883848B2 (en) 2000-11-24 2007-02-21 香港科技大学 Method for producing photo-alignment film
JP3985261B2 (en) 2001-10-03 2007-10-03 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
JP3849138B2 (en) 2002-02-18 2006-11-22 Ｊｓｒ株式会社 Liquid crystal aligning agent, method for forming liquid crystal aligning film, and liquid crystal display element
JP2003313189A (en) * 2002-04-22 2003-11-06 Fuji Photo Film Co Ltd Optically active isosorbide derivative and method for producing the same, photoreactive chiral agent, liquid crystal composition, liquid crystal color filter, optical film and recording medium, method for changing spiral structure of liquid crystal and method for fixing spiral structure of liquid crystal
JP4104938B2 (en) 2002-08-28 2008-06-18 Ｄｉｃ株式会社 Composition for vertical alignment film and method for producing vertical alignment film
JP3885714B2 (en) 2002-11-13 2007-02-28 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
US20050054757A1 (en) * 2003-09-10 2005-03-10 Pearson Jason Clay Method for reducing the acetaldehyde level in polyesters
JP5668904B2 (en) 2008-09-18 2015-02-12 Jsr株式会社 Liquid crystal aligning agent and liquid crystal display element
JP2011153117A (en) * 2010-01-28 2011-08-11 Tokyo Institute Of Technology Fused ring aromatic polymer, and method for producing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0539901A1 (en) * 1991-10-29 1993-05-05 Japan Synthetic Rubber Co., Ltd. Process for producing thermoplastic resin
CN1312847A (en) * 1998-08-10 2001-09-12 美国3M公司 Tristable liquid crystal display device
CN101261403A (en) * 2007-03-06 2008-09-10 Jsr株式会社 Liquid crystal oriented agent and liquid crystal display element
CN101735825A (en) * 2008-11-17 2010-06-16 Jsr株式会社 Liquid crystal aligning agent, polyorganosiloxane, liquid crystal aligning film, forming method thereof and liquid crystal display element

Also Published As

Publication number Publication date
JP2012013861A (en) 2012-01-19
CN102329626A (en) 2012-01-25
TWI502029B (en) 2015-10-01
TW201300460A (en) 2013-01-01
KR101654018B1 (en) 2016-09-05
JP5642435B2 (en) 2014-12-17
KR20120002431A (en) 2012-01-05

Similar Documents

Publication Publication Date Title
CN101812303B (en) Liquid crystal aligning agent, forming liquid crystal aligning film, and liquid crystal display unit
CN102732263B (en) Liquid crystal orienting agent, liquid crystal orienting film and liquid crystal display element
CN102241991B (en) Liquid crystal aligning agent, liquid crystal alignment layer manufacturing method and liquid crystal display device
CN101735825B (en) Liquid crystal aligning agent, polyorganosiloxane, liquid crystal aligning film, forming method thereof and liquid crystal display element
CN102268264B (en) The formation method of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal orientation film, liquid crystal display device and polyorganosiloxane compounds
CN102337140B (en) Liquid crystal aligning agent for retardation film, liquid crystal alignment film for retardation film, and retardation film and process for production thereof
CN101821671B (en) Liquid crystal aligning agent, method for producing liquid crystal alignment film, and liquid crystal display device
CN101851516B (en) Liquid crystal aligning agent and liquid crystal display device
CN102618299B (en) Liquid crystal aligning agent, liquid crystal display device, liquid crystal orientation film and polyorganosiloxane compounds
CN102604652B (en) Liquid crystal aligning agent, liquid crystal display device and manufacture method thereof
CN103980911B (en) Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells and its manufacture method
CN101805618B (en) Liquid crystal aligning agent, process for forming liquid crystal aligning film, liquid crystal display device, process for producing liquid crystal display device
CN102385192B (en) The manufacture method of cholesteric lcd display, cholesteric lcd display and aligning agent for liquid crystal
CN102241989B (en) Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display device and polyorganosilioxane compound
CN103289711B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device
CN102041007B (en) Liquid crystal aligning agent, liquid crystal display element and polyorganosiloxane compound
CN102533280B (en) Liquid crystal aligning agent and liquid crystal display element
CN102559209B (en) The formation method of liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
CN102591070B (en) Liquid crystal display cells and alignment agent
CN102329626B (en) Liquid crystal aligning agent, method for forming liquid crystal alignment film, liquid crystal display device, and related compounds
CN102311738B (en) Liquid crystal aligning agent, method for forming liquid crystal alignment film, liquid crystal display device, and related compounds
CN103525436A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150114

Termination date: 20200629

CF01 Termination of patent right due to non-payment of annual fee