CN102268264B - The formation method of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal orientation film, liquid crystal display device and polyorganosiloxane compounds - Google Patents

The formation method of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal orientation film, liquid crystal display device and polyorganosiloxane compounds Download PDF

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CN102268264B
CN102268264B CN201110152309.9A CN201110152309A CN102268264B CN 102268264 B CN102268264 B CN 102268264B CN 201110152309 A CN201110152309 A CN 201110152309A CN 102268264 B CN102268264 B CN 102268264B
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CN102268264A (en
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秋池利之
中田正一
平井刚
菅野尚基
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JSR Corp
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    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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    • C09K19/56—Aligning agents
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    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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Abstract

The present invention relates to a kind of liquid crystal aligning agent, liquid crystal orientation film, the formation method of liquid crystal orientation film, liquid crystal display device and polyorganosiloxane compounds.The invention provides a kind of liquid crystal orientation film fully met as characteristics such as liquid crystal aligning, voltage retention and the photostabilization required by liquid crystal display device is in practical; The formation method of this liquid crystal orientation film; The storage stability being suitable as the formation material of liquid crystal orientation film is excellent, and optical alignment method can be adopted to form the liquid crystal aligning agent of liquid crystal orientation film; And possess the liquid crystal display device of liquid crystal orientation film.The present invention is a kind of liquid crystal aligning agent, and it contains [A] has the polyorganosiloxane compounds of at least one structure selected in the group be made up of piperidine structure, phenol structure or aniline structure.

Description

The formation method of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal orientation film, liquid crystal display device and polyorganosiloxane compounds
Technical field
The present invention relates to a kind of be suitable as liquid crystal aligning film formation material liquid crystal aligning agent, the polyorganosiloxane compounds used in this liquid crystal aligning agent, the liquid crystal orientation film formed by this liquid crystal aligning agent, the forming method and possess the liquid crystal display device of this liquid crystal orientation film of liquid crystal orientation film.
Background technology
It is little that liquid crystal display device has power consumption, and the advantages such as easy miniaturization and complanation, therefore can be widely used in the liquid crystal indicator such as portable phone, LCD TV.As the display mode of liquid crystal indicator, such as, in patent documentation 1 ~ 4, disclose the change according to liquid crystal molecular orientation state, and there is the liquid crystal display device of the liquid crystal cell such as switch type (IPS type), vertical orientating type (VA type) in twisted nematic (TN type), super-twist nematic (STN type), face.
The operation logic of above-mentioned various liquid crystal display device can roughly divide into infiltration type and reflection-type.Infiltration type is by showing from the backlight at the element back side.The liquid crystal orientation film that this permeation type liquid crystal display element possesses, owing to being exposed to the light from backlight for a long time, therefore when using the high backlight of the exposure intensities such as metal halide lamp to irradiate, has the defect relating to temperature rising and generation.On the other hand, reflection-type does not use backlight, but is shown by the reflected light from the light of outside such as sunlight, therefore little power consumption compared with infiltration type, but it is exposed to intensive ultraviolet always.In addition, in the manufacturing process of liquid crystal display device, consider from viewpoints such as reduction steps, the liquid crystal drop under type that can adopt, comprises uviolizing operation.Therefore, any one liquid crystal display device all requires excellent thermotolerance and photostabilization.In addition, liquid crystal display device in recent years also wishes that its electrical specification such as liquid crystal aligning, voltage retention is excellent, and can not produce image retention problem.
Therefore, have developed and a kind of to be formed by specific polysiloxane solution, the technology (reference patent documentation 5) of thermotolerance and the excellent liquid crystal orientation film of photostabilization.But along with manufacturing environment and environment for use are more and more stricter in recent years, even if adopt this technology also cannot meet above-mentioned requirements performance, the storage stability of coating fluid is also not enough in addition, is therefore not easy to use in the industry.
In view of this situation, wish that exploitation is a kind of and in practical, fully meet the characteristics such as required liquid crystal aligning, voltage retention and photostabilization as liquid crystal display device, and the liquid crystal aligning agent that the storage stability of optical alignment method formation liquid crystal orientation film can be adopted excellent.
Prior art
[patent documentation]
[patent documentation 1] Japanese Unexamined Patent Publication 4-153622 publication
[patent documentation 2] Japanese Laid-Open Patent Publication 60-107020 publication
[patent documentation 3] Japanese Laid-Open Patent Publication 56-91277 publication
[patent documentation 4] U.S. No. 5928733 patent
[patent documentation 5] Japanese Unexamined Patent Publication 9-281502 publication
[patent documentation 6] Japanese Unexamined Patent Publication 6-287453 publication
[patent documentation 7] Japanese Unexamined Patent Publication 2003-307736 publication
[patent documentation 8] Japanese Unexamined Patent Publication 2004-163646 publication
Summary of the invention
The present invention is based on above-mentioned situation and carry out, its objective is and a kind of liquid crystal orientation film fully meeting the characteristics such as required liquid crystal aligning, voltage retention and photostabilization as liquid crystal display device in practical is provided; The formation method of this liquid crystal orientation film; The storage stability being suitable as liquid crystal aligning film formation material is excellent, and optical alignment method can be adopted to form the liquid crystal aligning agent of liquid crystal orientation film; And possess the liquid crystal display device of liquid crystal orientation film.
Invention for solving the problem is a kind of liquid crystal aligning agent, and it contains [A] polyorganosiloxane compounds with piperidine structure, phenol structure or aniline structure.
The storage stability of this liquid crystal aligning agent is excellent, and the liquid crystal orientation film formed by this liquid crystal aligning agent fully meets the characteristics such as required liquid crystal aligning, voltage retention and photostabilization as liquid crystal display device in practical.
Above-mentioned piperidine structure is preferably represented by following formula (A-1 '), and phenol structure optimization is represented by following formula (A-2 '), and aniline structure is preferably represented by following formula (A-3 ').
(formula (A-1 ') in,
R 1for aralkyl or 1,3-bis-oxygen-butyl that hydrogen atom, the carbonatoms alkyl that is 1 ~ 6, the carbonatoms aryl that is 6 ~ 20, carbonatoms are 7 ~ 13.
R 2~ R 5the alkyl, the carbonatoms that are 1 ~ 6 for carbonatoms be independently of one another 6 ~ 12 aryl or carbonatoms be the aralkyl of 7 ~ 13.
X 1for singly-bound, carbonyl or * *-CONH-.X 2~ X 5be singly-bound, carbonyl, * *-CH independently of one another 2-CO-or * *-CH 2-CH (OH)-.Connecting key represented by * is connected with piperidine ring.
Main chain or the side chain of * represented connecting key and organopolysiloxane skeleton are connected.)
(formula (A-2 ') in, R 6for carbonatoms is the alkyl of 1 ~ 16.Further, abovementioned alkyl can have Sauerstoffatom, sulphur atom, carbonyl, ester group or by the two or more groups combined in them in skeletal chain.N is the integer of 0 ~ 4.Main chain or the side chain of * represented connecting key and organopolysiloxane skeleton are connected.)
(formula (A-3 ') in, R 7and R 8independently of one another for carbonatoms is the alkyl of 1 ~ 16.Further, abovementioned alkyl can have Sauerstoffatom, sulphur atom, carbonyl, ester group or by the two or more groups combined in them in skeletal chain.Main chain or the side chain of * represented connecting key and organopolysiloxane skeleton are connected.)
In this liquid crystal aligning agent, [A] polyorganosiloxane compounds, preferably containing the part coming from least one selected in the group that is made up of the condenses of the organopolysiloxane of the structural unit had represented by following formula (1), its hydrolyzate and this hydrolyzate, and come from the part of at least one compound selected in group that the compound represented by following formula (A-1), formula (A-2) and formula (A-3) forms.
(in formula (1), X afor having 1 valency organic group of epoxy group(ing).Y afor hydroxyl, carbonatoms be 1 ~ 10 alkoxyl group, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the aryl of 6 ~ 20.)
(in formula (A-1), R 1~ R 5and X 1~ X 5with above-mentioned formula (A-1 ') synonym.
In formula (A-2), R 6with above-mentioned formula (A-2 ') synonym.
In formula (A-3), R 7and R 8with above-mentioned formula (A-3 ') synonym.
In formula (A-1) ~ (A-3), Y is singly-bound, carbonatoms is the alkane 2 basis of 1 ~ 16.Further, above-mentioned alkane 2 basis can have Sauerstoffatom, sulphur atom, carbonyl, ester group, amide group or by the two or more groups combined in them in the structure.Z is carboxyl or hydroxyl.)
In this liquid crystal aligning agent, [A] polyorganosiloxane compounds is due to containing the part coming from least one selected in the group that is made up of the condenses of the organopolysiloxane of the structural unit had represented by above-mentioned formula (1), its hydrolyzate and this hydrolyzate, the structure that therefore easily piperidine structure etc. can be had radical-scavenging ability imports in [A] polyorganosiloxane compounds, thus improves photostabilization.
In this liquid crystal aligning agent, the X in above-mentioned formula (1) a, be preferably following formula (X a-1) or formula (X a-2) group represented by, and be more preferably following formula (X a-1-1) or (X a-2-1) represented by group.
(formula (X a-1) and formula (X a-2), in, s is the integer of 0 ~ 3.T is the integer of 1 ~ 6.U is the integer of 0 ~ 2.V is the integer of 0 ~ 6.* represented connecting key is connected with Siliciumatom.)
(formula (X a-1-1) and formula (X a-2-1) in, the connecting key represented by * is connected with Siliciumatom.)
By adopting above-mentioned special groups as the above-mentioned 1 valency organic group with epoxy group(ing), be easy to the part of the compound come from represented by above-mentioned formula (A-1), formula (A-2) or formula (A-3) to import in [A] polyorganosiloxane compounds of this liquid crystal aligning agent.
In this liquid crystal aligning agent, [A] polyorganosiloxane compounds preferably comprises the structure with liquid crystal aligning energy.[A] polyorganosiloxane compounds, by comprising the structure with liquid crystal aligning energy, can improve liquid crystal aligning energy further.
Above-mentioned have liquid crystal aligning can structure, the fluoro-alkyl that the alkyl that organic group, carbonatoms that preferably to have by the carbonatoms with steroid skeleton be 17 ~ 51 are 2 ~ 20, carbonatoms are 1 ~ 20, cyclohexyl, to have alkoxy aryl that carbonatoms is the alkyl of 2 ~ 20, have alkyl-cyclohexyl that carbonatoms is the alkyl of 1 ~ 20, have fluoro-alkyl cyclohexyl that carbonatoms is the fluoro-alkyl of 1 ~ 20 and have carbonatoms be at least one group selected in the group that forms of the fluoroalkyl cyclohexyl of the fluoroalkyl of 1 ~ 20.There is the structure of liquid crystal aligning energy, by having above-mentioned special groups (following, to be sometimes referred to as " liquid crystal aligning group "), more excellent liquid crystal aligning energy can be given to this liquid crystal aligning agent.
The above-mentioned structure with liquid crystal aligning energy, preferably has the structure represented by following formula (B-1).
(in formula (B-1), m is the integer of 0 ~ 4.)
Because the structure with liquid crystal aligning energy has above-mentioned ad hoc structure, even if therefore by optical alignment method, also liquid crystal orientation film can be formed by this liquid crystal aligning agent.
This liquid crystal aligning agent, at least one polymkeric substance selected in the group be preferably made up of polyamic acid and polyimide containing [B] further (following, to be sometimes referred to as " [B] polymkeric substance ").By using the liquid crystal aligning agent further containing [B] polymkeric substance to make liquid crystal orientation film, the liquid crystal display device that the electrical specifications such as voltage retention are improved further can be obtained.
This liquid crystal aligning agent preferably has the polyorganosiloxane compounds (following, to be sometimes referred to as " [C] other polyorganosiloxane compounds ") of the structural unit represented by following formula (2) further containing [C].
(in formula (2), X bfor hydroxyl, halogen atom, carbonatoms be 1 ~ 20 alkyl, carbonatoms be 1 ~ 6 alkoxyl group or carbonatoms be the aryl of 6 ~ 20.Y bfor hydroxyl or carbonatoms are the alkoxyl group of 1 ~ 10.)
This liquid crystal aligning agent, by further containing [C] other polyorganosiloxane compounds, can promote the crosslinked of [A] polyorganosiloxane compounds, thus can improve the voltage retention etc. of the liquid crystal display device of gained further.
The formation method of liquid crystal orientation film of the present invention, has:
(1) liquid crystal aligning agent comprising [A] polyorganosiloxane compounds is coated on substrate, form the operation of film, be somebody's turn to do the structure with liquid crystal aligning energy that [A] polyorganosiloxane compounds comprises the structure had represented by above-mentioned formula (B-1), and
(2) to the operation of irradiating radioactive rays at least partially of the film that operation (1) is formed.
By using the formation method of the present invention of this liquid crystal aligning agent, the liquid crystal orientation film fully meeting the characteristics such as required liquid crystal aligning, voltage retention and photostabilization as liquid crystal display device in practical can be formed.
The liquid crystal orientation film formed by this liquid crystal aligning agent and the liquid crystal display device possessing this liquid crystal orientation film also suitably comprise in the present invention.Possess the liquid crystal display device of the application of the liquid crystal orientation film formed by this liquid crystal aligning agent, can suitably for display unit such as such as clock and watch, portable game machine, word processor, notebook computer, auto-navigation system, pick up camera, portable data assistance, digital camera, mobile telephone, various indicating meter, LCD TV.
In addition, above-mentioned R 1aralkyl, R that the aryl that represented carbonatoms is 6 ~ 20, carbonatoms are 7 ~ 13 2~ R 5part or all of the aryl that the alkyl that represented carbonatoms is 1 ~ 6, carbonatoms are 6 ~ 12 and the hydrogen atom that the aralkyl that carbonatoms is 7 ~ 13 has can be substituted.
According to the present invention, can provide a kind of as liquid crystal display device fully meet in practical the liquid crystal orientation film of the characteristics such as required liquid crystal aligning, voltage retention and photostabilization, this liquid crystal orientation film formation method, be suitable as liquid crystal aligning film formation material storage stability excellent, and optical alignment method can be adopted to form the liquid crystal aligning agent of liquid crystal orientation film and possess the liquid crystal display device of liquid crystal orientation film.Possess the liquid crystal display device of the application of the liquid crystal orientation film formed by this liquid crystal aligning agent, can suitably for display unit such as such as clock and watch, portable game machine, word processor, notebook computer, auto-navigation system, pick up camera, portable data assistance, digital camera, mobile telephone, various indicating meter, LCD TV.
Embodiment
Below, embodiments of the present invention are described in detail.
< liquid crystal aligning agent >
Liquid crystal aligning agent of the present invention, containing [A] polyorganosiloxane compounds with at least one structure selected in the group that is made up of piperidine structure, phenol structure or aniline structure.The storage stability of this liquid crystal aligning agent is excellent, the liquid crystal orientation film formed by this liquid crystal aligning agent, fully meets the characteristics such as required liquid crystal aligning, voltage retention and photostabilization as liquid crystal display device in practical.In addition, [A] polyorganosiloxane compounds preferably comprises the structure with liquid crystal aligning energy, and this liquid crystal aligning agent is preferably (following containing the polymkeric substance beyond [A] polyorganosiloxane compounds, be sometimes referred to as " other polymkeric substance "), further, only otherwise damage effect of the present invention, this liquid crystal aligning agent can contain optional member.Below, [A] polyorganosiloxane compounds, the structure with liquid crystal aligning energy, other polymkeric substance and optional member are described in detail.
< [A] polyorganosiloxane compounds >
[A] polyorganosiloxane compounds, has at least one structure selected in the group be made up of piperidine structure, phenol structure or aniline structure.In addition, [A] polyorganosiloxane compounds is preferably (following containing the organopolysiloxane coming from the structural unit had represented by above-mentioned formula (1), be sometimes referred to as " organopolysiloxane with epoxy group(ing) ") part, and come from the part of at least one compound selected in group that the compound represented by above-mentioned formula (A-1), formula (A-2) and formula (A-3) forms.This [A] polyorganosiloxane compounds, can by having the reaction of the compound represented by the organopolysiloxane of epoxy group(ing) and above-mentioned formula (A-1), formula (A-2) or formula (A-3) and obtaining.In this liquid crystal aligning agent, [A] polyorganosiloxane compounds, due to containing the part coming from least one selected in the group that is made up of the condenses of the organopolysiloxane of the structural unit had represented by above-mentioned formula (1), its hydrolyzate and this hydrolyzate, the structure that therefore easily piperidine structure etc. can be had radical-scavenging ability imports in [A] polyorganosiloxane compounds, thus improves photostabilization.Below, the organopolysiloxane with piperidine structure, phenol structure, aniline structure and epoxy group(ing) is described in detail.
[piperidine structure]
As the piperidine structure that [A] polyorganosiloxane compounds has, be preferably the structure represented by above-mentioned formula (A-1 ').
There is [A] polyorganosiloxane compounds of this piperidine structure, can by there is the reaction of the compound represented by the organopolysiloxane of epoxy group(ing) and above-mentioned formula (A-1) and obtaining.
As above-mentioned R 1~ R 5represented carbonatoms is the alkyl of 1 ~ 6, can be straight-chain or branched any one, can enumerate such as methyl, ethyl, propyl group, butyl, amyl group, hexyl etc.
As above-mentioned R 1represented carbonatoms is the aryl of 6 ~ 20, can enumerate such as phenyl, naphthyl, aminobenzoic acid etc.In addition, part or all alkoxyl group being preferably 1 ~ 4 by formyl radical or carbonatoms of hydrogen atom that the aromatic nucleus of aryl has replaces.
As above-mentioned R 1~ R 5represented carbonatoms is the aralkyl of 7 ~ 13, can enumerate such as benzyl, styroyl etc.In addition, part or all alkoxyl group being preferably 1 ~ 4 by formyl radical or carbonatoms of hydrogen atom that the aromatic nucleus of aralkyl has replaces.
As above-mentioned R 2~ R 5represented carbonatoms is the aryl of 6 ~ 12, can enumerate such as phenyl, naphthyl etc.In addition, part or all alkoxyl group being preferably 1 ~ 4 by formyl radical or carbonatoms of hydrogen atom that the aromatic nucleus of aryl has replaces.
As above-mentioned R 2~ R 5represented carbonatoms is the alkoxyl group of 1 ~ 4, can enumerate such as methoxyl group, oxyethyl group, positive propoxy etc.
As the Z in above-mentioned formula (A-1), be preferably carboxyl, such as, the compound represented by following formula (A-1-1) ~ (A-1-4), can be enumerated as the preference of formula (A-1).
As the ratio of (A-1 ') structure in [A] polyorganosiloxane compounds, relative to X a, be preferably 2 % by mole ~ 80 % by mole, be more preferably 5 % by mole ~ 75 % by mole, and be particularly preferably 25 % by mole ~ 60 % by mole.
[phenol structure]
As the phenol structure that [A] polyorganosiloxane compounds has, be preferably the structure represented by above-mentioned formula (A-2 ').
There is [A] polyorganosiloxane compounds of this phenol structure, can by there is the reaction of the compound represented by the organopolysiloxane of epoxy group(ing) and above-mentioned formula (A-2) and obtaining.
As above-mentioned R 6represented carbonatoms is the alkyl of 1 ~ 16, can be straight-chain or branched any one, can enumerate such as methyl, ethyl, propyl group, butyl, amyl group, hexyl etc.
As the Z in above-mentioned formula (A-2), be preferably carboxyl, such as, the compound represented by following formula (A-2-1) ~ (A-2-7), can be enumerated as the preference of formula (A-2).
As the ratio of (A-2 ') structure in [A] polyorganosiloxane compounds, relative to X a, be preferably 10 % by mole ~ 90 % by mole, be more preferably 20 % by mole ~ 80 % by mole, and be particularly preferably 25 % by mole ~ 75 % by mole.
[aniline structure]
As the aniline structure that [A] polyorganosiloxane compounds has, be preferably the structure represented by above-mentioned formula (A-3 ').
There is [A] polyorganosiloxane compounds of this aniline structure, can by there is the reaction of the compound represented by the organopolysiloxane of epoxy group(ing) and above-mentioned formula (A-3) and obtaining.
As above-mentioned R 7and R 8represented carbonatoms is the alkyl of 1 ~ 16, can enumerate the alkyl identical with alkyl illustrated in above-mentioned formula (A-2).
As the Z in above-mentioned formula (A-3), be preferably carboxyl, such as, the compound represented by following formula (A-3-1) ~ (A-3-8), can be enumerated as the preference of formula (A-3).
As the ratio of (A-3 ') structure in [A] polyorganosiloxane compounds, relative to X a, be preferably 10 % by mole ~ 90 % by mole, be more preferably 20 % by mole ~ 80 % by mole, and be particularly preferably 25 % by mole ~ 75 % by mole.
[there is the organopolysiloxane of epoxy group(ing)]
There is the organopolysiloxane of epoxy group(ing), refer in the structure of [A] polyorganosiloxane compounds, comprise the organopolysiloxane skeleton as main polymer chain, and from this organopolysiloxane branch out as main polymer chain containing the concept of epoxy group(ing) skeleton.
As the X in above-mentioned formula (1) athe represented 1 valency organic group with epoxy group(ing), as long as have 1 valency organic group of epoxy group(ing), is just not particularly limited, can enumerates the group etc. such as comprising glycidyl, glycidoxypropyl, expoxycyclohexyl.Wherein, X abe preferably above-mentioned formula (X a-1) or (X a-2) group represented by, and be more preferably above-mentioned formula (X a-1-1) or (X a-2-1) represented by group.By adopting above-mentioned special groups as the above-mentioned 1 valency organic group with epoxy group(ing), be easy to the part of the compound come from represented by above-mentioned formula (A-1), formula (A-2) or formula (A-3) to import in [A] polyorganosiloxane compounds of this liquid crystal aligning agent.
As the Y in above-mentioned formula (1) arepresented carbonatoms is the alkoxyl group of 1 ~ 10, can enumerate such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy etc.
As the Y in above-mentioned formula (1) arepresented carbonatoms is the alkyl of 1 ~ 20, can enumerate such as straight-chain or branched methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, lauryl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc.
As the Y in above-mentioned formula (1) arepresented carbonatoms is the aryl of 6 ~ 20, can enumerate such as phenyl, naphthyl etc.
[there is the synthetic method of the organopolysiloxane of epoxy group(ing)]
There is the organopolysiloxane of epoxy group(ing), can by preferably under the existence of suitable organic solvent, water and catalyzer, preferably 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 or hydrolytic condensation and synthesizing.
As the silane compound with epoxy group(ing), such as 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl dimethyl methoxy silane, 3-glycidoxypropyl dimethylethoxysilane, 2-(3 can be enumerated, 4-expoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-expoxycyclohexyl) ethyl triethoxysilane etc.They can be used alone or are used in combination of two or more.
As other silane compound, 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, chlorine trimethyl silane, trimethylammonium bromide silane, iodine trimethyl silane, 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 etc. of 1 Siliciumatom.They can be used alone or are used in combination of two or more.
As the material of commodity purchasing, can enumerate 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, chemical industrial company of SHIN-ETSU HANTOTAI),
グ ラ ス レ ジ Application (Showa electrician company);
SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above ， East レ ダ ウ コ mono-ニ Application グ society);
FZ3711, FZ3722 (more than, Japanese ユ ニ power one society);
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 company);
Methyl silicate MS51, methyl silicate MS56 (more than, Mitsubishi Chemical Ind);
Tetraethyl silicate 28, ethyl silicate 40, tetraethyl silicate 48 (more than, コ Le コ mono-ト company);
The partial condensate of GR100, GR650, GR908, GR950 (more than, Showa electrician company) etc.
In these other silane compounds, preferred 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, dimethyldimethoxysil,ne or dimethyldiethoxysilane.
As the epoxy equivalent (weight) of organopolysiloxane with epoxy group(ing), be preferably 100g/ mole ~ 10000g/ mole, be more preferably 150g/ mole ~ 1000g/ mole, and be particularly preferably 150g/ mole ~ 300g/ mole.Therefore, when synthesis has the organopolysiloxane of epoxy group(ing), as the usage ratio of the silane compound He other silane compound with epoxy group(ing), be preferably set to and make the epoxy equivalent (weight) of the organopolysiloxane of gained reach above-mentioned scope.
As the operable organic solvent when synthesis has the organopolysiloxane of epoxy group(ing), such as hydrocarbon compound, ketone compound, ester cpds, ether compound, alkylol cpd etc. can be enumerated.They can be used alone or are used in combination of two or more.
As hydrocarbon compound, such as toluene, dimethylbenzene etc. can be enumerated.
As ketone compound, such as methylethylketone, mibk, MAK, diethyl ketone, pimelinketone etc. can be enumerated.
As ester cpds, such as ethyl acetate, n-butyl acetate, Isoamyl Acetate FCC, propylene glycol methyl ether acetate, 3-methoxybutyl acetic ester, ethyl lactate etc. can be enumerated.
As ether compound, such as glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), dioxan etc. can be enumerated.
As alkylol cpd, 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.
As the usage quantity of organic solvent, relative to the whole silane compound of 100 mass parts, be preferably 10 mass parts ~ 10000 mass parts, and be more preferably 50 mass parts ~ 1000 mass parts.
As the water usage quantity of synthesizing when there is the organopolysiloxane of epoxy group(ing), relative to whole silane compound, be preferably 0.5 times mole ~ 100 times moles, and be more preferably 1 times mole ~ 30 times moles.
As catalyzer, such as acid, alkali metal compound, organic bases, titanium compound, zirconium compounds etc. can be enumerated.They can be used alone or are used in combination of two or more.
As alkali metal compound, such as sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate etc. can be enumerated.
As 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;
The organic quaternary ammonium etc. such as Tetramethylammonium hydroxide.
As the catalyzer manufactured 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 organopolysiloxane with high hydrolytic condensation speed, therefore production stability is excellent.
In addition, this liquid crystal aligning agent of the reactant of the compound represented by distinguishing containing the organopolysiloxane with epoxy group(ing) using alkali metal compound or organic bases synthesize as catalyzer and above-mentioned formula (A-1), formula (A-2) or formula (A-3), because storage stability is extremely excellent, therefore highly beneficial.Its reason can be speculated as, as science (the ア グ ネ Cheng Wind society of sol-gel method, 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.That is can infer, because the silanol base of this organopolysiloxane is containing proportional few, therefore silanol groups condensation reaction each other can be suppressed, 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 more preferably organic bases, and be particularly preferably trimethylamine and organic quaternary ammonium.As the usage quantity of organic bases, different according to the reaction conditions such as kind, temperature of organic bases, such as, relative to whole silane compound, be preferably 0.01 times mole ~ 3 times moles, and be more preferably 0.05 times mole ~ 1 times mole.
Synthesize hydrolysis when there is the organopolysiloxane of epoxy group(ing) or hydrolysis-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 and water, and is implemented by heating such as such as oil baths.
As the Heating temperature of oil bath during hydrolysis-condensation reaction, be preferably less than 130 DEG C, and be more preferably 40 DEG C ~ 100 DEG C.As heat-up time, be preferably 0.5 hour ~ 12 hours, and be more preferably 1 hour ~ 8 hours.Add and hanker, can liquid be uniformly mixed, also can reflux.
After reaction terminates, preferably wash the organic solvent layer separated from reaction solution with water.During washing, use the water containing a small amount of salt, such as the aqueous ammonium nitrate solution etc. of about 0.2 quality % washs, and it is preferred for becoming easily this one side making washing operation.Wash, until the water layer after washing is in neutral, then uses the desiccant dryness such as anhydrous calciumsulphate, molecular sieve organic solvent layer 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 company) etc. can be enumerated.
The weight-average molecular weight of the polystyrene conversion measured by gel permeation chromatography as the organopolysiloxane with epoxy construction is (following, be sometimes referred to as " Mw "), be preferably 500 ~ 100000, be more preferably 1000 ~ 10000, and be particularly preferably 1000 ~ 5000.In addition, in this manual, Mw is the polystyrene conversion value measured by gel permeation chromatography described below.
Post: eastern ソ mono-company, TSKgelGRCXLII
Solvent: tetrahydrofuran (THF)
Temperature: 40 DEG C
Pressure: 6.8MPa
< has the structure > of liquid crystal aligning energy
In this liquid crystal aligning agent, [A] polyorganosiloxane compounds preferably comprises the structure with liquid crystal aligning energy.[A] polyorganosiloxane compounds, by comprising the structure with liquid crystal aligning energy, can improve liquid crystal aligning energy further.
As the group that the structure with liquid crystal aligning energy has, be preferably above-mentioned liquid crystal aligning group.There is the structure of liquid crystal aligning energy by having above-mentioned special groups, more excellent liquid crystal aligning energy can be given to this liquid crystal aligning agent.
Be the organic group of 17 ~ 51 as the above-mentioned carbonatoms with steroid skeleton, the carbonatoms preferably with steroid skeleton is the 1 valency organic group of 17 ~ 30, such as cholestane-3-base, courage steroid-5-alkene-3-base, courage steroid-24-alkene-3-base, courage steroid-5,24-diene-3-base, lanostane-3-base etc. can be enumerated.
Be the alkyl of 2 ~ 20 as above-mentioned carbonatoms, such as ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, positive decyl, positive lauryl, dodecyl, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, positive stearyl, NSC 62789 base etc. can be enumerated.As the carbonatoms of alkyl, be more preferably 4 ~ 20.
Be the fluoro-alkyl of 1 ~ 20 as above-mentioned carbonatoms, such as trifluoromethyl, perfluoro-ethyl, 3,3,3-trifluoro propyls, 4,4,4-triRuorobutyl, 4,4,5,5,5-five fluorine amyl groups, 3,3,4,4,5,5,5-seven fluorine amyl groups etc. can be enumerated.
As above-mentioned, there is the alkoxy aryl that carbonatoms is the alkyl of 2 ~ 20, can enumerate such as positive propoxy aryl, n-butoxy aryl, n-pentyloxy aryl, positive hexyloxy aryl, positive heptan oxygen Ji Fangji, n-octyloxy aryl etc.
As above-mentioned, there is the alkyl-cyclohexyl that carbonatoms is the alkyl of 1 ~ 20, such as n-propyl cyclohexyl, normal-butyl cyclohexyl, n-pentyl cyclohexyl, n-hexyl cyclohexyl, n-heptyl cyclohexyl, n-octyl cyclohexyl etc. can be enumerated.
As above-mentioned, there is the fluoro-alkyl cyclohexyl that carbonatoms is the fluoro-alkyl of 1 ~ 20, such as trifluoromethyl cyclohexyl etc. can be enumerated.
As above-mentioned, there is the fluoroalkyl cyclohexyl that carbonatoms is the fluoroalkyl of 1 ~ 20, such as 4,4,4-trifluoro butoxy cyclohexyl, 4,4,5,5,5-five fluorine pentyloxy cyclohexyl etc. can be enumerated.
There is the structure of liquid crystal aligning energy, preferably there is structure represented by above-mentioned formula (B-1) further.Due to the above-mentioned structure with liquid crystal aligning energy, there is specific structure, even if therefore by optical alignment method, also liquid crystal orientation film can be formed by this liquid crystal aligning agent.
Comprise have liquid crystal aligning can [A] polyorganosiloxane compounds of structure, can obtain by having the organopolysiloxane of epoxy group(ing) and the reaction with the compound of liquid crystal aligning energy represented by following formula (B-2).
R E-T(B-2)
In above-mentioned formula (B-2), R efor comprising the group of the structure with liquid crystal aligning energy.T is carboxyl or hydroxyl.
As the preferred example of above-mentioned formula (B-2), the compound such as represented by following formula (B-2-1) ~ (B-2-8) can be enumerated.
In above-mentioned formula (B-2-1), R ffor above-mentioned liquid crystal aligning group.X cfor singly-bound, Sauerstoffatom, sulphur atom, phenylene, cyclohexylidene ,-COO-,-NHCO-,-CONH-,-CO-,-OCO-or by the two or more linking groups combined in them.X dfor singly-bound, Sauerstoffatom, phenylene ,-CO-,-OCO-,-(CH 2) a-or by the two or more linking groups combined in them.A is the integer of 1 ~ 6.T and above-mentioned formula (B-2) synonym.
In above-mentioned formula (B-2-2), R f, X dand T, with above-mentioned formula (B-2-1) synonym.
X efor singly-bound, Sauerstoffatom, sulphur atom, phenylene ,-COO-,-NHCO-,-CONH-,-CO-,-OCO-or by the two or more linking groups combined in them.
In above-mentioned formula (B-2-3), R fwith T and above-mentioned formula (B-2-1) synonym.
X ffor singly-bound, Sauerstoffatom ,-CO-,-(CH 2) a-or by the two or more linking groups combined in them.A is the integer of 1 ~ 6.M is the integer of 0 ~ 4.
In above-mentioned formula (B-2-4) ~ (B-2-6), R fwith T and above-mentioned formula (B-2-1) synonym.
X gfor singly-bound, Sauerstoffatom, sulphur atom ,-COO-,-NHCO-,-CONH-,-CO-,-OCO-or by the two or more linking groups combined in them.
X hfor singly-bound, Sauerstoffatom, sulphur atom ,-(CH 2) a-,-CO-or by the two or more linking groups combined in them.A is the integer of 1 ~ 6.
In above-mentioned formula (B-2-7) and (B-2-8), R fwith T and above-mentioned formula (B-2-1) synonym.X jfor singly-bound, Sauerstoffatom ,-COO-,-OCO-,-(CH 2) a-or by the two or more linking groups combined in them.A is the integer of 1 ~ 6.
In addition, in above-mentioned formula (B-2-1) ~ (B-2-8), form O-O key or α, the substituent combination of beta-diketon structure is unallowed.
In above-mentioned formula (B-2-1) ~ (B-2-8), the compound represented by more preferably following formula (B-2-1-1) ~ formula (B-2-8-2).
In above-mentioned formula (B-2-1-1) ~ (B-2-8-2), R fwith above-mentioned formula (B-2-1) synonym.A is the integer of 1 ~ 6.
When comprising the group of the structure represented by above-mentioned formula (B-1), as have liquid crystal aligning can other preferred example of compound, the compound represented by such as following formula (B-2-1-1 ') ~ formula (B-2-8-1 ') can be enumerated.
In above-mentioned formula, R fwith above-mentioned formula (B-2-1) synonym.
On the other hand, as the R in above-mentioned formula (B-2) ehaving by the carbonatoms with steroid skeleton is the organic group of 17 ~ 51, carbonatoms is the alkyl of 2 ~ 20, carbonatoms is the fluoro-alkyl of 1 ~ 20, cyclohexyl, there is the alkoxy aryl that carbonatoms is the alkyl of 2 ~ 20, there is the alkyl-cyclohexyl that carbonatoms is the alkyl of 1 ~ 20, having fluoro-alkyl cyclohexyl that carbonatoms is the fluoro-alkyl of 1 ~ 20 and having carbonatoms is at least one selected in the group that forms of the fluoroalkyl cyclohexyl of the fluoroalkyl of 1 ~ 20, but the compound (B-2) do not contained during the structure represented by above-mentioned formula (B-1), be preferably the compound etc. represented by following formula (B-2-9) ~ formula (B-2-11).
R f-T(B-2-9)
R in above-mentioned formula (B-2-9) ~ formula (B-2-11) fand T, with above-mentioned formula (B-2-1) synonym.X kfor singly-bound, Sauerstoffatom ,-COO-or-OCO-.
In above-mentioned formula (B-2-11), p is 1 or 2.
Be the compound of carboxyl as T in above-mentioned formula (B-2-9), such as butanic acid, positive valeric acid, n-caproic acid, positive enanthic acid, n-caprylic acid, pelargonic acid, n-capric acid, positive lauric acid, positive laurostearic acid, positive tridecylic acid, positive TETRADECONIC ACID, positive pentadecanoic acid, n-hexadecanoic, margaric acid, positive stearic acid, positive nonadecanoic acid, positive 20 acid, tetrahydrogenated rosin sour, single cholestane base succinate, single cholestane base glutarate, compound etc. represented by following formula can be enumerated.
C hF 2h+1-C iH 2i-COOH
In above-mentioned formula, h is the integer of 1 ~ 3.I is the integer of 3 ~ 18.
Be the compound of hydroxyl as T in above-mentioned formula (B-2-9), such as n-butyl alcohol, 1-amylalcohol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-undecyl alcohol, 1-lauryl alcohol, 1-tridecanol, 1-tetradecyl alcohol, 1-pentadecanol, Cetyl OH, 1-heptadecyl alcohol, 1-stearyl alcohol, 1-nonadecanol, 1-eicosanol etc. can be enumerated.
Be the compound of carboxyl as T in above-mentioned formula (B-2-10), such as 4-tolyl acid can be enumerated, 4-ethyl benzoate, 4-n-propylbenzene formic acid, 4-n-butylbenzoic acid, 4-n-amylbenzene formic acid, 4-positive hexyl phenenyl formic acid, 4-n-heptylphenyl formic acid, 4-n-octyl formic acid, 4-n-nonyl phenylformic acid, the positive decyl phenylformic acid of 4-, 4-n-dodecane yl benzoic acid, 4-Octadecane yl benzoic acid, the positive methoxybenzoic acid of 4-, the positive ethoxybenzoic acid of 4-, 4-positive propoxy phenylformic acid, 4-n-butoxy phenylformic acid, 4-n-pentyloxy phenylformic acid, the positive hexyloxybenzoate of 4-, the positive heptyloxybenzene formic acid of 4-, 4-n-octyloxy phenylformic acid, 4-aminobenzoic acid in the positive ninth of the ten Heavenly Stems, 4-n-decyloxy phenylformic acid, 4-n-dodecane aminobenzoic acid, 4-Octadecane aminobenzoic acid, compound etc. represented by following formula.
In above-mentioned formula, j is the integer of 5 ~ 20.K is the integer of 1 ~ 3.Ma is the integer of 0 ~ 18.N is the integer of 1 ~ 18.
Be the compound of carboxyl as T in above-mentioned formula (B-2-11), such as 4-(normal-butyl) cyclohexane carboxylic acid, 4-(n-pentyl) cyclohexane carboxylic acid, 4-(normal-butyl) dicyclohexyl carboxylic acid, 4-(n-pentyl) dicyclohexyl carboxylic acid etc. can be enumerated.
< has the synthetic method > of the compound of liquid crystal aligning energy
Compound represented by above-mentioned formula (B-2-1) ~ formula (B-2-11), can obtain as commercially available product, or can by synthesizing appropriately combined for vitochemical ordinary method.Below, with R fcompound for alkyl is that example is described synthetic method, and for R ffor the compound beyond alkyl, also can to operate equally or synthetic method by referring to the method is synthesized, this is readily understood that for those skilled in the art.
Compound represented by above-mentioned formula (B-2-1-1), such as, can by under the existence of the suitable alkali such as salt of wormwood, Hydroxycinnamic acid is equivalent to R with having fthe haloalkyl of alkyl heat, make it react, be then hydrolyzed in the alkali aqueous solution that sodium hydroxide etc. is suitable and obtain.
Compound represented by above-mentioned formula (B-2-1-2), such as, can by making hydroxyl TRANSCINNAMIC ACID and have to be equivalent to R fthe alkyl acyl chloride of alkyl under the existence of the suitable alkali such as salt of wormwood, reaction at the temperature of 0 DEG C ~ room temperature and obtaining.
Compound represented by above-mentioned formula (B-2-1-4), such as, can by making methyl hydroxybenzoate and have to be equivalent to R fthe haloalkyl of alkyl or alkyl tosylate under the existence of the suitable alkali such as salt of wormwood, at the temperature of room temperature ~ 100 DEG C after reaction, be hydrolyzed in the alkali aqueous solution that sodium hydroxide etc. is suitable, and after being formed acyl chlorides by thionyl chloride further, make it react at the temperature of 0 DEG C ~ room temperature with hydroxyl TRANSCINNAMIC ACID under the existence of the suitable alkali such as salt of wormwood and obtain.
Compound represented by above-mentioned formula (B-2-1-5), such as, can by making hydroxy-benzoic acid and have to be equivalent to R fthe alkyl acyl chloride of alkyl under the existence of the suitable alkali such as triethylamine, at the temperature of 0 DEG C ~ room temperature after reaction, form acyl chlorides by thionyl chloride, and make it react at the temperature of 0 DEG C ~ room temperature with hydroxyl TRANSCINNAMIC ACID under the existence of the suitable alkali such as salt of wormwood and obtain.
Compound represented by above-mentioned formula (B-2-1-6), such as, can by 4-alkylbenzoic acid being formed acyl chlorides by thionyl chloride, and make it react at the temperature of 0 DEG C ~ room temperature with hydroxyl TRANSCINNAMIC ACID under the existence of the suitable alkali such as salt of wormwood and obtain.
Compound represented by above-mentioned formula (B-2-1-7), such as, can by making 4-hydroxy-cyclohexyl carboxylate methyl ester and have to be equivalent to R fthe haloalkyl of alkyl after reaction forms ether under the existence of the suitable alkali such as sodium hydride or sodium Metal 99.5, in alkali aqueous solution hydrolysis such as sodium hydroxide, after forming acyl chlorides by thionyl chloride further, it is made to react at the temperature of 0 DEG C ~ room temperature with hydroxyl TRANSCINNAMIC ACID under the existence of the suitable alkali such as salt of wormwood and obtain.
Compound represented by above-mentioned formula (B-2-1-8), such as, can be equivalent to R by having by thionyl chloride fthe 4-alkyl yl carboxylic acid of alkyl form acyl chlorides, and make it react at the temperature of 0 DEG C ~ room temperature with hydroxyl TRANSCINNAMIC ACID under the existence of the suitable alkali such as salt of wormwood and obtain.
Compound represented by above-mentioned formula (B-2-1-9), can be equivalent to R by making to have fthe haloalkyl of alkyl and hydroxy benzaldehyde react under the existence of the alkali such as salt of wormwood and form ehter bond, under sodium hydroxide exists, carry out aldol condensation with 4-acetylbenzoic acid and obtain.Compound represented by above-mentioned formula (B-2-1-10) ~ formula (B-2-1-15) can obtain by referring to the method for the method.
Compound represented by above-mentioned formula (B-2-2-1), such as, can by using palladium and amine as catalyzer, make 4-iodophenol be equivalent to R with having falkyl alkyl acrylate reaction (Heck reaction) after, the cyclic acid anhydride that Succinic anhydried or Pyroglutaric acid etc. are wished and resultant of reaction carry out open loop addition and obtain.
Compound represented by above-mentioned formula (B-2-2-2), can be equivalent to R by making to have fthe 4-alkylacetophenone of alkyl and 4-formylbenzoate under sodium hydroxide exist, carry out aldol condensation and obtain.Compound represented by above-mentioned formula (B-2-2-3) can obtain by referring to the method for the method.
Compound represented by above-mentioned formula (B-2-2-4), can be equivalent to R by making to have fthe 4-alkylacetophenone of alkyl and 4-hydroxy benzaldehyde under sodium hydroxide exist, carry out aldol condensation and obtain.Compound represented by above-mentioned formula (B-2-2-5) can obtain by referring to the method for the method.
Compound represented by above-mentioned formula (B-2-3-1), can pass through to use palladium catalyst, makes to have to be equivalent to R fthe acrylate of alkyl and the 4-bromine TRANSCINNAMIC ACID method of reacting and obtaining.By referring to the method for the method, the compound represented by above-mentioned formula (B-2-3-2) can also be obtained.
Compound represented by above-mentioned formula (B-2-4-1), such as, works as R fduring for alkyl, R can be equivalent to by making to have fthe dialkyl succinylsuccinate acid anhydride of alkyl and the condition that refluxes in acetic acid of the amino TRANSCINNAMIC ACID of 4-under or the method for reacting under the condition that refluxes in toluene or dimethylbenzene under the alkaline catalysts that triethylamine etc. is suitable exists and obtaining, work as R fduring for fluoro-alkyl, can by by after protection such as blocking group suitable for maleic anhydride para-totuidine etc., by being equivalent to R with having 1the Grignard reaction of fluoroalkyl iodide etc. of fluoro-alkyl carry out coupling after, by hydrolysis deprotection, after carrying out dehydration closed-loop, the method for reacting with the amino TRANSCINNAMIC ACID of 4-and obtaining.
Compound represented by above-mentioned formula (B-2-4-2), such as, can be synthesized by any one method following.As the first method, following method can be enumerated: by protection such as blocking group suitable for maleic anhydride para-totuidine etc., and make to have under the alkali suitable with salt of wormwood etc. exists and be equivalent to R fthe alcohol of alkyl carry out Michael addition with it after, by hydrolysis deprotection, carry out dehydration closed-loop further, and, this resultant reacted with 4-amino TRANSCINNAMIC ACID during compou nd synthesis represented by above-mentioned formula (B-2-4-1) similarly.As the second method, following method can be enumerated: make oxysuccinic acid methyl esters under existing and have to be equivalent to R at such as silver suboxide fthe haloalkyl reaction of alkyl formed after ether, is hydrolyzed, and carries out dehydration closed-loop further, and the synthetic method of compound represented by above-mentioned formula (B-2-4-1) operates equally, and this resultant is reacted with 4-amino TRANSCINNAMIC ACID.
Compound represented by above-mentioned formula (B-2-4-3), such as, is equivalent to R except using to have fthe mercaptan of alkyl replace having and be equivalent to R falkyl alcohol beyond, can operate equally with the first method during compou nd synthesis represented by above-mentioned formula (B-2-4-2) and obtain.
Compound represented by above-mentioned formula (B-2-5-1), such as, can by 1,2,4-tricarboxylic butylcyclohexane acid anhydride being formed after acyl chlorides by thionyl chloride, be equivalent to R with having falcohol reaction under the alkali that triethylamine etc. is suitable exists of alkyl carry out esterification, and and the synthetic method of compound represented by above-mentioned formula (B-2-4-1) operate equally, make this resultant react with 4-amino TRANSCINNAMIC ACID and obtain.
Compound represented by above-mentioned formula (B-2-6-1), such as, can by making the compound R corresponding to required compound f-OH and trimellitic acid 1,2-anhydride halide reaction, synthesize the ester cpds as intermediate, then makes this ester cpds and the amino TRANSCINNAMIC ACID of 4-react and synthesize.The synthesis of intermediate ester compound, preferably carries out in suitable solvent under basic cpd exists.As operable solvent, such as tetrahydrofuran (THF) etc. can be enumerated, as basic cpd, such as triethylamine etc. can be enumerated.The reaction of the amino TRANSCINNAMIC ACID of ester cpds and 4-, can enumerate the method such as making both reflux in acetic acid, the method etc. making both reflux under the existence of the suitable catalyzer alkaline catalystss such as acid catalyst or triethylamine such as () such as sulfuric acid in toluene or dimethylbenzene.
Compound represented by above-mentioned formula (B-2-6-2), after dehydration closed-loop formation acid anhydrides can being carried out by being refluxed in such as diethylbenzene by 5-hydroxyl phthalic, by reacting with above-mentioned same method and the amino TRANSCINNAMIC ACID of 4-, synthesize the imide compound as the first intermediate, and then make this imide compound and the compound R corresponding to required compound f-H (H is halogen atom) reaction is synthesized.Now, preferably in suitable solvent, carry out under basic cpd exists.As operable solvent, the amide compounds etc. such as such as N,N-dimethylacetamide can be enumerated, as basic cpd, such as salt of wormwood etc. can be enumerated.
Compound represented by above-mentioned formula (B-2-7-1), such as, can be equivalent to R with having by making 4-nitro TRANSCINNAMIC ACID in the presence of potassium carbonate fthe haloalkyl reaction of alkyl form ester, and use after such as this nitro of tin chloride reduction forms amino, make this resultant and 1,2,4-tri-carboxycyclohexyl hexanaphthene anhydride reactant and obtain.A rear reaction, such as, can be undertaken by the method refluxed in acetic acid by starting compound or the method refluxed in toluene or dimethylbenzene under the suitable alkaline catalystss such as triethylamine exist.By referring to the method for the method, the compound represented by above-mentioned formula (B-2-8-1) can be synthesized.
Compound represented by above-mentioned formula (B-2-8-2), can by the synthesis of the compound represented by above-mentioned formula (B-2-7-1), hydroxyl phthalic is used to replace 1,2,4-tri-carboxycyclohexyl hexanaphthene acid anhydride, after synthesis has the cinnamic acid derivative of imide ring, react with Succinic anhydried or Pyroglutaric acid and obtain.
Compound represented by above-mentioned formula (B-2-1-1 '), can be equivalent to R by making to have fthe haloalkyl of alkyl and 4-hydroxy benzaldehyde react under the alkali such as salt of wormwood exist, after forming ehter bond, under sodium hydroxide exist, carry out aldol condensation with 4-hydroxyacetophenone and obtain.Compound represented by above-mentioned formula (B-2-1-2 ') ~ (B-2-1-7 ') can obtain by referring to the method for the method.
Compound represented by above-mentioned formula (B-2-2-1 '), such as, can by with palladium and amine for catalyzer, make 4-iodophenol be equivalent to R with having falkyl alkyl acrylate reaction and obtain.
Compound represented by above-mentioned formula (B-2-2-2 '), can be equivalent to R by making to have fthe 4-alkylacetophenone of alkyl and 4-hydroxy benzaldehyde under sodium hydroxide exist, carry out aldol condensation and obtain.Compound represented by above-mentioned formula (B-2-1-3 ') can obtain by referring to the method for the method.
Compound represented by above-mentioned formula (B-2-8-1 '), such as, after can forming acyl chlorides by making by thionyl chloride 4-nitro TRANSCINNAMIC ACID, is equivalent to R with having fthe alcohol reaction of alkyl form ester, and use after such as this nitro of tin chloride reduction forms amino, make this resultant and hydroxyl phthalic anhydride react and obtain.A rear reaction, such as, can be undertaken by the method refluxed in acetic acid by starting compound or the method refluxed in toluene or dimethylbenzene under the suitable alkaline catalystss such as triethylamine exist.
In these compounds (B-2), preferred above-mentioned formula (B-2-1-1), formula (B-2-1-3), formula (B-2-1-4), formula (B-2-1-6) ~ formula (B-2-1-8), formula (B-2-1-16), formula (B-2-1-19), formula (B-2-1-21), formula (B-2-4-1), formula (B-2-4-2), formula (B-2-5-1) and the compound represented by formula (B-2-7-1).
In addition, as the material of structure containing the structure represented by above-mentioned formula (B-1) with liquid crystal aligning energy, butanic acid can be enumerated, n-caproic acid, n-caprylic acid, positive lauric acid, positive stearic acid, 4-Octadecane yl benzoic acid, 4-n-dodecane yl benzoic acid, 4-n-octyl formic acid, 4-positive hexyl phenenyl formic acid, 4-Octadecane aminobenzoic acid, 4-n-dodecane aminobenzoic acid, 4-n-octyloxy phenylformic acid, the positive hexyloxybenzoate of 4-, 1-hexylmercaptan, 1-heptanthiol, 1-spicy thioalcohol, 1-mercaptan in the ninth of the ten Heavenly Stems, 1-decyl mercaptan, 1-undecane thiol, 1-dodecyl mercaptans, 1-tetradecane mercaptan, 1-hexadecanethiol, 1-octadecanethiol, single cholestane base succinate and the compound represented by following formula.
In this manual, will the compound of structure containing the structure represented by above-mentioned formula (B-1) of liquid crystal aligning energy be had, be called " other tilt angle expression power compound ".As the ratio with the structure of liquid crystal aligning energy of this polyorganosiloxane compounds, relative to X a, be preferably 10 % by mole ~ 90 % by mole, be more preferably 20 % by mole ~ 80 % by mole, and be particularly preferably 25 % by mole ~ 75 % by mole.
[A] polyorganosiloxane compounds in the present invention, preferably remaining have the Si-X had in the organopolysiloxane of epoxy construction aa part for key.Therefore, when reacting, compound (A-1), compound (A-2), compound (A-3) and have liquid crystal aligning can the total mole number of compound, be preferably less than the radicals X that the organopolysiloxane with epoxy construction has amole number.At this moment, when having the usage ratio with the compound of liquid crystal aligning energy of the group represented by above-mentioned formula (B-1), when being preferably more than 50 % by mole relative to the total amount of compound, this liquid crystal aligning agent containing [A] polyorganosiloxane compounds can form by optical alignment method the liquid crystal orientation film demonstrating good liquid crystal aligning.
The synthetic method > of < [A] polyorganosiloxane compounds
[A] polyorganosiloxane compounds, can pass through the compound had represented by the organopolysiloxane of epoxy group(ing), above-mentioned formula (A-1) ~ formula (A-3) and the compound as required with liquid crystal aligning energy, preferably in the presence of a catalyst, react in organic solvent and synthesize.This manufacture method is easy, and the Drug delivery rate of various structure is high, is therefore applicable from the viewpoint of these.
Compound represented by formula (A-1) ~ formula (A-3) and have liquid crystal aligning can compound, can be used alone or be used in combination of two or more.
In addition, when the compound represented by formula (A-1) ~ formula (A-3) and have liquid crystal aligning can structure there is carboxyl time, can react by a part for other carboxylic acid displacement compound.At this moment, as the usage ratio of other carboxylic acid, relative to the total of compound with other carboxylic acid, be preferably less than 50 % by mole.
As above-mentioned catalyzer, the so-called curing catalyst of such as organic bases or promotion epoxy compounds and anhydride reaction can be used.
As organic bases, can enumerate such as:
The organic primary amine that ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles are such or secondary amine;
The trimethylamines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo undecylene;
The organic quaternary ammonium etc. such as Tetramethylammonium hydroxide.Wherein, preferred trimethylamine and organic quaternary ammonium.
As 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 salts such as Bian base triphenyl phosphonium muriate, Si Zheng Ding Ji Phosphonium bromide, Jia base triphenyl phosphonium bromide, Yi base triphenyl phosphonium bromide, normal-butyl triphenyl phosphonium bromide, tetraphenylphosphoniphenolate bromide, Yi base triphenyl phosphonium iodide, Yi base triphenyl phosphonium acetate, Si Zheng Ding Ji Phosphonium, o, o-diethyl phosphorothioate, Si Zheng Ding Ji Phosphonium benzotriazole salt, Si Zheng Ding Ji Phosphonium a tetrafluoro borate, Si Zheng Ding Ji 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 tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride;
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 polymer overmold imidazolium compounds, 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, preferred quaternary ammonium salt, and more preferably tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride.
As the usage quantity of catalyzer, there is relative to 100 mass parts the organopolysiloxane of epoxy group(ing), be preferably below 100 mass parts, be more preferably 0.01 mass parts ~ 100 mass parts, and be particularly preferably 0.1 mass parts ~ 20 mass parts.
As temperature of reaction, be preferably 0 DEG C ~ 200 DEG C, and be more preferably 50 DEG C ~ 150 DEG C.As the reaction times, be preferably 0.1 hour ~ 50 hours, and be more preferably 0.5 hour ~ 20 hours.
As when synthesizing [A] polyorganosiloxane compounds, operable organic solvent, can enumerate such as hydrocarbon compound, ether compound, ester cpds, ketone compound, amide compound, alkylol cpd etc.Wherein, ether compound, ester cpds, ketone compound, it is preferred for easily refining from the viewpoint of the solvability of raw material and resultant and resultant.As the content of solvent, its solid component concentration (the total quality of the composition beyond desolventizing in reaction soln accounts for the ratio of solution total mass) is preferably more than 0.1 quality %, and is more preferably the amount of 5 quality % ~ 50 quality %.
As the Mw of [A] polyorganosiloxane compounds, be preferably 1000 ~ 10000000, be more preferably 2000 ~ 100000, and be particularly preferably 3000 ~ 50000.
Other polymkeric substance of < >
Other polymkeric substance, may be used for the electrical specification improving the solution properties of this liquid crystal aligning agent and the liquid crystal orientation film of gained further, therefore can suitably contain in this liquid crystal aligning agent.As other polymkeric substance, at least one polymkeric substance, [C] other polyorganosiloxane compounds, poly amic acid ester, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc. of selecting in the group that [B] be made up of polyamic acid and polyimide can be enumerated such as.
Wherein, preferably [B] polymkeric substance, [C] other polyorganosiloxane compounds.By using the liquid crystal aligning agent of this liquid crystal aligning agent further containing [B] polymkeric substance to make liquid crystal orientation film, can be further improved the liquid crystal display device of the electrical specifications such as voltage retention.In addition, this liquid crystal aligning agent, by further containing [C] other polyorganosiloxane compounds, can promote the crosslinked of [A] polyorganosiloxane compounds, thus can improve the voltage retention etc. of the liquid crystal display device of gained further.Below, [B] polymkeric substance, [C] other polyorganosiloxane compounds are described in detail.
< [B] polymkeric substance >
[polyamic acid]
As the polyamic acid of [B] polymkeric substance, can react by making tetracarboxylic dianhydride and diamine compound and obtain.
As tetracarboxylic dianhydride, such as aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc. can be enumerated.In addition, tetracarboxylic dianhydride described in No. 2009-157556, Japanese Patent Application can also be used.These tetracarboxylic dianhydrides can be used alone or are used in combination of two or more.
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 [5.3.1.0 2,6] 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 Patent Application 2009-84462 can also be enumerated.
In these tetracarboxylic dianhydrides, preferred ester ring type tetracarboxylic dianhydride, more preferably 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides or 1,2,3,4-tetramethylene tetracarboxylic dianhydride, and particularly preferably 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides.
As 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride or 1, the usage quantity of 2,3,4-tetramethylene tetracarboxylic dianhydride, relative to whole tetracarboxylic dianhydride, preferably containing more than 10 % by mole, be more preferably more than 20 % by mole, and particularly preferably only by 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride or 1,2,3,4-tetramethylene tetracarboxylic dianhydride is formed.
As diamine compound, such as aliphatie diamine, ester ring type diamines, diamino organo-siloxane, aromatic diamine etc. can be enumerated.These diamine compounds, can be used alone or be used in combination of two or more.In addition, diamines described in No. 2009-157556, Japanese Patent Application can also be used.
As aliphatie diamine, such as m-xylene diamine, 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 diamino organo-siloxane, such as 1,3-bis-(3-aminopropyl)-tetramethyl-bicyclohexane etc. can be enumerated, in addition, diamines described in Japanese Patent Application 2009-84462 can also be enumerated.
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 phenylene diisopropylidene) two (aniline), 4,4 '-(metaphenylene 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-aminopropyl) piperazine, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane 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, 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, 2,4-diamino-N, N-diallyl aniline, 4-amino-benzylamine, 3-amino-benzylamine and the diamine compound etc. represented by following formula (6).
In above-mentioned formula (6), Za to be carbonatoms be 1 ~ 3 alkyl ,-O-,-COO-or-OCO-.Pa is 0 or 1.Q is the integer of 0 ~ 2.R is the integer of 1 ~ 20.
In above-mentioned formula (6), as C rh 2r+1base, can enumerate such as straight-chain or branched methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc.
As the diamine compound represented by above-mentioned formula (6), the compound etc. such as represented by following formula (6-1) ~ (6-5) can be enumerated.
Be provided in the tetracarboxylic dianhydride of polyamic acid building-up reactions and the usage ratio of diamine compound, relative to amino contained in 1 equivalent diamine compound, the anhydride group of tetracarboxylic dianhydride is preferably 0.2 equivalent ~ 2 equivalent, is more preferably 0.3 equivalent ~ 1.2 equivalent.
Preferably carry out building-up reactions in organic solvent.As temperature of reaction, be preferably-20 DEG C ~ 150 DEG C, be more preferably 0 DEG C ~ 100 DEG C.As the reaction times, be preferably 0.1 hour ~ 24 hours, be more preferably 0.5 hour ~ 12 hours.
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 (NMP), N, N-N,N-DIMETHYLACETAMIDE, N, the non-proton system polar solvents such as dinethylformamide, N, N-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA; The phenol series solvents such as meta-cresol, xylenol, phenol, halogenated phenol.
As the usage quantity (a) of organic solvent, relative to tetracarboxylic dianhydride and the total amount (b) of diamines and the total amount (a+b) of organic solvent usage quantity (a), be preferably 0.1 quality % ~ 50 quality %, be more preferably 5 quality % ~ 30 quality %.
The polyamic acid solution of gained after reaction, 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.As the separation method of polyamic acid, can enumerate such as by reaction soln is injected in a large amount of poor solvents, and the method for the precipitate drying under reduced pressure of gained, use vaporizer are reduced pressure and distillate the method etc. of reaction soln.As the process for purification of polyamic acid, can enumerate and the polyamic acid of separation is dissolved in organic solvent again, and the method making it separate out with poor solvent, carry out one or many and use vaporizer decompression to distillate the method for the operation of organic solvent etc.
[polyimide]
As the polyimide of [B] polymkeric substance, by the amido acid structure dehydration closed-loop making above-mentioned polyamic acid have, imidization can be carried out and manufactures.
Polyimide, can be the complete imide compound of the whole amido acid structure dehydration closed-loops had as the polyamic acid of its precursor, also can be partial amides acid structure dehydration closed-loop and form amido acid structure and imide structure and the part imide compound of depositing.The imide rate of polyimide, is preferably more than 30%, is more preferably 40% ~ 80%.In addition, the imide rate in polyimide is put in pure water by the solution of polyimide, and after the precipitation of at room temperature drying under reduced pressure gained, be dissolved in deuterodimethylsulfoxide, using tetramethylsilane as standard substance, at room temperature measure 1h-NMR, and by gained 1h-NMR spectrogram, the formula represented by following formula (7) is obtained.
Imide rate (%)={ 1-(A 1/ A 2) × α } × 100 (7)
In above-mentioned formula (7), A 1it is the peak area (10ppm) coming from NH matrix.A 2it is the peak area coming from other proton.α is the ratio of number relative to 1 proton of the NH base in polyamic acid of other proton.
As the synthetic method of polyimide, such as (i) can be enumerated and heat the method for polyamic acid (below, be sometimes referred to as " method (i) "), (ii) by polyamic acid dissolve in organic solvent, and dewatering agent and dehydration closed-loop catalyzer is added in this solution, and the method heated as required (following, be sometimes referred to as " method (ii) ") etc. uses the method for the dehydration closed-loop reaction of polyamic acid.
As the temperature of reaction in method (i), be preferably 50 DEG C ~ 200 DEG C, and be more preferably 60 DEG C ~ 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.As the reaction times, be preferably 0.5 hour ~ 48 hours, be more preferably 2 hours ~ 20 hours.
The polyimide of gained in method (i), directly can supply the modulation of liquid crystal aligning agent, also polyimide can be separated the modulation of rear supply liquid crystal aligning agent, or after isolated polyimide can also being refined or resupply the modulation of liquid crystal aligning agent after being refined by the polyimide of gained.
As the dewatering agent in method (ii), the acid anhydrides such as such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride can be enumerated.
As the content of dewatering agent, suitably can select according to desired imide rate, but relative to the amido acid structure of 1 mole of polyamic acid, be preferably 0.01 mole ~ 20 moles.
As the dehydration closed-loop catalyzer in method (ii), such as pyridine, collidine, lutidine, triethylamine etc. can be enumerated.
As the content of dehydration closed-loop catalyzer, relative to the dewatering agent that 1 mole contains, be preferably 0.01 mole ~ 10 moles.In addition, the content of above-mentioned dewatering agent and dehydration closed-loop catalyzer is more, then more can improve imide rate.
As organic solvent used in method (ii), can enumerate such as and the organic solvent of illustrating is same as solvent used in polyamic acid synthesis organic solvent etc.
As the temperature of reaction in method (ii), be preferably 0 DEG C ~ 180 DEG C, be more preferably 10 DEG C ~ 150 DEG C.As the reaction times, be preferably 0.5 hour ~ 20 hours, be more preferably 1 hour ~ 8 hours.By making reaction conditions be above-mentioned scope, dehydration closed-loop reaction can fully be carried out, and can obtain the suitable molecular weight of gained polyimide.
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 can resupply the modulation of liquid crystal aligning agent after remove dewatering agent and dehydration closed-loop catalyzer from reaction soln, and resupply the modulation of liquid crystal aligning agent after polyimide can being separated or after being refined by isolated polyimide, resupply the modulation of liquid crystal aligning agent.As the method removing dewatering agent and dehydration closed-loop catalyzer from reaction soln, the method etc. of such as solvent exchange can be enumerated.As separation method and the process for purification of polyimide, such as identical with the method that the separation method as polyamic acid is illustrated with process for purification method etc. can be enumerated.
Other polyorganosiloxane compounds > of < [C]
In this liquid crystal aligning agent, preferably except [A] polyorganosiloxane compounds, also further containing [C] other polyorganosiloxane compounds, as [C] other polyorganosiloxane compounds, be more preferably the organopolysiloxane of the structural unit had represented by above-mentioned formula (2).In addition, when this liquid crystal aligning agent contains [C] other polyorganosiloxane compounds, as long as [C] other major part and [A] polyorganosiloxane compounds of polyorganosiloxane compounds independently exists, then its part also can exist as the condenses with specific polyorganosiloxane compounds.
In above-mentioned formula (2), X bfor hydroxyl, halogen atom, carbonatoms be 1 ~ 20 alkyl, carbonatoms be 1 ~ 6 alkoxyl group or carbonatoms be the aryl of 6 ~ 20.Y 2for hydroxyl or carbonatoms are the alkoxyl group of 1 ~ 10.
Be the alkyl of 1 ~ 20 as carbonatoms, such as straight-chain or branched methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, lauryl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc. can be enumerated.
Be the alkoxyl group of 1 ~ 6 as carbonatoms, such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy etc. can be enumerated.
Be the aryl of 6 ~ 20 as carbonatoms, such as phenyl, naphthyl etc. can be enumerated.
As [C] other the Mw of polyorganosiloxane compounds, be preferably 500 ~ 100000, be more preferably 500 ~ 10000.
[C] other polyorganosiloxane compounds, such as, can by preferably in suitable organic solvent, under the existence of water and catalyzer, the at least one silane compound making to select in the group be made up of organoalkoxysilane and silane halide compound is (following, be sometimes referred to as " raw silicon hydride compounds "), be hydrolyzed or hydrolytic condensation and synthesizing.
As raw silicon hydride compounds, such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane, four tert-butoxy silane, tetrachloro silicane etc. 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 etc.,
Dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyldichlorosilane(DMCS) etc.;
Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane etc.
Wherein, tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane is preferably.
As when synthesizing [C] other polyorganosiloxane compounds, can arbitrarily used organic solvent, such as alkylol cpd, ketone compound, amide compound, ester cpds or other aprotic compound can be enumerated.They can be used alone or are used in combination of two or more.
As alkylol cpd, such as methyl alcohol can be enumerated, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, 2-methyl butanol, sec.-amyl alcohol, tertiary amyl alcohol, 3-methoxybutanol, n-hexyl alcohol, 2-methyl amyl alcohol, secondary hexyl alcohol, 2-ethyl butanol, secondary enanthol, 3-enanthol, n-Octanol, 2-Ethylhexyl Alcohol, sec-octyl alcohol, nonanol-, 2, 6-2,6-dimethyl-4-heptanol, nonylcarbinol, secondary undecyl alcohol, Exxal 12, secondary tetradecyl alcohol, secondary heptadecyl alcohol, phenol, hexalin, methyl-cyclohexanol, 3, 3, 5-cyclonol, benzylalcohol, the single methanol compounds such as Pyranton,
Ethylene glycol, 1,2-PD, 1,3 butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexylene glycols, 2, the polyol compounds such as 4-heptanediol, 2-ethyl-1,3-hexylene glycol, Diethylene Glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol ether, ethyleneglycol monophenylether, ethylene glycol list-2-ethyl-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, Diethylene Glycol monohexyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPE, the part ether etc. of the polyol compounds such as dipropylene glycol monopropyl ether.
As ketone compound, the single ketones compounds such as such as acetone, methylethylketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, ethyl normal-butyl ketone, methyl n hexyl ketone, diisobutyl ketone, trimethylammonium nonanone, pimelinketone, methyl-n-butyl ketone, methylcyclohexanone, 2,4-diacetylmethanes, acetonyl-acetone, methyl phenyl ketone, fenchone can be enumerated;
Acetyl Acetone, 2,4-hexanediones, 2,4-heptadione, 3,5-heptadione, 2; 4-acetyl caproyl, 3,5-acetyl caproyls, 2,4-the ninth of the ten Heavenly Stems diketone, 3; 5-diketone in the ninth of the ten Heavenly Stems, 5-methyl-2,4-hexanedione, 2,2; 6,6-tetramethyl--3,5-heptadione, 1; 1,1,5; the beta-diketone compounds etc. such as 5,5-hexafluoro-2,4-heptadione.
As amide compound; such as methane amide, N-METHYLFORMAMIDE, N can be enumerated; dinethylformamide, N-ethyl-formamide, N; N-diethylformamide, ethanamide, N-methylacetamide, N; N-N,N-DIMETHYLACETAMIDE, N-ethyl acetamide, N, N-diethyl acetamide, N-methyl propanamide, N-Methyl pyrrolidone, N-formyl morpholine, N-formyl piperidine, N-carbonyl pyrrolidine, N-acetylmorpholine, N-Acetylpiperidin, N-acetyl-pyrrolidine etc.
As ester cpds, such as diethyl carbonate can be enumerated, NSC 11801, propylene carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, γ-valerolactone, 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, hexalin acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, methyl aceto acetate, acetic acid ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid Diethylene Glycol mono-n-butyl ether, propyleneglycolmethyletheracetate monomethyl ether, propyleneglycolmethyletheracetate list ether, propyleneglycolmethyletheracetate list propyl ether, propyleneglycolmethyletheracetate monobutyl ether, acetic acid dipropylene glycol monomethyl ether, acetic acid DPE, oxalic acid glycol, acetic acid methoxy triglycol, ethyl propionate, n-butyl propionate, isoamyl propionate, oxalic acid diethyl ester, dibutyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, N_amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate etc.
As other aprotic compound, such as acetonitrile, dimethyl sulfoxide (DMSO), N can be enumerated, N, N ', N '-tetraethyl-sulphonamide, hexamethyl phosphoric triamide, N-methylmorpholine ketone, N-methylpyrrole, N-N-ethyl pyrrole N-, N-methyl-Δ 3-pyrroline, N-methyl piperidine, N-ethylpiperidine, N, N-lupetazin, N-Methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, NMP, 1,3-dimethyl-2-imidazolinone, 1,3-dimethyl tetrahydro-2 (1H)-pyrimidone etc.
In these solvents, the part ether of preferred polyol compound, polyol compound and ester cpds.
As the water yield used when synthesizing [C] other polyorganosiloxane compounds, the total of the alkoxyl group had relative to raw silicon hydride compounds and halogen atom 1 mole, be preferably 0.5 mole ~ 100 moles, be more preferably 1 mole ~ 30 moles, be particularly preferably 1 mole ~ 1.5 moles.
As the operable catalyzer when synthesizing [C] other polyorganosiloxane compounds, such as metallo-chelate, organic acid, mineral acid, organic bases, alkali metal compound, alkali earth metallic compound, ammonia etc. can be enumerated.They can be used alone or are used in combination of two or more.
As metallo-chelate, such as triethoxy list (methyl ethyl diketone) titanium can be enumerated, three positive propoxy list (methyl ethyl diketone) titaniums, three isopropoxy list (methyl ethyl diketone) titaniums, three n-butoxy list (methyl ethyl diketone) titaniums, three sec-butoxy list (methyl ethyl diketone) titaniums, three tert.-butoxy list (methyl ethyl diketone) titaniums, diethoxy bis(acetylacetonate) titanium, two positive propoxy bis(acetylacetonate) titaniums, diisopropoxy bis(acetylacetonate) titanium, two n-butoxy bis(acetylacetonate) titaniums, two sec-butoxy bis(acetylacetonate) titaniums, two tert.-butoxy bis(acetylacetonate) titaniums, monosubstituted ethoxy tri acetylacetonato titanium, single positive propoxy tri acetylacetonato titanium, single isopropoxy tri acetylacetonato titanium, single n-butoxy tri acetylacetonato titanium, single sec-butoxy tri acetylacetonato titanium, single tert.-butoxy tri acetylacetonato titanium, four (methyl ethyl diketone) titanium, triethoxy list (ethyl acetoacetic ester) titanium, three positive propoxy list (ethyl acetoacetic ester) titaniums, three isopropoxy list (ethyl acetoacetic ester) titaniums, three n-butoxy list (ethyl acetoacetic ester) titaniums, three sec-butoxy list (ethyl acetoacetic ester) titaniums, three tert.-butoxy list (ethyl acetoacetic ester) titaniums, diethoxy two (ethyl acetoacetic ester) titanium, two positive propoxy two (ethyl acetoacetic ester) titaniums, diisopropoxy two (ethyl acetoacetic ester) titanium, two n-butoxy two (ethyl acetoacetic ester) titaniums, two sec-butoxy two (ethyl acetoacetic ester) titaniums, two tert.-butoxy two (ethyl acetoacetic ester) titaniums, monosubstituted ethoxy three (ethyl acetoacetic ester) titanium, single positive propoxy three (ethyl acetoacetic ester) titanium, single isopropoxy three (ethyl acetoacetic ester) titanium, single n-butoxy three (ethyl acetoacetic ester) titanium, single sec-butoxy three (ethyl acetoacetic ester) titanium, single tert.-butoxy three (ethyl acetoacetic ester) titanium, four (ethyl acetoacetic ester) titanium, single (methyl ethyl diketone) three (ethyl acetoacetic ester) titanium, two (methyl ethyl diketone) two (ethyl acetoacetic ester) titanium, the titanium chelate compounds such as tri acetylacetonato list (ethyl acetoacetic ester) titanium,
Triethoxy list (methyl ethyl diketone) zirconium, three positive propoxy list (methyl ethyl diketone) zirconiums, three isopropoxy list (methyl ethyl diketone) zirconiums, three n-butoxy list (methyl ethyl diketone) zirconiums, three sec-butoxy list (methyl ethyl diketone) zirconiums, three tert.-butoxy list (methyl ethyl diketone) zirconiums, diethoxy two (methyl ethyl diketone) zirconium, two positive propoxy two (methyl ethyl diketone) zirconiums, diisopropoxy two (methyl ethyl diketone) zirconium, two n-butoxy two (methyl ethyl diketone) zirconiums, two sec-butoxy two (methyl ethyl diketone) zirconiums, two tert.-butoxy two (methyl ethyl diketone) zirconiums, monosubstituted ethoxy tri acetylacetonato zirconium, single positive propoxy tri acetylacetonato zirconium, single isopropoxy tri acetylacetonato zirconium, single n-butoxy tri acetylacetonato zirconium, single sec-butoxy tri acetylacetonato zirconium, single tert.-butoxy tri acetylacetonato zirconium, four (methyl ethyl diketone) zirconium, triethoxy list (ethyl acetoacetic ester) zirconium, three positive propoxy list (ethyl acetoacetic ester) zirconiums, three isopropoxy list (ethyl acetoacetic ester) zirconiums, three n-butoxy list (ethyl acetoacetic ester) zirconiums, three sec-butoxy list (ethyl acetoacetic ester) zirconiums, three tert.-butoxy list (ethyl acetoacetic ester) zirconiums, diethoxy two (ethyl acetoacetic ester) zirconium, two positive propoxy two (ethyl acetoacetic ester) zirconiums, diisopropoxy two (ethyl acetoacetic ester) zirconium, two n-butoxy two (ethyl acetoacetic ester) zirconiums, two sec-butoxy two (ethyl acetoacetic ester) zirconiums, two tert.-butoxy two (ethyl acetoacetic ester) zirconiums, monosubstituted ethoxy three (ethyl acetoacetic ester) zirconium, single positive propoxy three (ethyl acetoacetic ester) zirconium, single isopropoxy three (ethyl acetoacetic ester) zirconium, single n-butoxy three (ethyl acetoacetic ester) zirconium, single sec-butoxy three (ethyl acetoacetic ester) zirconium, single tert.-butoxy three (ethyl acetoacetic ester) zirconium, four (ethyl acetoacetic ester) zirconium, single (methyl ethyl diketone) three (ethyl acetoacetic ester) zirconium, two (methyl ethyl diketone) two (ethyl acetoacetic ester) zirconium, the zirconium chelate compounds such as tri acetylacetonato list (ethyl acetoacetic ester) zirconium,
The aluminum chelate compounds etc. such as aluminium tris(acetylacetonate), three (ethyl acetoacetic ester) aluminium.
As organic acid, such as acetic acid can be enumerated, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, oxalic acid, toxilic acid, Methylpropanedioic acid, hexanodioic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, Ara, shikimic acid, 2 ethyl hexanoic acid, oleic acid, stearic acid, linolic acid, linolenic acid, Whitfield's ointment, phenylformic acid, para-amino benzoic acid, tosic acid, Phenylsulfonic acid, monochloro acetic acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, formic acid, propanedioic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartrate etc.
As mineral acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid etc. can be enumerated.
As organic bases, such as pyridine, pyrroles, piperazine, tetramethyleneimine, piperidines, picoline, Trimethylamine 99, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, trolamine, diazabicyclo octane, diazabicyclo nonane, diazabicyclo undecylene, tetramethyl ammonium hydroxide etc. can be enumerated.
As alkali metal compound, such as sodium hydroxide, potassium hydroxide etc. can be enumerated.
As alkali earth metallic compound, such as hydrated barta, calcium hydroxide etc. can be enumerated.
Wherein, preferable alloy chelate compound, organic acid and mineral acid, more preferably titanium chelate compound and organic acid.
As the usage quantity of catalyzer, relative to 100 mass parts raw silicon hydride compounds, be preferably 0.001 mass parts ~ 10 mass parts, be more preferably 0.001 mass parts ~ 1 mass parts.
The water added when synthesizing [C] other polyorganosiloxane compounds, can add in the silane compound as raw material or add to being dissolved in the solution of organic solvent by silane compound intermittently or continuously to.Catalyzer can add in the silane compound as raw material in advance or add to and is dissolved in the solution of organic solvent by silane compound, also can be dissolved or dispersed in the water of interpolation.
As temperature of reaction during synthesis [C] other polyorganosiloxane compounds, be preferably 0 DEG C ~ 100 DEG C, and be more preferably 15 DEG C ~ 80 DEG C.As the reaction times, be preferably 0.5 hour ~ 24 hours, be more preferably 1 hour ~ 8 hours.
[containing of other polymkeric substance is proportional]
When this liquid crystal aligning agent contains other polymkeric substance, as other polymkeric substance containing proportional, different according to the kind of other polymkeric substance, but relative to 100 mass parts [A] polyorganosiloxane compounds, preferably below 10000 mass parts.
When this liquid crystal aligning agent contains [B] polymkeric substance, as polyamic acid and polyimide total amount containing proportional, relative to 100 mass parts [A] polyorganosiloxane compounds, be preferably 200 mass parts ~ 5000 mass parts.
When this liquid crystal aligning agent contains [C] other organopolysiloxane, as [C] other polyorganosiloxane compounds containing proportional, relative to 100 mass parts organopolysiloxane, be preferably 100 mass parts ~ 2000 mass parts.
When this liquid crystal aligning agent contains other polymkeric substance, as the kind of other polymkeric substance, preferably other organopolysiloxane of [B] polymkeric substance or [C], is more preferably [B] polymkeric substance.
< optional member >
Optionally composition, such as solidifying agent, curing catalysts, curing catalyst, the compound (following, to be sometimes referred to as " epoxy compounds ") in molecule with at least one epoxy group(ing), functional silanes compound, tensio-active agent etc. can be enumerated.Below, these optional members are described in detail.
[solidifying agent, curing catalysts and curing catalyst]
In order to make the crosslinking reaction of [A] polyorganosiloxane compounds more firm, solidifying agent and curing catalysts can be contained in this liquid crystal aligning agent.In addition, the curing reaction controlled to promote solidifying agent, can contain above-mentioned curing catalyst in this liquid crystal aligning agent.
As 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 polybasic acid anhydride, acid anhydride and other the polybasic acid anhydride etc. of such as cyclohexanetricarboxylic acid can be enumerated.As cyclohexanetricarboxylic acid's acid anhydride, such as hexanaphthene-1,2 can be enumerated, 4-tricarboxylic acid, hexanaphthene-1,3,5-tricarboxylic acid, hexanaphthene-1,2,3-tricarboxylic acid, hexanaphthene-1,3,4-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, methylnadic anhydride, dodecenyl succinic anhydride, Succinic anhydried, maleic anhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride and normally used tetracarboxylic dianhydride in the synthesis of polyamic acid can be enumerated, 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 the usage ratio of solidifying agent, relative to 100 mass parts [A] polyorganosiloxane compounds, be preferably below 100 mass parts.
As curing catalysts, such as antimony hexafluoride compound, phosphorus hexafluoride compound, aluminium triacetoacetate etc. can be enumerated.As the usage ratio of curing catalysts, relative to 100 mass parts [A] polyorganosiloxane compounds, be preferably below 2 mass parts.
As 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.
As the usage ratio of curing catalyst, relative to 100 mass parts [A] organopolysiloxane, be preferably below 10 mass parts.
[epoxy compounds]
In order to improve the cementability of liquid crystal orientation film relative to substrate surface of formation further, epoxy compounds can be contained in this liquid crystal aligning agent.
As 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.
As epoxy compounds containing proportional, relative to [A] polyorganosiloxane compounds and total 100 mass parts of other polymkeric substance that contains arbitrarily, preferably below 40 mass parts, be more preferably 0.1 mass parts ~ 30 mass parts.In addition, when this liquid crystal aligning agent contains epoxy compounds, in order to effectively produce crosslinking reaction, can be used together the alkaline catalystss such as 1 benzyl 2 methyl imidazole.
[functional silanes compound]
In order to improve the cementability of liquid crystal orientation film for substrate surface of formation, 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, tetracarboxylic dianhydride and the reactant etc. with amino silane compound, in addition, can also enumerate tetracarboxylic dianhydride described in Japanese Laid-Open Patent Publication 63-291922 publication and the reactant etc. with amino silane compound.
As functional silanes compound containing proportional, relative to [A] polyorganosiloxane compounds and total 100 mass parts of other polymkeric substance that contains arbitrarily, preferably below 50 mass parts, be more preferably below 20 mass parts.
[tensio-active agent]
As tensio-active agent, such as nonionogenic tenside, anion surfactant, cats product, amphoterics, polysiloxane surfactant, polyoxyalkylene surfactants, fluorochemical surfactant etc. can be enumerated.
As the usage ratio of tensio-active agent, relative to entirety 100 mass parts of this liquid crystal aligning agent, be preferably below 10 mass parts, be more preferably below 1 mass parts.
The modulator approach > of < liquid crystal aligning agent
As mentioned above, this liquid crystal aligning agent contains [A] polyorganosiloxane compounds as neccessary composition, and as required containing other composition, and preferably modulate as the composition of each component dissolves solution shape in organic solvent.
As organic solvent, be preferably and dissolve [A] polyorganosiloxane compounds and other composition arbitrarily used, and the solvent that can not react with them.As the organic solvent that can be preferred for this liquid crystal aligning agent, different from the kind of other polymkeric substance contained arbitrarily.
Contain [A] polyorganosiloxane compounds and preferred organic solvent during [B] polymkeric substance as this liquid crystal aligning agent, 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 this liquid crystal aligning agent only containing [A] polyorganosiloxane compounds as polymkeric substance or containing preferred organic solvent during other polyorganosiloxane compounds of [A] polyorganosiloxane compounds and [C], 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.
May be used for the preferred solvent of modulating this liquid crystal aligning agent, according to or without the kind using other polymkeric substance and this polymkeric substance, one or more of above-mentioned organic solvent can be combinationally used and obtain.This solvent, in following preferred solid component concentration, can not separate out each composition contained in liquid crystal aligning agent, and makes 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 quality of all the components beyond that is desolventizing in liquid crystal aligning agent accounts for the ratio of liquid crystal aligning agent total mass, considers that viscosity, volatility etc. are selected, and is preferably 1 quality % ~ 10 quality %.When solid component concentration is less than 1 quality %, the thickness having a liquid crystal orientation film formed by this liquid crystal aligning agent is too small and cannot obtain the situation of good liquid crystal orientation film.On the other hand, when solid component concentration is more than 10 quality %, have film thickness excessive and good liquid crystal orientation film cannot be obtained, and the viscosity of liquid crystal aligning agent increases and causes the situation of coating characteristics deficiency.The scope of preferred solid component concentration is different according to the method adopted during coating of liquid crystalline alignment agent on substrate.Such as, adopt solid component concentration scope during spin-coating method, be preferably 1.5 quality % ~ 4.5 quality %.When adopting print process, solid component concentration is preferably the scope of 3 quality % ~ 9 quality %, and makes soltion viscosity be the scope of 12mPas ~ 50mPas thus.When adopting ink jet method, solid component concentration is preferably the scope of 1 quality % ~ 5 quality %, and makes soltion viscosity be the scope of 3mPas ~ 15mPas thus.
Modulate temperature during this liquid crystal aligning agent, be preferably 0 DEG C ~ 200 DEG C, and be more preferably 10 DEG C ~ 60 DEG C.
< liquid crystal orientation film and forming method thereof >
The liquid crystal orientation film formed by this liquid crystal aligning agent also suitably comprises in the present invention.As the method using this liquid crystal aligning agent to form liquid crystal orientation film, according in [A] polyorganosiloxane compounds, the situation of structure containing the structural unit represented by above-mentioned formula (B-1) that [B] has liquid crystal aligning energy is (following, in this case formation method is called " formation method (i) "), have liquid crystal aligning can structure contain the situation (following, formation method is in this case called " formation method (ii) ") of the structural unit represented by above-mentioned formula (B-1) and different.Below, formation method (i) and (ii) are described in detail.
[formation method (i)]
First, two panels is provided with the substrate of the nesa coating forming pattern as a pair, and by the coating process that such as rolling method, spin-coating method, print process, ink jet method etc. are suitable, its each nesa coating forming surface is coated with this liquid crystal aligning agent.Then, coated face being preheated (prebake), then forming film by burning till (curing afterwards).As the condition of prebake, such as, for carry out 0.1 minute ~ 5 minutes at 40 DEG C ~ 120 DEG C.As after the condition of curing, be preferably at 120 DEG C ~ 300 DEG C, more preferably at 150 DEG C ~ 250 DEG C, preferably carry out 5 minutes ~ 200 minutes, more preferably carry out 10 minutes ~ 100 minutes.After cure after film thickness, be preferably 0.001 μm ~ 1 μm, be more preferably 0.005 μm ~ 0.5 μm.
As aforesaid substrate, the transparency carrier etc. such as comprising the plastic basis materials such as the glass baseplate such as float glass, soda-lime glass, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate can be enumerated.
As nesa coating, can enumerate containing SnO 2nESA film, containing In 2o 3-SnO 2ito film etc.As the formation patterning method of these nesa coatings, such as photoetch method can be enumerated or use the method etc. of mask when forming nesa coating.
When coating of liquid crystalline alignment agent, in order to make the cementability of substrate or nesa coating and film more good, functional silanes compound, titanate compound etc. can be coated with in advance on substrate and nesa coating.
When by the liquid crystal orientation film of this liquid crystal aligning agent for the formation of vertical alignment-type liquid crystal display device, the film formed as mentioned above directly can be used as the liquid crystal orientation film of vertical alignment-type liquid crystal display device, also can execute grinding process to this coated surface arbitrary real.On the other hand, by liquid crystal aligning agent of the present invention for the formation of the liquid crystal orientation film that horizontally oriented type is used for liquid crystal display element time, liquid crystal orientation film can be formed by implementing grinding process on the film formed as mentioned above.
Above-mentioned grinding process, can carry out rubbing and implementing by using the roller of the cloth that the fibers such as such as nylon, artificial silk, cotton are formed that reeled in a certain direction.Herein, such as Japanese Unexamined Patent Publication 6-222366 publication can be passed through, described such such as Japanese Unexamined Patent Publication 6-281937 publication, to a part of irradiation ultraviolet radiation of liquid crystal orientation film, thus the process changing tilt angle is implemented to formed liquid crystal orientation film, or can described in Japanese Unexamined Patent Publication 5-107544 publication, after implementing to form etchant resist in the part on formed liquid crystal orientation film surface, with previous grinding process different directions on carry out grinding process, then etchant resist is removed, liquid crystal orientation film is made to have the process of different liquid crystal aligning energy on each zone, thus the field-of-view characteristics of the horizontal type liquid crystal display device of gained can be improved.
[formation method (ii)]
The formation method (ii) of the liquid crystal orientation film that the present invention comprises, comprising:
(1) liquid crystal aligning agent comprising [A] polyorganosiloxane compounds is coated on substrate, form the operation of film, be somebody's turn to do the structure with liquid crystal aligning energy that [A] polyorganosiloxane compounds comprises the structural unit had represented by above-mentioned formula (B-1), and
(2) to the operation of irradiating radioactive rays at least partially of the film that operation (1) is formed.
By using the formation method of the present invention of this liquid crystal aligning agent, the liquid crystal orientation film fully meeting the characteristics such as required liquid crystal aligning, voltage retention and photostabilization as liquid crystal display device in practical can be formed.
As above-mentioned (1) film formation process, can be suitable for and operation that film formation process illustrated in formation method (i) is same.
In formation method (ii), can by (2) to the operation of irradiating radioactive rays at least partially of the film that operation (1) is formed to replace being formed in method (i) illustrated grinding process, manufacture liquid crystal orientation film.
As radioactive rays, the radioactive rays of rectilinearly polarized light or partial poolarized light or the radioactive rays of non-polarized light can be used, the ultraviolet and visible rays that such as comprise 150nm ~ 800nm wavelength light can be enumerated, and preferably comprise the ultraviolet of 300nm ~ 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 enumerated.The ultraviolet in above-mentioned optimal wavelength region, can by obtaining above-mentioned 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, be more preferably 10J/m 2~ 3000J/m 2.In addition, when giving liquid crystal aligning energy 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 this liquid crystal aligning agent, even if radiation exposure amount during optical alignment method is 3000J/m 2below, be 1000J/m further 2below, and be in particular 500J/m 2below, also can give good liquid crystal aligning energy, and contribute to the decline of liquid crystal display device manufacturing cost.
< liquid crystal display device >
The liquid crystal display device possessing this liquid crystal orientation film also suitably comprises in the present invention.Therefore, possess the liquid crystal display device of the application of the liquid crystal orientation film formed by this liquid crystal aligning agent, can suitably for display unit such as such as clock and watch, portable game machine, word processor, notebook computer, auto-navigation system, pick up camera, portable data assistance, digital camera, mobile phone, various indicating meter, LCD TV.
The manufacture method > of < liquid crystal display device
This liquid crystal display device such as can manufacture as follows.
As first method, it is in the past known method, wherein, first, by two plate bases across gap (box gap) relative configuration, 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, the method being called ODF (OneDropFill instils) 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, then the liquid crystal that drips on liquid crystal aligning face, another block substrate of then fitting, make liquid crystal orientation film relative, then to substrate whole irradiation ultraviolet radiation, make sealant cures, can liquid crystal cell be manufactured thus.
When adopting either method, being next all wish liquid crystal cell to be heated to the temperature that liquid crystal used is isotropic phase, then slowly cooling to room temperature, removing 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.
As sealing agent, can enumerate and such as contain as the alumina balls of separator and the epoxy resin etc. of solidifying agent.
As above-mentioned liquid crystal, such as nematic liquid crystal and smectic liquid crystal etc. can be enumerated.Under TN type liquid crystal cell or STN type liquid crystal cell situation, preferably there is the nematic liquid crystal of positive dielectric anisotropy.As this liquid crystal, 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. can be enumerated.In addition, the chiral agent that use is such as carried out as cholesteryl liquid crystals (メ ルク company, " C-15 ", " CB-15 ") such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonates selling can also be added further in above-mentioned liquid crystal; 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.
On the other hand, when vertical alignment-type liquid crystal box, preferably there is the nematic liquid crystal of negative dielectric anisotropic.As this liquid crystal, such as dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc. can be enumerated.
As the polarization plates that the outside of liquid crystal cell uses, can enumerate while clamping make polyvinyl alcohol stretch orientation with rhodia protective membrane, absorb the polarizing coating being referred to as " H film " of iodine gained and polarization plates that the polarization plates that formed or H film are formed self.
Embodiment
Below, based on embodiment, the present invention is described in detail, but the present invention and can't help this embodiment record and restrictively explain.
In addition, as required, repeat the synthesis of starting compound in the synthetic route shown in following synthesis example and polymkeric substance, guarantee starting compound used below in an example and the necessary amount of polymkeric substance.Epoxy equivalent (weight) measures according to " hydrochloric acid-methylethylketone method " of JISC2105.Soltion viscosity (mPas) uses E type rotational viscosimeter to measure the solution in each synthesis example, the polymer concentration of polymers soln being adjusted to 10 quality %.
< has the synthesis > of the organopolysiloxane of epoxy group(ing)
[synthesis example 1]
In the reaction vessel with agitator, thermometer, dropping funnel and reflux condensing tube, add 100.0g2-(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 water of the aqueous ammonium nitrate solution washing of 0.2 quality % to washing in neutral, then under reduced pressure distillate solvent and water, obtain the organopolysiloxane (EPS-1) with epoxy group(ing) as clear viscous liquid.
(EPS-1) 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.(EPS-1) Mw is 2200, and epoxy equivalent (weight) is 186g/ mole.
The synthesis > of < compound (A-1-1)
[synthesis example 2]
According to following synthetic route, synthetic compound (A-1-1).
In the eggplant type flask of 500mL, add 23.6g2,2,6,6-tetramethyl--4-hydroxy piperidine, 15.0g Succinic anhydried, 200mL pyridine, stirring reaction 9 hours at 80 DEG C.After reaction terminates, at room temperature leave standstill 1 day, crystallization, except desolventizing, obtains the white crystals of 37.1g compound (A-1-1).
< has the synthesis > of the compound of liquid crystal aligning energy
[synthesis example 3]
According to following synthetic route, synthetic compound (b-1).
In the eggplant type flask of 1L, add 82g Hydroxycinnamic acid, 304g salt of wormwood and 400mLN-N-methyl-2-2-pyrrolidone N-, at room temperature stir after 1 hour, add 166g1-bromo pentane silane, stir 5 hours at 100 DEG C.Then, under reduced pressure solvent is distillated.Add 48g sodium hydroxide and 400mL water wherein, reflux 3 hours, be hydrolyzed reaction.After reaction terminates, by hydrochloric acid neutralization reaction system, reclaim the precipitation generated, and carry out recrystallization with ethanol, obtain the white crystals of 80g compound (b-1).
[synthesis example 4]
According to following synthetic route synthetic compound (b-2).
In the eggplant type flask of 1L, add 91.3g4-methyl hydroxybenzoate, 182.4g salt of wormwood and 320mLN-N-methyl-2-2-pyrrolidone N-, at room temperature stir after 1 hour, add 99.7g1-bromo pentane silane, stir 5 hours at 100 DEG C.After reaction terminates, carry out redeposition with water.Then, add 48g sodium hydroxide and 400mL water in this precipitation, reflux 3 hours, be hydrolyzed reaction.After reaction terminates, with hydrochloric acid neutralization, and with ethanol, recrystallization is carried out to the precipitation generated, obtain the white crystals of (104g) compound (b-2 ').104g compound (b-2 ') is put in reaction vessel, adds 1L thionyl chloride and 770 μ LN wherein, dinethylformamide, stir 1 hour at 80 DEG C.Then, under reduced pressure distillate thionyl chloride, add methylene dichloride, with sodium bicarbonate aqueous solution washing, and by dried over mgso, concentrate, then add tetrahydrofuran (THF) and form solution.Then, from an above-mentioned different 5L there-necked flask, 74g4-hydroxyl TRANSCINNAMIC ACID, 138g salt of wormwood, 4.8g TBuA, 500mL tetrahydrofuran (THF) and 1L water is added.Frozen water cooling is carried out to this aqueous solution, and slowly drips the tetrahydrofuran solution of the reactant containing above-claimed cpd (b-2 ') and thionyl chloride, more under agitation reaction 2 hours.After reaction terminates, add hydrochloric acid in the reactive mixture and neutralize, and extract by ethyl acetate, then use dried over mgso extracting solution, concentrate, then carry out recrystallization with ethanol, obtain the white crystals of 90g compound (b-2) thus.
[synthesis example 5]
According to following synthetic route synthetic compound (b-3).
In the eggplant type flask of 1L, add 82g4-methyl hydroxybenzoate, 166g salt of wormwood and 400mLN, N-N,N-DIMETHYLACETAMIDE, at room temperature stir after 1 hour, add 95g4, the fluoro-1-butyl iodide of 4,4-tri-, at room temperature stir 5 hours, react.After reaction terminates, carry out redeposition with water.Then, add 32g sodium hydroxide and 400mL water in this precipitation, reflux 4 hours, be hydrolyzed reaction.After reaction terminates, with hydrochloric acid neutralization, and with ethanol, recrystallization is carried out to the precipitation generated, obtain the white crystals of 80g compound (b-3 ').46.4g in compound (b-3 ') is put in reaction vessel, adds 200mL thionyl chloride and 0.2mLN wherein, dinethylformamide, stir 1 hour at 80 DEG C.Then, under reduced pressure distillate thionyl chloride, add methylene dichloride, with sodium bicarbonate aqueous solution washing, and by dried over mgso, concentrate, then add tetrahydrofuran (THF) and form solution.Then, from an above-mentioned different 2L there-necked flask, 36g4-hydroxyl TRANSCINNAMIC ACID, 55g salt of wormwood, 2.4g TBuA, 200mL tetrahydrofuran (THF) and 400mL water is added.Frozen water cooling is carried out to this aqueous solution, and slowly drips the tetrahydrofuran solution of the reactant containing above-claimed cpd (b-3 ') and thionyl chloride, more under agitation reaction 2 hours.After reaction terminates, in reaction mixture, add hydrochloric acid neutralize, and extract by ethyl acetate, then use dried over mgso extracting solution, concentrate, then carry out recrystallization with ethanol, obtain the white crystals of 39g compound (b-3) thus.
[synthesis example 6]
According to following synthetic route, synthetic compound (b-4).
Except in above-mentioned synthesis example 4, and use 9.91g4-amyl group-trans cvclohexvl yl carboxylic acid replacement compound (b-2 ') outward, and synthesis example 4 operates equally, obtains the white crystals of 13g compound (b-4).
[synthesis example 7]
According to following synthetic route synthetic compound (b-5).
In the 500mL there-necked flask with return line, thermometer and nitrogen ingress pipe, add 31g compound (b-5 '), 0.23g acid chloride, 1.2g tri-(o-tolyl) phosphine, 56mL triethylamine, 8.2mL vinylformic acid and 200mLN, N-N,N-DIMETHYLACETAMIDE, and at 120 DEG C, under agitation react 3 hours.After reaction terminates, filter reaction mixture, in the solution of gained, add 1L ethyl acetate, and the organic layer to gained, wash twice with dilute hydrochloric acid successively, wash 3 times with water.Then dry over magnesium sulfate is used, and concentrated, solid, then carry out recrystallization with the mixed solvent of ethyl acetate and tetrahydrofuran (THF), obtain the crystallization of 15g compound (b-5) thus.
[synthesis example 8]
According to following synthetic route, synthetic compound (b-6).
Except using 36g compound (b-6 ') to replace except compound (b-5 '), and above-mentioned synthesis example 7 operates equally, obtains 16g compound (b-6).
[synthesis example 9]
According to following synthetic route, synthetic compound (b-7).
In the 200mL eggplant type flask with return line, add 12g decyl Succinic anhydried, the amino TRANSCINNAMIC ACID of 8.2g4-and 100mL acetic acid, react 2 hours under reflux.After reaction terminates, with ethyl acetate abstraction reaction mixture, wash organic layer with water, and by dried over mgso, then refine with silicon post, and carry out recrystallization with the mixed solvent of ethanol and tetrahydrofuran (THF) further, obtain the white crystals (purity is 98.0%) of 10g compound (b-7) thus.
[synthesis example 10]
Except in above-mentioned synthesis example 7, use the compound represented by 28g following formula (b-8 ') to replace compound (b-5 ') outward, and synthesis example 7 operate equally, obtains the compound (b-8) represented by 14g following formula.
[synthesis example 11]
According to following synthetic route, synthetic compound (b-9).
In the 500mL there-necked flask with return line and nitrogen ingress pipe, add 39g β-cholesterol, 20g Succinic anhydried, 1.5gN, N-dimethyl aminopyridine, 200mL ethyl acetate and 17mL triethylamine, react 8 hours under reflux.After reaction terminates, in reaction mixture, add 200mL tetrahydrofuran (THF), and the organic layer to gained, wash twice with 1N dilute hydrochloric acid successively, wash 3 times with water.And by dried over mgso, then under reduced pressure except desolventizing, and by ethyl acetate, recrystallization is carried out to the solid of gained, obtain the white crystals of 38g compound (b-9) thus.
The synthesis > of < [A] polyorganosiloxane compounds
[synthesis example 12]
In the there-necked flask of 200mL, add 10.0g (EPS-1), 69.5g mibk, 2.77g compound (A-1-1) (relative to the epoxy group(ing) that organopolysiloxane EPS-1 has, be equivalent to 20 % by mole), 4.60g stearic acid is (relative to the epoxy group(ing) that organopolysiloxane (EPS-1) has, be equivalent to 30 % by mole) and 1.00g Tetrabutyl amonium bromide, stir 8 hours at 100 DEG C, react.After reaction terminates, carry out redeposition with methyl alcohol, and by precipitate dissolves in ethyl acetate, obtain solution, and with water to solution washing 5 times, then distillate solvent, obtain 15.8g [A] polyorganosiloxane compounds (S-1) as white powder thus.
[synthesis example 13 ~ synthesis example 33]
Make kind and the use level of the compound of cooperation, as shown in table 1 respectively, and operate equally with synthesis example 12, synthesis [A] polyorganosiloxane compounds (S-2) ~ (S-22).
In addition, the usage ratio of the compound in table 1, be the epoxy group(ing) had relative to (EPS-1) % by mole.In addition, the Mw of organopolysiloxane (S-1) ~ (S-22), is shown in table 1 together.In addition, Whitfield's ointment, the benzoic structure of 4-diethylamino are as follows successively.
[comparing synthesis example 1]
In the there-necked flask of 200mL, add 10.0g (EPS-1), 58.4g mibk, 4.60g stearic acid (relative to the epoxy group(ing) that organopolysiloxane EPS-1 has, be equivalent to 30 % by mole) and 1.00g Tetrabutyl amonium bromide, stir 8 hours at 100 DEG C, react.After reaction terminates, carry out redeposition with methyl alcohol, and precipitate dissolves is obtained solution in ethyl acetate, with water to this solution washing 5 times, then distillate solvent, obtain the organopolysiloxane (CS-1) of 12.4g as white powder thus.
[comparing synthesis example 2 ~ 4]
Make the kind of the compound of cooperation and use level as shown in table 1 respectively, and and compare synthesis example 1 and operate equally, synthesis polyorganosiloxane compounds (CS-2) ~ (CS-4).In addition, the Mw of organopolysiloxane (CS-1) ~ (CS-4) is shown in table 1 together.
The synthesis > of < [B] polymkeric substance (polyamic acid)
[synthesis example 34]
Using the 196g (1.0 moles) 1 as tetracarboxylic dianhydride, 2,3,4-tetramethylene tetracarboxylic dianhydride, with the 212g (1.0 moles) 2 as diamines, 2 '-dimethyl-4,4 '-benzidine is dissolved in 4050gNMP, react 3 hours at 40 DEG C, obtain the polyamic acid solution (PA-1) that solid component concentration is 10%, soltion viscosity is 170mPas.
[synthesis example 35]
Using the 86.3g (0.44 mole) 1 as tetracarboxylic dianhydride, 2,3,4-tetramethylene tetracarboxylic dianhydride and 96.0g (0.44 mole) pyromellitic acid dianhydride, with the 191.0g (0.90 mole) 2 as diamines, 2 '-dimethyl-4,4 '-benzidine is dissolved in 1490gNMP, react 4 hours at 40 DEG C, then add NMP further, obtain the polyamic acid solution (PA-2) that solid component concentration is 10%, soltion viscosity is 43mPas.
The synthesis > of < [B] polymkeric substance (polyimide)
[synthesis example 36]
Using the 20.9g (0.093 mole) 2 as tetracarboxylic dianhydride, 3,5-tricarboxylic cyclopentyl acetic acid dianhydride, with as the compound represented by 9.2g (0.085 mole) Ursol D of diamines and 4.9g (0.009 mole) following formula (DA), be dissolved in 140gNMP, react 4 hours at 60 DEG C, take a morsel the polyamic acid solution of gained, and add NMP, obtain that solid component concentration is 10%, soltion viscosity is the polyamic acid solution of 126mPas.Then, in the polyamic acid solution of gained, add 325gNMP, and add 7.4g pyridine and 9.5g diacetyl oxide, at 110 DEG C, carry out 4 hours dehydration closed-loops.After dehydration closed-loop reaction, with new NMP, solvent exchange is carried out to the solvent in system, obtain about 210g and contain the solution that 16.1 % by weight imide rates are about the polyimide (PI-1) of 54%.Take a morsel the polyimide solution of gained, adds NMP, make solid component concentration be 10%, and its soltion viscosity measured is 75mPas.
[synthesis example 37]
Using the 20.0g (0.089 mole) 2 as tetracarboxylic dianhydride, 3,5-tricarboxylic cyclopentyl acetic acid dianhydride, with 6.8g (0.063 mole) Ursol D, the 3.6g (0.018 mole) 4 as diamines, 4 '-diaminodiphenyl-methane and the compound represented by 4.7g (0.0090 mole) above-mentioned formula (DA), be dissolved in 140gNMP, react 4 hours at 60 DEG C, obtain that solid component concentration is 20%, soltion viscosity is the polyamic acid solution of 2200mPas.Then, in the polyamic acid solution of gained, add 325gNMP, and add 10.5g pyridine and 13.6g diacetyl oxide, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new NMP, solvent exchange is carried out to the solution in system, obtain the solution (solid component concentration is 20%) that about 160g imide rate is about the polyimide (PI-2) of 65%.
[synthesis example 38]
Using the 19.2g (0.086 mole) 2 as tetracarboxylic dianhydride, 3,5-tricarboxylic cyclopentyl acetic acid dianhydride, with the 5.2g (0.034 mole) 3 as diamines, 5-diaminobenzoic acid and 25.5g (0.052 mole) diamines represented by following formula, be dissolved in 200gNMP, react 4 hours at 60 DEG C, obtain that solid component concentration is 20%, soltion viscosity is the polyamic acid solution of 1450mPas.Then, in the polyamic acid solution of gained, add 250gNMP, and add 10.2g pyridine and 13.2g diacetyl oxide, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new NMP, solvent exchange is carried out to the solution in system, obtain about 230g and contain the solution that 20 % by weight imide rates are about the polyimide (PI-3) of 67%.
Other the synthesis > of polyorganosiloxane compounds of < [C]
[synthesis example 39]
In the 200mL there-necked flask with prolong, add 20.8g tetraethoxysilane and 28.2g1-oxyethyl group-2-propyl alcohol, be heated to 60 DEG C and stir.The 0.26g maleic anhydride modulated in other flask that the capacity that is added in wherein is 20mL is dissolved in the maleic anhydride aqueous solution of gained in 10.8g water, then stirs 4 hours at 60 DEG C, reacts.After reaction terminates, from the reaction mixture of gained, distillate solvent, in remnant, add 1-oxyethyl group-2-propyl alcohol, again concentrate, obtain organopolysiloxane (PS-1) solution that solid component concentration is 10% thus.Mw is 5100.
The modulation > of < liquid crystal aligning agent
[embodiment 1]
By 100 mass parts organopolysiloxane (S-1) be scaled polyamic acid (PA-1) and be equivalent to mixing containing the solution of polyamic acid (PA-1) of 1000 mass parts, and adding NMP and ethylene glycol mono-n-butyl ether wherein, formation solvent composition is NMP: ethylene glycol mono-n-butyl ether=50: 50 (mass ratioes), solid component concentration are the solution of 3.0 quality %.Use aperture is this solution of metre filter of 1 μm, and modulation liquid crystal aligning agent (AF-1), it can be used as embodiment 1.
[embodiment 2 ~ 39 and comparative example 1 ~ 7]
Make the kind of the mixture of cooperation and usage quantity respectively as shown in table 2 described later, and operate equally with embodiment 1, modulation liquid crystal aligning agent (AF-2) ~ (AF-39) and (CAF-1) ~ (CAF-7), using them as embodiment 2 ~ 39, comparative example 1 ~ 7.
< storage stability >
For above-mentioned each liquid crystal aligning agent, evaluate storage stability according to following (method 1) or (method 2).Result is shown in table 2.
(method 1)
Use spin-coating method, and be variable with rotation number, by liquid crystal aligning agent (AF-1) ~ (AF-12) and (CAF-1) ~ (CAF-3) coating on the glass substrate, then heat 60 minutes at 200 DEG C, form film thus, investigation makes except the film thickness after desolventizing is rotation number.Then, get a part for above-mentioned liquid crystal aligning agent, it is preserved 5 weeks at-15 DEG C.Liquid crystal aligning agent after visual observation preservation, is evaluated as storage stability " bad " when observing insolubles and separating out.When preservation 5 Zhou Houwei observes insolubles, further by spin-coating method, and to preserve front thickness be rotation number, by the liquid crystal aligning agent coating after preserving on the glass substrate, then heat 60 minutes at 200 DEG C, form film, measure except the thickness after desolventizing.When this thickness by when having changed more than 10%, be evaluated as storage stability " bad ", when thickness change less than 10% time, be evaluated as storage stability " well ".In addition, the mensuration of above-mentioned film thickness, the contact pin type section difference film thickness gauge using KLA-Tencor company to manufacture carries out.
(method 2)
Liquid crystal aligning agent (AF-13) ~ (AF-39) and (CAF-4) ~ (CAF-7) is taken care of 6 months at-15 DEG C.Before and after keeping, E type viscometer is used to measure viscosity at 25 DEG C.When soltion viscosity keeping before and after velocity of variation less than 10% time, be evaluated as storage stability " well ", when it is more than 10%, be evaluated as storage stability " bad ".
[table 2]
The manufacture > of < liquid crystal display device
[embodiment 40]
Spin coater is used to be coated on the transparent electrical pole-face of the glass substrate with the transparency electrode formed by ito film by liquid crystal aligning agent (AF-1), and on the hot plate of 80 DEG C prebake 1 minute, then in the baking oven carrying out nitrogen replacement, heat 1 hour at 200 DEG C, except desolventizing, form the film that thickness is 0.1 μm.Repeat this operation, make the substrate that a pair (two panels) has liquid crystal orientation film.Pass through silk screen printing, the periphery in an above-mentioned plate base with the face of liquid crystal orientation film is coated with and adds diameter is after the epoxy resin binder of the alumina balls of 5.5 μm, by overlapping for the liquid crystal aligning face of a pair substrate also pressing, and heat 1 hour at 150 DEG C, make tackiness agent thermofixation.Then, in the gap of substrate, nematic liquid crystal (メ ルク company is filled by liquid crystal injecting port, MLC-6608) after, with epoxy adhesive encapsulated liquid crystals inlet, in addition, in order to eliminate flow orientation during Liquid crystal pour, after heating 10 minutes at its 150 DEG C, slowly cool to room temperature.To fit on the two sides, outside of substrate further polarization plates, make the direction of polarized light of two panels polarization plates orthogonal, manufacture the liquid crystal display device of vertical orientating type thus, it can be used as embodiment 40.
[embodiment 41 ~ 51, comparative example 8 ~ 10]
Use liquid crystal aligning agent (AF-2) ~ (AF-12) and (CAF-1) ~ (CAF-3), and embodiment 40 operates equally, manufacture liquid crystal display device, using them as embodiment 41 ~ 51, comparative example 8 ~ 10.
[embodiment 52]
Spin coater is used to be coated on the transparent electrical pole-face of the glass substrate with the transparency electrode formed by ito film by liquid crystal aligning agent (AF-13), and on the hot plate of 80 DEG C prebake 1 minute, then in the baking oven carrying out nitrogen replacement, heat 1 hour at 200 DEG C, except desolventizing, form the film that thickness is 0.1 μm.Then, use Hg-Xe lamp and Glan-Taylor prism, by the direction of opposing substrate normal slope 40 °, 200J/m is irradiated to this film coated surface 2comprise the polarized UV rays that wavelength is 313nm bright line, form liquid crystal orientation film.Repeat same operation, make the substrate that a pair (two panels) has liquid crystal orientation film.Pass through silk screen printing, the periphery in an above-mentioned plate base with the face of liquid crystal orientation film is coated with and adds diameter is after the epoxy resin binder of the alumina balls of 5.5 μm, make the liquid crystal aligning face of a pair substrate relative and carry out pressing, the projecting direction of each substrate middle-ultraviolet lamp optical axis on real estate is made to be antiparallel, and heat 1 hour at 150 DEG C, make tackiness agent thermofixation.Then, after filling nematic liquid crystal (メ ルク company, MLC-6608) by liquid crystal injecting port in the gap between substrate, with epoxy adhesive encapsulated liquid crystals inlet.In addition, in order to eliminate flow orientation during Liquid crystal pour, after heating 10 minutes at its 150 DEG C, room temperature is slowly cooled to.Then, to fit in the two sides, outside of substrate polarization plates, make the direction of polarized light of polarization plates orthogonal, and make the projecting direction of the ultraviolet optical axis of liquid crystal orientation film on real estate be 45° angle, manufacture the liquid crystal display device of vertical orientating type thus, it can be used as embodiment 52.
[embodiment 53 ~ 78, comparative example 11 ~ 14]
Use liquid crystal aligning agent (AF-13) ~ (AF-39) and (CAF-4) ~ (CAF-7), and embodiment 52 operates equally, manufacture liquid crystal display device, using them as embodiment 53 ~ 78, comparative example 11 ~ 14.
To the liquid crystal display device of embodiment 40 ~ 78 and comparative example 8 ~ 14, carry out following evaluation, result is displayed in Table 3.
< liquid crystal aligning >
By visual observation abnormal area with or without light and shade change when liquid crystal display device switch (apply remove) the 5V voltage to above-mentioned manufacture.Do not observe box light leak when voltage closes, and when applying voltage box drive area display white, and region does not in addition have the situation of light leak, is liquid crystal aligning " well ".Observe box light leak when voltage closes, or observe the situation of the region light leak beyond box drive area when voltage is opened, be liquid crystal aligning " bad ".
< 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 under the envrionment temperature of 60 DEG C after, measure from applying to remove the voltage retention after 167 milliseconds.Determinator uses the VHR-1 of Dongyang テ Network ニ power company.When voltage retention is more than 97%, be evaluated as voltage retention " well ".
< photostabilization >
Under the condition identical with the evaluation of voltage retention, the liquid crystal display device of above-mentioned manufacture is measured to the voltage retention at initial stage.Then, be configured in the 5cm distance under 100 tile-type white fluorescent lamps, after the irradiation 500 little time, again under condition same as described above, measured voltage retention.When the reduced rate of the voltage retention compared with initial value is less than 1%, be evaluated as photostabilization " A ", when its more than 1% and be less than 2% time, be evaluated as photostabilization " B ", when it is more than 2%, be evaluated as photostabilization " C ".
[table 3]
Known from the result of table 2 and 3, the storage stability of liquid crystal aligning agent of the present invention is excellent.And known, the liquid crystal orientation film formed by this liquid crystal aligning agent, fully meets required liquid crystal aligning, voltage retention and photostabilization as liquid crystal display device in practical.
Industrial applicibility
According to the present invention, a kind of liquid crystal orientation film fully meeting the characteristics such as required liquid crystal aligning, voltage retention and photostabilization as liquid crystal display device in practical can be provided; The formation method of this liquid crystal orientation film; The storage stability being suitable as liquid crystal aligning film formation material is excellent, and optical alignment method can be adopted to form the liquid crystal aligning agent of liquid crystal orientation film; And possess the liquid crystal display device of liquid crystal orientation film.Possess the liquid crystal display device of the application of the liquid crystal orientation film formed by this liquid crystal aligning agent, can suitably for display unit such as such as clock and watch, portable game machine, word processor, notebook computer, auto-navigation system, pick up camera, portable data assistance, digital camera, mobile telephone, various indicating meter, LCD TV.

Claims (13)

1. a liquid crystal aligning agent, it contains, and [A] has the polyorganosiloxane compounds of piperidine structure, this polyorganosiloxane compounds comprises the structure with liquid crystal aligning energy, this have liquid crystal aligning can structure have from being the organic group of 17 ~ 51 by the carbonatoms with steroid skeleton, carbonatoms is the alkyl of 2 ~ 20, carbonatoms is the fluoro-alkyl of 1 ~ 20, cyclohexyl, there is the alkoxy aryl that carbonatoms is the alkyl of 2 ~ 20, there is the alkyl-cyclohexyl that carbonatoms is the alkyl of 1 ~ 20, having fluoro-alkyl cyclohexyl that carbonatoms is the fluoro-alkyl of 1 ~ 20 and having carbonatoms is at least one group selected in the group that forms of the fluoroalkyl cyclohexyl of the fluoroalkyl of 1 ~ 20.
2. liquid crystal aligning agent as claimed in claim 1, wherein above-mentioned piperidine structure is represented by following formula (A-1 '),
Formula (A-1 ') in,
R 1for aralkyl or 1,3-bis-oxygen-butyl that hydrogen atom, the carbonatoms alkyl that is 1 ~ 6, the carbonatoms aryl that is 6 ~ 20, carbonatoms are 7 ~ 13,
R 2~ R 5the alkyl, the carbonatoms that are 1 ~ 6 for carbonatoms be independently of one another 6 ~ 12 aryl or carbonatoms be the aralkyl of 7 ~ 13,
X 1for singly-bound, carbonyl or *-CONH-; X 2~ X 5be independently of one another singly-bound, carbonyl, *-CH 2-CO-or *-CH 2-CH (OH)-, the connecting key represented by * * is connected with piperidine ring, and main chain or the side chain of the connecting key represented by * and organopolysiloxane skeleton are connected.
3. liquid crystal aligning agent as claimed in claim 1, wherein [A] polyorganosiloxane compounds contains: the part selecting at least one in the group that the condenses coming from organopolysiloxane, its hydrolyzate and this hydrolyzate is formed, and this organopolysiloxane has the structural unit represented by following formula (1); Come from the part of the compound represented by following formula (A-1),
In formula (1), X afor there is 1 valency organic group of epoxy group(ing), Y afor hydroxyl, carbonatoms be 1 ~ 10 alkoxyl group, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the aryl of 6 ~ 20,
In formula (A-1), R 1~ R 5and X 1~ X 5with above-mentioned formula (A-1 ') synonym,
Y is singly-bound, carbonatoms is the alkane 2 basis of 1 ~ 16, and above-mentioned alkane 2 basis can have Sauerstoffatom, sulphur atom, carbonyl, ester group, amide group in the structure or by the two or more groups combined in them, Z is carboxyl or hydroxyl.
4. liquid crystal aligning agent as claimed in claim 3, the X wherein in above-mentioned formula (1) afor following formula (X a-1) or formula (X a-2) group represented by,
Formula (X a-1) and formula (X a-2) in, s is the integer of 0 ~ 3, and t is the integer of 1 ~ 6, and u is the integer of 0 ~ 2, and v is the integer of 0 ~ 6, and the connecting key represented by * is connected with Siliciumatom.
5. liquid crystal aligning agent, wherein above-mentioned formula (X as claimed in claim 4 a-1) or formula (X a-2) group represented by, is respectively following formula (X a-1-1) or (X a-2-1) represented by group,
Formula (X a-1-1) and formula (X a-2-1) in, the connecting key represented by * is connected with Siliciumatom.
6. liquid crystal aligning agent as claimed in claim 1, the structure wherein with above-mentioned liquid crystal aligning energy is represented by following formula (B-1),
In formula (B-1), m is the integer of 0 ~ 4.
7. the liquid crystal aligning agent as described in any one of Claims 1 to 5, at least one polymkeric substance selected in its group be made up of polyamic acid and polyimide containing [B] further.
8. the liquid crystal aligning agent as described in any one of Claims 1 to 5, it has the polyorganosiloxane compounds of the structural unit represented by following formula (2) further containing [C],
In formula (2), X bfor hydroxyl, halogen atom, carbonatoms be 1 ~ 20 alkyl, carbonatoms be 1 ~ 6 alkoxyl group or carbonatoms be the aryl of 6 ~ 20, Y bfor hydroxyl or carbonatoms are the alkoxyl group of 1 ~ 10.
9. a formation method for liquid crystal orientation film, has:
(1) claim 6, claim 7 or liquid crystal aligning agent according to claim 8 are coated on substrate, form the operation of film, and
(2) to the operation of irradiating radioactive rays at least partially of the film that operation (1) is formed.
10. the liquid crystal orientation film formed by the liquid crystal aligning agent described in any one of claim 1 ~ 8.
11. 1 kinds of liquid crystal display device possessing liquid crystal orientation film according to claim 10.
12. 1 kinds of polyorganosiloxane compounds, it has piperidine structure and comprises the structure with liquid crystal aligning energy, this have liquid crystal aligning can structure have from being the organic group of 17 ~ 51 by the carbonatoms with steroid skeleton, carbonatoms is the alkyl of 2 ~ 20, carbonatoms is the fluoro-alkyl of 1 ~ 20, cyclohexyl, there is the alkoxy aryl that carbonatoms is the alkyl of 2 ~ 20, there is the alkyl-cyclohexyl that carbonatoms is the alkyl of 1 ~ 20, having fluoro-alkyl cyclohexyl that carbonatoms is the fluoro-alkyl of 1 ~ 20 and having carbonatoms is at least one group selected and have the structure represented by following formula (B-1) in the group that forms of the fluoroalkyl cyclohexyl of the fluoroalkyl of 1 ~ 20,
In formula (B-1), m is the integer of 0 ~ 4.
13. polyorganosiloxane compounds as claimed in claim 12, wherein above-mentioned piperidine structure is the structure represented by following formula (A-1 '),
Formula (A-1 ') in,
R 1for aralkyl or 1,3-bis-oxygen-butyl that hydrogen atom, the carbonatoms alkyl that is 1 ~ 6, the carbonatoms aryl that is 6 ~ 20, carbonatoms are 7 ~ 13,
R 2~ R 5the alkyl, the carbonatoms that are 1 ~ 6 for carbonatoms be independently of one another 6 ~ 12 aryl or carbonatoms be the aralkyl of 7 ~ 13,
X 1for singly-bound, carbonyl or *-CONH-, X 2~ X 5be independently of one another singly-bound, carbonyl, *-CH 2-CO-or *-CH 2-CH (OH)-, the connecting key represented by * * is connected with piperidine ring,
Main chain or the side chain of * represented connecting key and organopolysiloxane skeleton are connected.
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JP6828360B2 (en) * 2016-01-07 2021-02-10 Jsr株式会社 A liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, and a method for manufacturing a liquid crystal alignment film and a liquid crystal element.
US20190040320A1 (en) * 2016-02-03 2019-02-07 Sharp Kabushiki Kaisha Alignment film, polymer, and liquid crystal display device
WO2018163802A1 (en) * 2017-03-07 2018-09-13 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, and polyorganosiloxane
TWI735595B (en) * 2017-06-12 2021-08-11 奇美實業股份有限公司 Positive photosensitive polyalkylsiloxane composition and application of the same
CN110803990B (en) * 2018-08-04 2023-08-08 石家庄诚志永华显示材料有限公司 Compound, liquid crystal composition, liquid crystal display element and liquid crystal display

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2295619A (en) * 1994-11-30 1996-06-05 Ciba Geigy Ag Siloxanes containing piperidine triazine groups as stabilisers
US5561179A (en) * 1994-11-30 1996-10-01 Ciba-Geigy Corporation Piperidine compounds containing silane groups as stabilizers for organic materials
CN101591544A (en) * 2008-05-26 2009-12-02 Jsr株式会社 Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
CN101687996A (en) * 2007-08-01 2010-03-31 Jsr株式会社 Polyorganosiloxane, liquid crystal alignment film, and liquid crystal display element

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5691277A (en) 1979-12-25 1981-07-24 Citizen Watch Co Ltd Liquiddcrystal display panel
CH664027A5 (en) 1983-07-12 1988-01-29 Bbc Brown Boveri & Cie LCD with twisted nematic crystal between support plates
JP2869511B2 (en) 1990-10-17 1999-03-10 日本航空電子工業株式会社 TN type liquid crystal display device
JPH04247091A (en) * 1991-01-31 1992-09-03 Shin Etsu Chem Co Ltd Organic silicon compound
SG64893A1 (en) 1993-02-17 1999-08-17 Rolic Ag Orientating layers for liquid crystals
JPH0784266A (en) * 1993-09-14 1995-03-31 Toshiba Corp Production of liquid crystal display element
DE19535939A1 (en) * 1995-09-27 1997-04-03 Agfa Gevaert Ag Photographic material
JP3757514B2 (en) 1996-02-16 2006-03-22 日産化学工業株式会社 Method for forming liquid crystal vertical alignment film
EP0806698B1 (en) 1996-05-08 2005-01-12 Hitachi, Ltd. In-plane switching-mode active-matrix liquid crystal display
US5959057A (en) * 1997-01-21 1999-09-28 Dow Corning Toray Silicone Co., Ltd. Polyorganosiloxane and method for the preparation thereof
JPH10204179A (en) * 1997-01-21 1998-08-04 Toray Dow Corning Silicone Co Ltd Polyorganosiloxane and its production
US6482912B2 (en) * 2001-01-29 2002-11-19 Ndsu Research Foundation Method of preparing aminofunctional alkoxy polysiloxanes
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
JP3885714B2 (en) 2002-11-13 2007-02-28 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
CN101484537B (en) * 2006-07-05 2013-07-17 西巴控股有限公司 Coloured organic electrophoretic particles
JP5454772B2 (en) * 2008-11-17 2014-03-26 Ｊｓｒ株式会社 Liquid crystal aligning agent, liquid crystal aligning film, method for forming the same, and liquid crystal display element

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2295619A (en) * 1994-11-30 1996-06-05 Ciba Geigy Ag Siloxanes containing piperidine triazine groups as stabilisers
US5561179A (en) * 1994-11-30 1996-10-01 Ciba-Geigy Corporation Piperidine compounds containing silane groups as stabilizers for organic materials
CN101687996A (en) * 2007-08-01 2010-03-31 Jsr株式会社 Polyorganosiloxane, liquid crystal alignment film, and liquid crystal display element
CN101591544A (en) * 2008-05-26 2009-12-02 Jsr株式会社 Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device

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