CN102604652B - Liquid crystal aligning agent, liquid crystal display device and manufacture method thereof - Google Patents

Liquid crystal aligning agent, liquid crystal display device and manufacture method thereof Download PDF

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CN102604652B
CN102604652B CN201210014797.1A CN201210014797A CN102604652B CN 102604652 B CN102604652 B CN 102604652B CN 201210014797 A CN201210014797 A CN 201210014797A CN 102604652 B CN102604652 B CN 102604652B
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liquid crystal
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aligning agent
display device
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CN102604652A (en
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德久博昭
宫本佳和
吉泽纯司
清水成夫
西川通则
樫下幸志
秋池利之
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JSR Corp
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
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    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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Abstract

The present invention relates to liquid crystal aligning agent, liquid crystal display device and manufacture method thereof, its object is to provide: the liquid crystal aligning agent of the liquid crystal display device of the PSA mode of all excellents such as high-speed response can be formed, possess the liquid crystal display device of the PSA mode of the liquid crystal orientation film formed by this liquid crystal aligning agent and the manufacture method of such liquid crystal display device.The present invention is the liquid crystal aligning agent of the liquid crystal orientation film formed in the liquid crystal display device of PSA mode, it is characterized in that, there is containing [A] compound (following, to be also called " [A] compound ") of the group represented by following formula (1). in formula (1), R 1for at least having the group of two single ring architectures.R 2for comprising the link group of double bond, triple bond, ehter bond, ester bond or Sauerstoffatom.A is the integer of 0 ~ 1.

Description

Liquid crystal aligning agent, liquid crystal display device and manufacture method thereof
Technical field
The present invention relates to liquid crystal aligning agent, liquid crystal display device and liquid crystal display device
Manufacture method.
Background technology
In recent years, power consumption is little owing to having for liquid crystal display device, miniaturization and the advantage such as flattening is easy, is therefore applied to the purposes of the such wide region of large-screen lc display unit from the small-scale liquid crystal device of mobile phone etc. to LCD TV etc.
At present, the drive pattern of liquid crystal indicator, according to the change of orientation (arrangement) state of liquid crystal molecule, there will be a known TN (twisted-nematic), STN (supertwist is to row), IPS (plane conversion), VA (vertical orientated) etc.In addition, with regard to VA pattern, visual angle is improved in order to be split by orientation, employing has MVA (multi-domain vertical alignment) mode, PVA (image is vertical orientated) mode, in order to improve high-speed response, panel aperture opening ratio further, studying and adopting PSA (polymer stabilizing orientation) mode.
This PSA mode refers to, in advance the monomer by light or thermopolymerization is mixed into liquid crystal, make monomer polymerization under state after applying voltage makes liquid crystal molecules tilt, thus remember the technology (with reference to Japanese Unexamined Patent Publication 2002-357830 publication, Japanese Unexamined Patent Publication 2003-307720 publication, Japanese Unexamined Patent Publication 2003-177418 publication) of the vergence direction of liquid crystal molecule.With regard to employing the liquid crystal display device of PSA mode, due to such as liquid crystal molecule be relative to substrate interface minimum tilt after state under support, therefore, when applying voltage, liquid crystal molecule can be made positively to swing to this vergence direction, consequently fast response time.
The state of orientation of the liquid crystal molecule in such liquid crystal display device is controlled by liquid crystal orientation film, and liquid crystal orientation film is responsible for the manifesting of the functional performance of liquid crystal display device, controls in sizable degree.In PSA mode, in order to improve the functions such as response speed, also a kind of liquid crystal indicator (Japanese Unexamined Patent Publication 2006-215326 publication) defining the composition of liquid crystal aligning agent for the formation of this liquid crystal orientation film is being developed, but in order to realize the high performance of response speed etc., require to realize further improving.
Prior art document
[patent documentation]
Patent documentation 1: Japanese Unexamined Patent Publication 2002-357830 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-307720 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2003-177418 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2006-215326 publication
Summary of the invention
The present invention is based on situation as described above and carry out, its object is to provide: the liquid crystal aligning agent of the liquid crystal display device of the PSA mode of all excellents such as high-speed response can be formed, possess the liquid crystal display device of the PSA mode of the liquid crystal orientation film formed by this liquid crystal aligning agent and the manufacture method of such liquid crystal display device.
In order to the feature solving the invention that above-mentioned problem is developed is, for the liquid crystal aligning agent of the liquid crystal orientation film in a kind of liquid crystal display device forming PSA mode, the compound containing [A] with the group represented by following formula (1) is (following, also be called " [A] compound ")
In formula (1), R 1for at least having the group of two single ring architectures.R 2for comprising the link group of double bond, triple bond, ehter bond, ester bond or Sauerstoffatom.A is the integer of 0 ~ 1.
This liquid crystal aligning agent contains [A] compound, should possess the above-mentioned group with dielectric anisotropy by [A] compound, and the tropism control of liquid crystal molecule is excellent.Thus, possess and use this liquid crystal aligning agent and in the liquid crystal display device of the PSA mode of liquid crystal orientation film that formed, the orientation of liquid crystal molecule is good and can shorten the time of response.
[A] compound can have: be derived from the part of the organopolysiloxane with epoxy group(ing), be derived from the part of the compound (following, to be also called " specific carboxylic acid ") represented by following formula (2),
In formula (2), R 1, R 2and a is same with above-mentioned formula (1) defines.R 3for the alkylidene group of methylene radical, carbonatoms 2 ~ 30, phenylene or cyclohexylidene, these groups can have substituting group further.
According to this liquid crystal aligning agent, by utilizing the reactivity of epoxy group(ing) and carboxyl, thus can easily to as the structure with dielectric anisotropy represented by above-mentioned formula (1) imported in the organopolysiloxane of main chain as side chain, using as [A] compound.Therefore, this liquid crystal aligning agent can give obtained liquid crystal display device effectively with high-speed response.
Above-mentioned R 1can be the group represented by following formula (3),
In formula (3), R 4for hydrogen atom, cyano group, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxyl group, trifluoromethoxy or alkyl-carbonyl oxygen base.R 5for removing (b+1) individual hydrogen atom from benzene, biphenyl, naphthalene, hexanaphthene, bis cyclohexane, phenylcyclohexane or heterogeneous ring compound and the group of (b+1) valency that obtains, these groups can have substituting group further.R 6for comprising the link group of any one in methylene radical, the alkylidene group of carbonatoms 2 ~ 10, double bond, triple bond, ehter bond, ester bond and heterocycle, these groups can have substituting group further.R 7be phenylene, biphenylene, naphthyl, cyclohexylidene, two cyclohexylidene, cyclohexylidene phenylene or heterocycle independently of one another, these groups can have substituting group further.B is the integer of 1 ~ 9.When b is more than 2, multiple R 4can identical also can be different.C is the integer of 0 ~ 1.D is the integer of 1 ~ 2.When d is 2, multiple R 6, R 7and c can be the same or different separately.
By importing the structure represented by above-mentioned formula (3) in [A] compound of this liquid crystal aligning agent, thus the responsiveness of the liquid crystal display device of acquisition can be made to become more at a high speed.
Above-mentioned epoxy group(ing) can be by following formula (X 1-1) or (X 1-2) group represented,
Formula (X 1-1), in, A is Sauerstoffatom or singly-bound.H is the integer of 1 ~ 3.I is the integer of 0 ~ 6.Wherein, when i is 0, A is singly-bound.
Formula (X 1-2), in, j is the integer of 0 ~ 6.
By comprising in above-mentioned organopolysiloxane by above-mentioned formula (X 1-1) or (X 1-2) group represented, thus be easy to import the group represented by above-mentioned formula (1) in [A] compound of this liquid crystal aligning agent.
This liquid crystal aligning agent can contain at least one polymkeric substance (following, to be also called " [B] polymkeric substance ") selected in the group that [B] be made up of polyamic acid and polyimide further.When using the liquid crystal aligning agent containing [B] polymkeric substance and form liquid crystal orientation film, high-speed response can be obtained and obtain the liquid crystal display device more improved.
Liquid crystal display device of the present invention is the liquid crystal display device of the PSA mode possessing the liquid crystal orientation film formed by this liquid crystal aligning agent.According to this liquid crystal display device, by forming liquid crystal orientation film by above-mentioned liquid crystal aligning agent, thus liquid crystal aligning is high, and can play excellent high-speed response.
The manufacture method of liquid crystal display device of the present invention is the manufacture method of the liquid crystal display device of PSA mode, and it has following operation:
Formed the operation of liquid crystal orientation film by this liquid crystal aligning agent at each internal surface of a pair substrate with transparency electrode,
The mode subtend configuration that above-mentioned a pair substrate is faced each other according to internal surface, to the operation of filling polymerizable liquid crystal compound between this substrate, and
The operation that above-mentioned polymerizable liquid crystal compound solidifies is made under the state being applied with voltage.
According to this manufacture method, by forming liquid crystal orientation film by above-mentioned liquid crystal aligning agent, thus it is high and have the liquid crystal display device of the PSA mode of excellent high-speed response to manufacture liquid crystal aligning.
As described above, according to liquid crystal aligning agent of the present invention, the liquid crystal display device of the PSA mode of all excellents such as high-speed response can be formed.In addition, liquid crystal display device of the present invention, as the element of PSA mode, can play high responsiveness etc.Manufacturing method according to the invention, can manufacture the liquid crystal display device of the PSA mode possessing high responsiveness etc.
Accompanying drawing explanation
Fig. 1: the pattern sectional view representing the liquid crystal display device of an embodiment of the invention.
Fig. 2 (a) ~ Fig. 2 (b): the pattern sectional view representing the liquid crystal display device of the form different from the liquid crystal display device of Fig. 1.
Fig. 3: the mode chart of the liquid crystal display device manufactured by embodiment.
Embodiment
Below, the embodiment of the manufacture method of liquid crystal aligning agent of the present invention, liquid crystal display device and liquid crystal display device is described in detail.
< liquid crystal aligning agent >
The feature of liquid crystal aligning agent of the present invention is, it is the liquid crystal aligning agent of the liquid crystal orientation film formed in the liquid crystal display device of PSA mode, containing [A] compound.In addition, this liquid crystal aligning agent can containing " other polymkeric substance " described later such as [B] polymkeric substance.Further, this liquid crystal aligning agent also can contain other optional member in the scope not damaging effect of the present invention.Below each composition is described in detail.
< [A] compound >
[A] compound is for having the compound of the group represented by above-mentioned formula (1).The group represented by above-mentioned formula (1) has dielectric anisotropy, and the liquid crystal aligning agent comprising [A] compound is excellent in the tropism control of liquid crystal molecule.Thus, use this liquid crystal aligning agent and for the liquid crystal display device of the PSA mode of liquid crystal orientation film that formed with regard to possessing, the orientation of liquid crystal molecule is good and can shorten the time of response.
In above-mentioned formula (1), R 1for at least having the group of two single ring architectures, preferably manifest the dielectric anisotropy of plus or minus.Single ring architecture refers to: a ring structure exists independent of other ring structure, and the structure without so-called condensed cyclic structure that the key of a ring structure and other ring structure have.In addition, as single ring architecture, can be any one in ester ring type structure, fragrant ring structures, hetero ring type structure, also may be combined with them and have.
R 1as long as at least have the group of two single ring architectures, be so not particularly limited, but say R typically 1the group preferably represented by above-mentioned formula (3).By importing the structure represented by above-mentioned formula (3) in the side chain of [A] compound to this liquid crystal aligning agent, thus the further high speed of electrooptics responsiveness of the liquid crystal aligning element of acquisition can be made.
In above-mentioned formula (3), R 4for any one in hydrogen atom, cyano group, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxyl group, trifluoromethoxy and alkyl-carbonyl oxygen base.As alkoxy carbonyl, such as, list methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl etc.; As alkyl, such as, list the straight or branched alkyl etc. that the carbonatomss such as methyl, ethyl, propyl group, normal-butyl, isobutyl-are 1 ~ 20; As alkoxyl group, such as, list methoxyl group, oxyethyl group, propoxy-etc.; As alkyl-carbonyl oxygen base, such as, list methyl ketonic oxygen base, ethylcarbonyl group oxygen base etc.
In above-mentioned formula (3), R 4when existing multiple, also may be combined with different group and use.As having multiple R 4when combination, in order to stably manifest desired dielectric anisotropy, the combination of the combination of the combination of preferred fluorine atom and cyano group, fluorine atom and alkyl, cyano group and alkyl.Again, b is the integer of 0 ~ 9.
In above-mentioned formula (3), R 5for removing (b+1) individual hydrogen atom from benzene, biphenyl, naphthalene, hexanaphthene, bis cyclohexane, phenylcyclohexane or heterogeneous ring compound and the group of (b+1) valency that obtains, these groups can have substituting group further.As above-mentioned heterogeneous ring compound, include, for example out pyridine, pyridazine, pyrimidine etc.
In above-mentioned formula (3), R 6for comprising the link R of any one in methylene radical, the alkylidene group of carbonatoms 2 ~ 10, double bond, triple bond, ehter bond, ester bond and heterocycle 5and R 7link group, these groups (alkylidene group, heterocycle) can have substituting group further.As R 6, list methane two base, ethane two base, propane two base, ethene two base, acetylene two base, ether, ester group, methane two base oxygen base, ethane two base oxygen base, fluoromethane two base oxygen base, methylene fluoride two base oxygen base etc.Among them, be preferably ethane two base, acetylene two base, ester group, methane two base oxygen base, methylene fluoride two base oxygen base.Suitably can select according to the necessary orientation of [A] compound, dielectric anisotropy.Again, because c is the integer of 0 or 1, thus can comprise and also can not comprise R 6.
In above-mentioned formula (3), R 7be phenylene, biphenylene, naphthyl, cyclohexylidene, two cyclohexylidene, cyclohexylidene phenylene or heterocycle independently of one another.As heterocycle, such as, list pyridine ring, pyridazine ring, pyrimidine ring etc.
In above-mentioned formula (3), d is the integer of 1 ~ 2.When d is 2, multiple R 6, R 7and c can be the same or different separately.
As the group represented by above-mentioned formula (3), such as, list the group represented by following formula (D-1) ~ (D-123),
In formula (D-1) ~ (D-123), R is the alkyl (methyl, ethyl, propyl group, normal-butyl, isobutyl-, n-pentyl, n-hexyl etc.) of carbonatoms 1 to 20 or the alkoxyl group (methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy etc.) of carbonatoms 1 ~ 20.X is hydrogen atom or fluorine atom independently of one another.
In above-mentioned formula (1), R 2for comprising the link group of any one in double bond, triple bond, ehter bond, ester bond and Sauerstoffatom.R 2comprise any one in above-mentioned key, but also may be combined with each key and comprise.As R 2, such as, list ethene two base, acetylene two base, ester group, methane two base oxygen base, fluoromethane two base oxygen base, methylene fluoride two base oxygen base etc.Again, R described later 3when for phenylene or cyclohexylidene, consider from the orientation of formed alignment films, deliquescent viewpoint in a solvent, R 2preferably comprise the alkylidene group that carbonatoms is 1 ~ 30.Again, a is the integer of 0 ~ 1.
As [A] compound, as long as there is the group represented by above-mentioned formula (1) be just not particularly limited, but preferably there is at side chain the polymkeric substance of the group represented by formula (1), from the viewpoint of electrical characteristic more preferably by organopolysiloxane, polyimide, polyamic acid, polyacrylic ester, polymethacrylate, poly-(vinylbenzene-phenyl maleimide) derivative, derivatived cellulose, polyester, polymeric amide, polystyrene derivative, poly amic acid ester makes the polymkeric substance of backbone structure, from the viewpoint of sunproof preferred polymkeric substance organopolysiloxane being made backbone structure further.
As [A] compound organopolysiloxane being made backbone structure, preferably have: the compound of the part being derived from the organopolysiloxane with epoxy group(ing) and the part that is derived from the specific carboxylic acid represented by above-mentioned formula (2).Because [A] compound in this liquid crystal aligning agent has specific structural unit, thus can import at side chain and have the structure of dielectric anisotropy, possess and use this liquid crystal aligning agent and the liquid crystal display device of liquid crystal orientation film that formed can shorten the time of response more.In addition, by utilizing the reactivity between epoxy group(ing) and carboxyl, thus can easily to as the structure with dielectric anisotropy represented by above-mentioned formula (1) imported in the organopolysiloxane of main chain as side chain.
[A] compound is when having the part being derived from the organopolysiloxane with epoxy group(ing) and the part being derived from above-mentioned specific carboxylic acid, can think and mainly can obtain in the mode of the reactant of the carboxyl of the epoxy group(ing) of organopolysiloxane and specific carboxylic acid, but in order to make explanation thereafter easily carry out, being divided into the part that is derived from the organopolysiloxane (and derivative) with epoxy group(ing) easily and being derived from the part of specific carboxylic acid so that [A] compound to be described.
[being derived from the part of the organopolysiloxane with epoxy group(ing)]
The concept of this part comprises: the organopolysiloxane skeleton as main polymer chain among the structure of [A] compound and the skeleton containing epoxy group(ing) as side chain extended from this organopolysiloxane main chain.Can think as described above in [A] compound, most epoxy group(ing) and specific carboxylic acid reaction and not there is its initial structure, but also can there is the situation that the part of specific carboxylic acid beyond epoxy group(ing) be combined.Therefore, the form comprising both is in the present invention called " being derived from the part of the organopolysiloxane with epoxy group(ing) ".
[A] compound by have comprise glycidyl, glycidyl oxygen base, epoxycyclohexyl the epoxy group(ing) such as group thus the such electrical characteristic of the orientation of this liquid crystal aligning agent, high-speed response are improved more.Be preferably by above-mentioned formula (X as epoxy group(ing) 1-1) or (X 1-2) group represented.By comprising in organopolysiloxane by above-mentioned formula (X 1-1) or (X 1-2) group represented, thus in [A] compound, easily by using specific carboxylic acid that the base represented by above-mentioned formula (1) is imported to side chain.
Above-mentioned formula (X 1-1) or (X 1-2) among, the group preferably represented by following formula,
The weight-average molecular weight through polystyrene conversion that the organopolysiloxane with epoxy group(ing) is measured by gel permeation chromatography (GPC) is preferably 500 ~ 100,000, is more preferably 1,000 ~ 50,000, is particularly preferably 1,000 ~ 20,000.
[there is the synthetic method of the organopolysiloxane of epoxy group(ing)]
The organopolysiloxane with epoxy group(ing) like this can preferably by synthesizing as follows: be hydrolyzed or hydrolytic condensation by the mixture of the silane compound with epoxy group(ing) or the silane compound and other silane compound with epoxy group(ing), be preferably hydrolyzed or hydrolytic condensation under the existence of suitable organic solvent, water and catalyzer.
As the above-mentioned silane compound with epoxy group(ing), such as, list 3-glycydoxy Trimethoxy silane, 3-glycydoxy triethoxyl silane, 3-glycydoxy methyl dimethoxysilane, 3-glycydoxy methyldiethoxysilane, 3-glycydoxy dimethyl methoxy silane, 3-glycydoxy dimethylethoxysilane, 2-glycidyl ether oxygen base ethyl trimethoxy silane, 2-glycidyl ether oxygen base ethyl triethoxysilane, 2-glycidyl ether oxygen base ethyl-methyl dimethoxysilane, 2-glycidyl ether oxygen base ethyl-methyl diethoxy silane, 2-glycidyl ether oxygen base ethyl dimethyl methoxy silane, 2-glycidyl ether oxygen base ethyl dimethylethoxysilane, 4-glycidyl ether oxygen base butyl trimethoxy silane, 4-glycidyl ether oxygen Ji Dingji triethoxyl silane, 4-glycidyl ether oxygen base butyl methyl dimethoxysilane, 4-glycidyl ether oxygen base butyl methyl diethoxy silane, 4-glycidyl ether oxygen base Butyldimethyl methoxy silane, 4-glycidyl ether oxygen base Butyldimethyl Ethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane, 3-(3,4-epoxycyclohexyl) propyl trimethoxy silicane, 3-(3,4-epoxycyclohexyl) propyl-triethoxysilicane etc.They can be used alone or use two or more.
As other silane compound above-mentioned, such as, for having the compound of 1 Siliciumatom, and
As other the silane compound with 4 hydrolization groups, list tetrachloro silicane, the tetraalkoxysilane etc. such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane;
As other the silane compound with 3 hydrolization groups, list the trihalosilanes such as trichlorosilane, Trimethoxy silane, the trialkoxy silanes such as triethoxyl silane, fluorine trichlorosilane, fluorine Trimethoxy silane, the fluorine trialkoxy silanes such as fluorine triethoxyl silane, the alkyltrichlorosilanes such as METHYL TRICHLORO SILANE, methyltrimethoxy silane, the alkyltrialkoxysilaneand such as Union carbide A-162, the fluoro-alkyl trichlorosilanes such as 2-(trifluoromethyl) ethyl trichlorosilane, 2-(trifluoromethyl) ethyl trimethoxy silane, the fluoro-alkyl trialkoxy silanes such as 2-(trifluoromethyl) ethyl triethoxysilane, the hydroxyalkyl trichlorosilanes such as hydroxymethyl trichlorosilane, hydroxymethyl Trimethoxy silane, the hydroxyalkyl trialkoxy silanes such as hydroxyethyl Trimethoxy silane, (methyl) acryloxyalkyl trichlorosilanes such as 3-(methyl) acryloxypropyl trichlorosilane, 3-(methyl) acryloxypropyl Trimethoxy silane, (methyl) acryloxyalkyl trialkoxy silanes such as 3-(methyl) acryloxypropyl triethoxyl silane, mercapto methyl trichlorosilane, the mercaptoalkyl trichlorosilanes such as 3-mercaptopropyi trichlorosilane, mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, 3-mercaptopropyi Trimethoxy silane, the mercaptoalkyl trialkoxy silanes such as 3-Mercaptopropyltriethoxysilane, vinyl trichloro silane, the thiazolinyl trichlorosilanes such as allyltrichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, the thiazolinyl trialkoxy silanes such as allyltriethoxysilane, the aryl trichlorosilanes such as phenyl-trichloro-silicane, phenyltrimethoxysila,e, the aryltrialkoxysilane etc. such as phenyl triethoxysilane,
As other the silane compound with 2 hydrolization groups, list the alkyl dichlorosilanes such as dimethyl dichlorosilane (DMCS), methyl dimethoxysilane, the alkyl-dialkoxysilanes such as methyldiethoxysilane, the dialkyldichlorosilan,s such as dimethyldichlorosilane(DMCS), dimethyldimethoxysil,ne, the dialkyl dialkoxy silicanes such as dimethyldiethoxysilane, the two fluoro-alkyl dichlorosilanes such as (methyl) [2-(n-perfluoro-octyl) ethyl] dichlorosilane, the two fluoro-alkyl dialkoxy silicanes such as (methyl) [2-(n-perfluoro-octyl) ethyl] dimethoxysilane, the alkyl thiol alkyl dichlorosilanes such as (methyl) (3-mercaptopropyi) dichlorosilane, the alkyl thiol alkyl-dialkoxysilanes such as (methyl) (3-mercaptopropyi) dimethoxysilane, the alkylalkenyl dichlorosilanes such as (methyl) (vinyl) dichlorosilane, divinyldichlorosilane etc. two (thiazolinyl) dichlorosilane, two (thiazolinyl) dialkoxy silicanes such as divinyl dimethoxysilane, the diaryl dichlorosilanes such as diphenyl dichlorosilane, the diaryl dialkoxy silane such as dimethoxydiphenylsilane,
As other the silane compound with 1 hydrolization group, list the dialkyl group chlorosilanes such as chlorodimethylsilane, the dialkyl group organoalkoxysilanes such as methoxyl group dimethylsilane, chlorine trimethyl silane, trimethylammonium bromide silane, the trialkylhalosilane such as iodine trimethyl silane, the trialkyl alkoxy silane such as methoxytrimethylsilane, the dialkyl group thiazolinyl chlorosilanes such as (chlorine) (vinyl) dimethylsilane, the dialkyl group alkenyl alkoxy silanes such as (methoxyl group) (vinyl) dimethylsilane, the alkyl diaryl chlorosilanes such as (chlorine) (methyl) diphenyl silane, the alkyl diaryl organoalkoxysilanes etc. such as (methoxyl group) (methyl) diphenyl silane.
As commercially available product, such as, list:
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 industry commercial firm of SHIN-ETSU HANTOTAI system),
グ ラ ス レ ジ Application (Showa electrician commercial firm system);
SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above ， East レ ダ ウ コ mono-ニ Application グ commercial firm system);
FZ3711, FZ3722 (more than, Japanese ユ ニ カ mono-commercial firm system);
DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (more than, チ Star ソ commercial firm system);
Methyl silicate MS51, methyl silicate MS56 (more than, Mitsubishi Chemical Ind's system);
Tetraethyl silicate 28, ethyl silicate 40, tetraethyl silicate 48 (more than, コ Le コ mono-ト commercial firm system);
The partial condensate of GR100, GR650, GR908, GR950 (more than, Showa electrician commercial firm system) etc.
Among these other silane compound, from the viewpoint of orientation and the storage stability of obtained liquid crystal aligning agent, 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, dimethyldiethoxysilane.
In order to make the organopolysiloxane with epoxy group(ing) preferably used in the present invention to measure the side chain importing and have dielectric anisotropy fully, its epoxy equivalent (weight) is preferably 100 ~ 10,000g/ mole, is more preferably 150 ~ 1,000g/ mole, is particularly preferably 150 ~ 300g/ mole.Therefore, when synthesis has the precursor of the organopolysiloxane of epoxy group(ing), have the silane compound of epoxy group(ing) and the usage ratio of other silane compound, the mode being preferably modulated into above-mentioned scope according to the obtained epoxy equivalent (weight) with the organopolysiloxane of epoxy group(ing) sets.Synthesize in the present invention use there is the organopolysiloxane of epoxy group(ing) time, more preferably only use and there is the silane compound of epoxy group(ing), do not use other silane compound.
As the spendable organic solvent when synthesis has the organopolysiloxane of epoxy group(ing), such as, list hydrocarbon compound, ketone compound, ester cpds, ether compound, alkylol cpd etc.
As above-mentioned hydrocarbon, such as, list toluene, dimethylbenzene etc.; As above-mentioned ketone, such as, list methylethylketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, metacetone, pimelinketone etc.; As above-mentioned ester, such as, list ethyl acetate, n-butyl acetate, Isoamyl Acetate FCC, propylene glycol methyl ether acetate, 3-methoxybutyl acetic ester, ethyl lactate etc.; As above-mentioned ether, such as, list ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, tetrahydrofuran (THF), diox etc.; As above-mentioned alcohol, such as, list 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol list n-propyl ether, ethylene glycol list n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list n-propyl ether etc.Preferred non-water-soluble organic solvent among them.These organic solvents can be used alone or use two or more.
Consumption about organic solvent is preferably 10 ~ 10 relative to persilylated compound 100 mass parts, and 000 mass parts, is more preferably 50 ~ 1,000 mass parts.The consumption manufacturing water when having the organopolysiloxane of epoxy group(ing) is preferably 0.5 ~ 100 times mole relative to persilylated compound, is more preferably 1 ~ 30 times mole.
As above-mentioned catalyzer, such as, can use acid, alkali metal compound, organic bases, titanium compound, zirconium compounds etc.
As above-mentioned alkali metal compound, such as, list sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate etc.
As above-mentioned organic bases, such as can list the organic primary amine ~ organic secondary such as ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles respectively, the trimethylamines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo undecylene, organic quaternary amine such as Tetramethylammonium hydroxide etc.Among these organic basess, consider the viewpoint that reacting balance carries out, the trimethylamines such as preferred triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, organic quaternary amine such as Tetramethylammonium hydroxide.
As the catalyzer manufactured when there is the organopolysiloxane of epoxy group(ing), preferred as alkali compound or organic bases.By alkali metal compound or organic bases are used as catalyzer, thus the side reactions such as the open loop of epoxy group(ing) do not occur, can obtain the organopolysiloxane of target with high hydrolytic condensation speed, therefore production stability is excellent therefore preferred.In addition, this liquid crystal aligning agent of the organopolysiloxane with epoxy group(ing) synthesized as catalyzer containing use alkali metal compound or organic bases and the reactant of specific carboxylic acid, its storage stability is extremely excellent, therefore easy to use.Its reason can be speculated as follows: as ChemicalReviews, 95 volumes, point out in the 1409th page (nineteen ninety-five), when using alkali metal compound or organic bases as catalyzer in hydrolysis, condensation reaction, form random structure, ladder shape structure or basket type structure, what can obtain silanol group contains proportional few organopolysiloxane.Can infer: because containing of silanol group is proportional few, therefore silanol group condensation reaction is each other suppressed, further, when this liquid crystal aligning agent contains other polymkeric substance described later, because the condensation reaction of silanol group and other polymkeric substance is suppressed, therefore result is excellent storage stability.
As catalyzer, particularly preferably organic bases.The consumption of organic bases is different from the reaction conditions such as kind, temperature etc. of organic bases, suitably should set, but is such as preferably 0.01 ~ 3 times mole relative to persilylated compound, be more preferably 0.05 ~ 1 times mole.
Manufacture hydrolysis when there is the organopolysiloxane of epoxy group(ing) or hydrolysis-condensation reaction is preferably as follows enforcement: the silane compound and other silane compound as required with epoxy group(ing) are dissolved in organic solvent, this solution is mixed with organic bases and water, such as, is heated by oil bath etc. thus implement.
When hydrolysis-condensation reaction, the Heating temperature of oil bath is preferably less than 130 DEG C, is more preferably 40 ~ 100 DEG C, preferably heats 0.5 ~ 12 hour, more preferably heats 1 ~ 8 hour.Add and hanker, mixed solution can be stirred, under also can being placed on backflow.
After reaction terminating, preferably will divide the organic solvent layer got washing from reaction solution with water.During this washing, by with comprising the water of a small amount of salt, such as using the washing such as aqueous ammonium nitrate solution of about 0.2 quality %, thus make washing operation transfiguration easy, consider this viewpoint and preferably.Washing proceeds to the water layer after washing becomes neutral, thereafter as required by after the desiccant dryness such as organic solvent layer anhydrous calciumsulphate, molecular sieve, removes solvent, thus can obtain the organopolysiloxane with epoxy group(ing) of target.
In the present invention, the organopolysiloxane with epoxy group(ing) can be also used as and commercially available product.As such commercially available product, such as, list DMS-E01, DMS-E12, DMS-E21, EMS-32 (more than, チ Star ソ commercial firm) etc.
[A] compound also can comprise: be derived from the part of organopolysiloxane itself hydrolysis with epoxy group(ing) and the hydrolyzate produced, be derived from organopolysiloxane hydrolytic condensation and the part of hydrolytic condensate that obtains each other with epoxy group(ing).Also can prepare with having in the same manner as the hydrolysis of organopolysiloxane of epoxy group(ing), condensation condition as these hydrolyzates of the constituent material of this part, hydrolytic condensate.
[being derived from the part of specific carboxylic acid]
This part being derived from the specific carboxylic acid represented by above-mentioned formula (2) is equivalent to: the side-chain structure of structure as starting point to be derived from carboxyl among the structure of [A] compound contained in this liquid crystal aligning agent, described in be derived from carboxyl structure mainly combine with the structure being derived from the epoxy group(ing) of extending from organopolysiloxane main chain.But in the present invention, also comprise being called " part being derived from specific carboxylic acid " of the situation that specific carboxylic acid is combined with the part except epoxy group(ing).
R in above-mentioned formula (2) 1and R 2with the R in above-mentioned formula (1) 1and R 2identical.
The R of above-mentioned formula (2) 3for the alkylidene group of methylene radical or carbonatoms 2 ~ 30, phenylene or cyclohexylidene, they can have substituting group further.
As the alkylidene group of carbonatoms 2 ~ 30, list ethylidene, propylidene, butylidene, pentylidene, hexylidene, octylene, nonamethylene, sub-decyl, sub-undecyl, sub-dodecyl, sub-tetradecyl, sub-hexadecyl, sub-octadecyl, sub-nonadecyl, sub-eicosyl, sub-heneicosyl, sub-docosyl, sub-tricosyl, sub-tetracosyl, sub-pentacosyl, sub-ceryl, sub-heptacosyl, sub-octacosyl, sub-nonacosyl and sub-triacontyl etc.Among them, be preferably to stably manifest liquid crystal aligning the alkylidene group that the carbonatomss such as pentylidene, hexylidene, octylene, nonamethylene, sub-decyl, sub-undecyl, sub-dodecyl, sub-tetradecyl, sub-hexadecyl, sub-octadecyl, sub-nonadecyl, sub-eicosyl are less than more than 5 20.
As the compound with carboxyl represented by above-mentioned formula (2), such as, list the compound represented by following formula (E-1) ~ (E-25),
In formula (E-1) ~ (E-25), R 1to define equally with above-mentioned formula (2).M is the integer of 1 ~ 30.
[synthetic method of specific carboxylic acid]
The synthesis procedure of specific carboxylic acid is not particularly limited, known method in the past capable of being combined and carrying out.Representatively synthesis procedure, such as exemplify following method: (1) makes to have the compound of phenol backbone in the basic conditions, with the compound reaction that the alkyl chain part of high-grade aliphatic ester is obtained by halogen substiuted, the hydroxyl of phenol backbone with form key by the carbon of halogen substiuted, thereafter ester reduction is made the method for specific carboxylic acid, (2) compound and the ethylene carbonate that make to have phenol backbone carry out reacting and generating terminal alcoholic compound, its hydroxyl and halogeno-benzene SULPHURYL CHLORIDE is made to carry out reacting and activating, thereafter activated partial is made to react with the methyl benzoate comprising hydroxyl, thus there is the disengaging of sulfonyl moieties and the hydroxyl of terminal alcoholic compound generates key with the hydroxyl comprising the hydroxyl alternatively methyl benzoate of base, then ester reduction is made the method etc. of specific carboxylic acid.But the synthesis procedure of specific carboxylic acid is not limited to them.
The synthetic method > of < [A] compound
As the synthetic method of [A] compound, be not particularly limited, synthesize by general known method.When [A] compound has the part being derived from the organopolysiloxane with epoxy group(ing) and the part being derived from specific carboxylic acid, by making that there is the organopolysiloxane of epoxy group(ing) and specific carboxylic acid reaction, preferably reacting in the presence of a catalyst and synthesizing.
The epoxy group(ing) 1 mole that specific carboxylic acid has relative to organopolysiloxane herein preferably uses 0.001 ~ 10 mole, more preferably uses 0.01 ~ 5 mole, preferably uses 0.05 ~ 2 mole further.
In the present invention, also can replace a part for specific carboxylic acid with the compound represented by following formula (4) in the scope not damaging effect of the present invention and use.In the case, the synthesis of [A] compound is undertaken reacting by the organopolysiloxane that makes to have epoxy group(ing) and, specific carboxylic acid and the mixture of compound that represented by following formula (4) and carries out.
A 1-L 0-L 1-Z(4)
In above-mentioned formula (4), A 1for the straight-chain of carbonatoms 1 ~ 30 or branched-chain alkyl, the cycloalkyl of carbonatoms 3 ~ 10 that can be replaced by the alkyl of carbonatoms 1 ~ 20 or alkoxyl group or the alkyl of carbonatoms 17 ~ 51 with steroid backbone.Wherein, part or all of the hydrogen atom of abovementioned alkyl and alkoxyl group also can be replaced by the substituting group such as cyano group, fluorine atom, trifluoromethyl.
L 0for singly-bound, *-O-, *-COO-or *-OCO-.With key end and the A of " * " 1in conjunction with.
L 1for the alkylidene group of singly-bound, carbonatoms 1 ~ 20, phenylene, biphenylene, cyclohexylidene, two cyclohexylidene or by following formula (L 1-1) or (L 1-2) group represented.
Z is for forming the organic group of 1 valency of linking group with the epoxy reaction in [A] polyorganosiloxane compounds.
Wherein, at L 1for L during singly-bound 0for singly-bound.
Above-mentioned formula (L 1-1) and (L 1-2) the key end with " * " in is combined with Z respectively.
Z is preferably carboxyl.
As A in above-mentioned formula (4) 1the straight-chain of represented carbonatoms 1 ~ 30 or branched-chain alkyl, such as, list: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, 3-methyl butyl, 2-methyl butyl, 1-methyl butyl, 2,2-dimethyl propyl, n-hexyl, 4-methyl amyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 4,4-dimethyl amyl group, 3,4-dimethyl amyl group, 2,4-dimethyl amyl group, Isosorbide-5-Nitrae-dimethyl amyl group, 3,3-dimethyl amyl group, 2,3-dimethyl amyl group, 1,3-dimethyl amyl group, 2,2-dimethyl amyl group, 1,2-dimethyl amyl group, 1,1-dimethyl amyl group, 2,3,3-trimethyl butyl, 1,3,3-trimethyl butyl, 1,2,3-trimethyl butyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base etc.
As the cycloalkyl of the carbonatoms 3 ~ 10 that can be replaced by the alkyl of carbonatoms 1 ~ 20 or alkoxyl group, such as, list cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, cyclo-dodecyl etc.
As the alkyl of carbonatoms 17 ~ 51 with steroid backbone, such as, list the group represented by following formula (A-1) ~ (A-3).
As the A in above-mentioned formula (4) 1, be preferably selected from the group in the alkyl of carbonatoms 1 ~ 20, the fluoroalkyl of carbonatoms 1 ~ 20 and above-mentioned formula (A-1) or (A-3).
As the compound represented by above-mentioned formula (4), the compound preferably represented any one of following formula (4-1) ~ (4 ~ 6).
C uF 2u+1-C vH 2v-COOH(4-1)
C wH 2w+1-COOH(4-2)
In above-mentioned formula (4-1) ~ (4-6), u is the integer of 1 ~ 5.V is the integer of 1 ~ 18.W is the integer of 1 ~ 20.K is the integer of 1 ~ 5.P is 0 or 1.Q is the integer of 0 ~ 18.R is the integer of 0 ~ 18.S and t is the integer of 0 ~ 2 independently of one another.
Among these compounds, be more preferably the compound represented by following formula (4-7) ~ (4-13).
C 17H 35-COOH(4-7)
The compound represented by above-mentioned formula (4) is: together react with the organopolysiloxane with epoxy group(ing) with specific carboxylic acid, and formation can give obtained liquid crystal orientation film with the compound at the position of slope (tilt angle) the manifesting property of regulation.Sometimes the compound represented by above-mentioned formula (4) is called " other manifesting property of tilt angle compound " in this manual.
In the present invention, when together using other manifesting property of tilt angle compound with specific carboxylic acid, the epoxy group(ing) 1 mole that the usage ratio of the total of specific carboxylic acid and other manifesting property of tilt angle compound has relative to organopolysiloxane is preferably 0.001 ~ 1.5 mole, be more preferably 0.01 ~ 1 mole, more preferably 0.05 ~ 0.9 mole.In the case, other manifesting property of tilt angle Compound Phase for itself and specific carboxylic acid total preferably with less than 75 % by mole, more preferably use with the scope of less than 50 % by mole.When the usage ratio of other manifesting property of tilt angle compound is more than 75 % by mole, has and occur dysgenic situation in the high-speed response of liquid crystal.
As the catalyzer used in the reaction of the epoxy group(ing) in organopolysiloxane and other manifesting property of tilt angle compound, organic bases can be used or as promoting the so-called curing catalyst of the reaction of epoxy compounds and acid anhydrides and known compound.
As above-mentioned organic bases, such as, list the organic primary amine ~ organic secondary such as ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles; The trimethylamines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo undecylene; Organic quaternary amine such as Tetramethylammonium hydroxide etc.Among these organic basess, preferred triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, Tetramethylammonium hydroxide.
As above-mentioned curing catalyst, such as, list:
The tertiary amines such as benzyl dimethyl amine, 2,4,6-tri-(dimethylaminomethyl) phenol, cyclohexyldimethyl amine, 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-cyanoethyl)-glyoxal ethyline, 1-(2-cyanoethyl)-2-n-undecane base imidazoles, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis-(hydroxymethyl) imidazoles, 1-(2-cyanoethyl)-2-phenyl-4,5-bis-[(2 '-cyanoethoxy) methyl] imidazoles, 1-(2-cyanoethyl)-2-n-undecane base imidazoles trimellitate, 1-(2-cyanoethyl)-2-phenylimidazole trimellitate, 1-(2-cyanoethyl)-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; Benzyl triphenyl phosphonium chloride squama, tetran-butylphosphonium bromide squama, methyltriphenylphospbromide bromide squama, ethyltriphenyl phosphonium bromide squama, normal-butyl triphenyl phosphonium bromide squama, tetraphenylphosphonibromide bromide squama, ethyltriphenylphosphiodide iodide squama, ethyl triphenyl squama acetic ester, tetra-n-butyl squama o, the season squama salt such as o-diethyl phosphorothioate, tetra-n-butyl squama benzotriazole salt, tetra-n-butyl squama a tetrafluoro borate, tetra-n-butyl squama tetraphenyl borate salts, tetraphenyl squama tetraphenyl borate salts;
The Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, its organic acid salt;
The organometallic compounds such as zinc octoate, stannous octoate, acetopyruvic acid aluminium coordination 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 compound;
The high-melting-point decentralized potentiality curing catalysts such as amine add-on type promotor such as the affixture of Dyhard RU 100, amine and epoxy resin;
By polymkeric substance by above-mentioned imidazolium compounds, organo phosphorous compounds, season the curing catalyst such as squama salt the microcapsule-type potentiality curing catalyst that obtains of surface coverage;
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 dissociative type.
Among these catalyzer, the quaternary ammonium salts such as preferred tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride.
Catalyzer relative to organopolysiloxane 100 mass parts with epoxy group(ing) preferably with below 100 mass parts, more preferably with 0.01 ~ 100 mass parts, preferably further to use with the amount of 0.1 ~ 20 mass parts.
Temperature of reaction is preferably 0 ~ 200 DEG C, is more preferably 50 ~ 150 DEG C.Reaction times is preferably 0.1 ~ 50 hour, is more preferably 0.5 ~ 20 hour.
The building-up reactions of [A] compound, can carry out as required in presence of organic solvent.As above-mentioned organic solvent, such as, list hydrocarbon compound, ether compound, ester cpds, ketone compound, amide compound, alkylol cpd etc.Among them, consider the viewpoint of the refining easness of the solvability of raw material and product and product and preferably ether compound, ester cpds, ketone compound.Solvent is preferably below more than 0.1 quality % 70 quality % with solid component concentration (ratio that the quality of the composition except solvent in reaction soln is shared in the total mass of solution), be more preferably the amount of below more than 5 quality % 50 quality % uses.
The weight-average molecular weight obtained through vinylbenzene conversion that [A] compound obtained so is measured by gel permeation chromatograph is not particularly limited, but is preferably 1,000 ~ 200,000, is more preferably 2,000 ~ 20,000.By being in such molecular weight ranges, thus the orientation that liquid crystal display device is good and stability can be guaranteed.
With regard to above-mentioned [A] compound, in the organopolysiloxane with epoxy group(ing), be imported with the structure being derived from specific carboxylic acid by the carboxylate moiety of specific carboxylic acid to the open loop addition of epoxy group(ing).This manufacture method is extremely preferred method from the viewpoint of Drug delivery rate that is easy and that can improve the structure being derived from specific carboxylic acid.
< optional member >
With regard to this liquid crystal aligning agent, except above-mentioned [A] compound, only otherwise damage effect of the present invention, so also can be (following containing the polymkeric substance such as except [A] compound, be sometimes referred to as " other polymkeric substance "), solidifying agent, curing catalysts, curing catalyst, the compound (following, be sometimes referred to as " epoxy compounds ") in molecule with at least one epoxy group(ing), other the optional member such as functional silanes compound, tensio-active agent.
[other polymkeric substance]
With regard to other polymkeric substance, can use in order to the electrical characteristic of the solution properties of changing this liquid crystal aligning agent kind and the liquid crystal display device obtained.As other polymkeric substance, such as, list:
At least one polymkeric substance ([B] polymkeric substance) selected in the group be made up of polyamic acid and polyimide;
At least one (following, to be sometimes referred to as " other organopolysiloxane ") in the group that the condenses of the organopolysiloxane represented by following formula (5), its hydrolyzate and its hydrolyzate forms;
Poly amic acid ester, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc.,
In formula (5), X 1for the aryl of the alkyl of hydroxyl, halogen atom, carbonatoms 1 ~ 20, the alkoxyl group of carbonatoms 1 ~ 6 or carbonatoms 6 ~ 20.Y 1for the alkoxyl group of hydroxyl or carbonatoms 1 ~ 10.
< [B] polymkeric substance >
[B] polymkeric substance is at least one polymkeric substance selected in the group be made up of polyamic acid and polyimide.Below, polyamic acid and polyimide are described in detail.
[polyamic acid]
Polyamic acid obtains by making tetracarboxylic dianhydride and diamine compound carry out reacting.
As tetracarboxylic dianhydride, such as, list aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.These tetracarboxylic dianhydrides can be used alone or combine two or more and use.
As aliphatics tetracarboxylic dianhydride, such as, list butane tetracarboxylic acid dianhydride etc.
As ester ring type tetracarboxylic dianhydride, such as list 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[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 acid anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl 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, except such as listing pyromellitic acid dianhydride etc., also list the tetracarboxylic dianhydride recorded in No. 2010-97188, Japanese Patent Application.
Among these tetracarboxylic dianhydrides, preferred ester ring type tetracarboxylic dianhydride, more preferably 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides or 1,2,3,4-cyclobutanetetracarboxylic dianhydride, particularly preferably 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides.
With regard to 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride or 1, the consumption of 2,3,4-cyclobutanetetracarboxylic dianhydride, more than 10 % by mole are preferably relative to whole tetracarboxylic dianhydride, be more preferably more than 20 % by mole, particularly preferably only comprise 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride.
As diamine compound, such as, list aliphatie diamine, ester ring type diamines, diamino organo-siloxane, aromatic diamine etc.These diamine compounds can be used alone or combine two or more and use.
As aliphatie diamine, such as, list m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexanediamine etc.
As ester ring type diamines, such as, list Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (hexahydroaniline), 1,3-two (amino methyl) hexanaphthenes etc.
As diamino organo-siloxane, outside such as listing two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc., also list the diamines recorded in No. 2009-97188, Japanese Patent Application.
As aromatic diamine, such as, list Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to phenylenediisopropylidene) two (aniline), 4,4 '-(metaphenylene two isopropylidene) two (aniline), Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(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 '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-dimethyl p-diaminodiphenyl, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-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 ester, 3,5-diaminobenzoic acid cholestene ester, 3,5-diaminobenzoic acid lanostane ester, two (the 4-aminobenzoic acyl-oxygen base) cholestane of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethylbenzoyl oxygen base) cyclohexyl-3,5-diaminobenzoic acid ester, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexane of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthene of 1,1-, 2,4-diamino-N, N-diallyl aniline, 4-amino-benzylamine, 3-amino-benzylamine and the diamine compound etc. represented by following formula (A-1).
In above-mentioned formula (A-1), X 1for the alkylidene group of methylene radical or carbonatoms 2 or 3 ,-O-,-COO-or-OCO-.R is 0 or 1.S is the integer of 0 ~ 2.T is the integer of 1 ~ 20.
Supply in the tetracarboxylic dianhydride of the building-up reactions of polyamic acid and the usage ratio of diamine compound, relative to amino 1 equivalent contained in diamine compound, the anhydride group of preferred tetracarboxylic dianhydride is 0.2 equivalent ~ 2 equivalent, is more preferably 0.3 equivalent ~ 1.2 equivalent.
Preferred building-up reactions is carried out 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 0.5 hour ~ 24 hours, be more preferably 2 hours ~ 12 hours.
As organic solvent, if the organic solvent of the polyamic acid synthesized by solubilized is then not particularly limited, such as list METHYLPYRROLIDONE (NMP), N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N, the non-proton system polar solvents such as N-methylimidazole alkane ketone, dimethyl sulfoxide (DMSO), gamma-butyrolactone, 4-methyl urea, hexamethyl phosphinylidyne triamide, the phenol series solvents such as meta-cresol, xylenol, phenol, halogenated phenol.
As the consumption (a) of organic solvent, relative to the total (a+b) of tetracarboxylic dianhydride and the total amount (b) of diamine compound and the consumption (a) of organic solvent, be preferably 0.1 quality % ~ 50 quality %, be more preferably 5 quality % ~ 30 quality %.
The polyamic acid solution obtained after reaction can directly for the preparation of liquid crystal aligning agent, for the preparation of liquid crystal aligning agent on the basis of polyamic acid that also can be contained in independent separating reaction solution, also can for the preparation of liquid crystal aligning agent on the basis of refining independent isolated polyamic acid.As the independent separation method of polyamic acid, such as, listing: the method for precipitate drying under reduced pressure will obtained by reaction soln being injected a large amount of poor solvents, reaction soln to be reduced pressure the method etc. distillated by vaporizer.As the process for purification of polyamic acid, list: again independent isolated polyamic acid is dissolved in organic solvent, the method separated out by poor solvent, the method for 1 time or the operation distillated of repeatedly carrying out with vaporizer, organic solvent etc. being reduced pressure.
[polyimide]
Polyimide, the amido acid structure by having above-mentioned polyamic acid is carried out dehydration closed-loop and imidization thus is manufactured.Polyimide can for carrying out dehydration closed-loop to whole amido acid structure had as the polyamic acid of its precursor and the complete imide compound that obtains, also can for only carrying out dehydration closed-loop to a part for amido acid structure, make amido acid structure and imide ring structure and the part imide compound of depositing.
As the synthetic method of polyimide, the heating means such as listing (i) polyamic acid are (following, be sometimes referred to as " method (i) "), polyamic acid is dissolved in organic solvent by (ii), dewatering agent and dehydration closed-loop catalyzer is added in this solution, the method that the method (following, be sometimes referred to as " method (ii) ") of heating etc. are reacted based on the dehydration closed-loop of polyamic acid as required.
As the temperature of reaction in method (i), be preferably 50 DEG C ~ 200 DEG C, be more preferably 60 DEG C ~ 170 DEG C.When temperature of reaction is less than 50 DEG C, dehydration closed-loop reaction is insufficient to be carried out, and the molecular weight of the polyimide obtained when temperature of reaction is more than 200 DEG C reduces sometimes.As the reaction times, be preferably 0.5 hour ~ 48 hours, be more preferably 2 hours ~ 20 hours.
The polyimide obtained in method (i) can directly for the preparation of liquid crystal aligning agent, also can for the preparation of liquid crystal aligning agent on the basis being separated separately polyimide, or also can for the preparation of liquid crystal aligning agent on the basis of the refining polyimide separated separately or on the basis of refining the polyimide obtained.
As the dewatering agent in method (ii), such as, list the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.
As the consumption of dewatering agent, suitably select according to desired imide rate, but relative to 1 mole, the amido acid structure of polyamic acid, be preferably 0.01 mole ~ 20 moles.
As the dehydration closed-loop catalyzer in method (ii), such as, list pyridine, trimethylpyridine, lutidine, triethylamine etc.
As the consumption of dehydration closed-loop catalyzer, relative to the dewatering agent contained 1 mole, preferably 0.01 mole ~ 10 moles.Again, with regard to imide rate, the content of above-mentioned dewatering agent and dehydration closed-loop agent more at most can be higher.
As the organic solvent used in method (ii), such as, list: the organic solvent etc. same with the illustrative organic solvent as the organic solvent used in the synthesis of polyamic acid.
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 sufficient reacting can be made to carry out, in addition, the molecular weight of obtained polyimide can be made to be appropriate molecular weight.
The reaction soln containing polyimide can be obtained in method (ii).Can by this reaction soln directly for the preparation of liquid crystal aligning agent, also can in the preparation of basis for liquid crystal aligning agent eliminating dewatering agent and dehydration closed-loop catalyzer from reaction soln, also can for the preparation of liquid crystal aligning agent on the basis being separated separately polyimide, or also can for the preparation of liquid crystal aligning agent on the basis of refining independent isolated polyimide.As the method removing dewatering agent and dehydration closed-loop catalyzer from reaction soln, such as, list the method etc. of solvent exchange.As independent separation method and the process for purification of polyimide, such as list with as the independent separation method of polyamic acid and process for purification and the same method etc. of illustrative method.
[other organopolysiloxane]
This liquid crystal aligning agent also can comprise other organopolysiloxane except [A] compound comprising the part being derived from organopolysiloxane.At least one selected in the group that the condenses of organopolysiloxane, its hydrolyzate and its hydrolyzate that other organopolysiloxane is preferably represented by above-mentioned formula (5) forms.Again, when this liquid crystal aligning agent comprises other organopolysiloxane, the major part of other organopolysiloxane can be used as and the material that exist independent with [A] compound and exists, and its part also can be used as and the condenses of [A] compound and existing.
X in above-mentioned formula (5) 1and Y 1in,
As the alkyl of carbonatoms 1 ~ 20, such as, list methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive lauryl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.;
As the alkoxyl group of carbonatoms 1 ~ 16, such as, list methoxyl group, oxyethyl group etc.;
As the aryl of carbonatoms 6 ~ 20, such as, list phenyl etc.
With regard to other organopolysiloxane, at least one silane compound such as by selecting in the group be made up of alkoxysilane compound containing trialkylsilyl group in molecular structure and halogenated silane compounds is (following, be sometimes referred to as " raw silicon hydride compounds "), preferably in suitable organic solvent, hydrolysis or hydrolytic condensation under the existence of water and catalyzer thus synthesis.
As spendable raw silicon hydride compounds herein, such as, list tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane, four tert-butoxy silane, tetrachloro silicane, methyltrimethoxy silane, Union carbide A-162, methyl three positive propoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three sec-butoxy silane, methyl three tert-butoxy silane, methyl triple phenoxyl silane, METHYL TRICHLORO SILANE, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three positive propoxy silane, ethyl three isopropoxy silane, ethyl three n-butoxy silane, ethyl three sec-butoxy silane, ethyl three tert-butoxy silane, ethyl trichlorosilane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl-trichloro-silicane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyldichlorosilane(DMCS), trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane etc.Among them, preferred tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane.
When synthesizing other organopolysiloxane, as can arbitrarily used organic solvent, such as, list alkylol cpd, ketone compound, amide compound or ester cpds or other aprotic compound.They can be used alone or use two or more.
As alkylol cpd, such as, list:
Methyl alcohol, 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, heptan-3-alcohol, n-Octanol, 2-Ethylhexyl Alcohol, sec-octyl alcohol, nonanol-, 2, 6-dimethyl enanthol-4, nonylcarbinol, secondary hendecanol, Exxal 12, secondary tetradecanol, secondary heptadecanol, phenol, hexalin, methyl ring hexalin, 3, 3, 5-cyclonol, benzylalcohol, the monohydroxy-alcohol compounds such as diacetone alcohol,
The polyol compound such as ethylene glycol, 1,2-PD, 1,3 butylene glycol, 2,4-pentanediols, 2-methyl-2,4-pentanediol, 2,5-hexylene glycols, 2,4-heptanediols, 2-ethyl-1,3-hexylene glycol, Diethylene Glycol, dipropylene glycol, triglycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol ether, ethylene glycol list phenyl ether, 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.These alkylol cpds can be used alone or use two or more.
As ketone compound, such as, list:
Acetone, methylethylketone, methyl n-propyl ketone, methyl n-butyl ketone, metacetone, methyl-isobutyl ketone, methyl-n-amyl ketone, ethyl normal-butyl ketone, methyl n hexyl ketone, diisobutyl ketone, trimethylammonium nonanone, pimelinketone, methyl-n-butyl ketone, methylcyclohexanone, 2, the single ketones compounds such as 4-pentane diketone, acetonyl-acetone, methyl phenyl ketone, fenchone
Acetopyruvic acid, 2,4-hexanedione, 2,4-heptane diketone, 3,5-heptane diketone, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl--3,5-heptane diketone, 1,1,1,5, the beta-diketone compounds etc. such as 5,5-hexafluoro-2,4-heptane diketone.These ketone compounds can be used alone or use two or more.
As above-mentioned amide compound; such as list methane amide, N-METHYLFORMAMIDE, N; 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.These amide compounds can be used alone or use two or more.
As ester cpds, such as, list diethyl carbonate, ethylene carbonate, Texacar PC, diethyl 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 list 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, diacetate glycol ester, acetic acid methoxy triethylene ester, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, oxalic acid di-n-butyl, methyl lactate, ethyl lactate, n-butyl lactate, N_amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate etc.These ester cpds can be used alone or use two or more.
As other aprotic compound, such as list acetonitrile, dimethyl sulfoxide (DMSO), N, N, N ', N '-tetraethyl-sulphamide, 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, METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolidone, 1,3-dimethyl tetrahydro-2 (1H)-pyrimidone etc.Among these solvents, the particularly preferably part ether of polyol compound, polyol compound or ester cpds.
As the amount of the water used when the synthesis of other organopolysiloxane, the alkoxyl group had relative to raw silicon hydride compounds and the total amount of halogen atom 1 mole, be preferably 0.01 ~ 100 mole, be more preferably 0.1 ~ 30 mole, more preferably 1 ~ 1.5 mole.
As catalyzer spendable when the synthesis of other organopolysiloxane, such as, list metallo-chelate, organic acid, mineral acid, organic bases, ammoniacal liquor, alkali metal compound etc.
As above-mentioned metallo-chelate, such as list: tri-alkoxy list (acetopyruvic acid) titaniums such as triethoxy list (acetopyruvic acid) titanium, two (acetopyruvic acid) titaniums of dialkoxy such as two (acetopyruvic acid) titaniums of diethoxy, monoalkoxy three (acetopyruvic acid) titaniums such as monosubstituted ethoxy three (acetopyruvic acid) titanium, four (acetopyruvic acid) titanium, tri-alkoxy list (ethyl acetoacetic acid) titaniums such as triethoxy list (ethyl acetoacetic acid) titanium, two (ethyl acetoacetic acid) titaniums of dialkoxy such as two (ethyl acetoacetic acid) titaniums of diethoxy, monoalkoxy three (ethyl acetoacetic acid) titaniums such as monosubstituted ethoxy three (ethyl acetoacetic acid) titanium, four (ethyl acetoacetic acid) titanium, single (acetopyruvic acid) three (ethyl acetoacetic acid) titanium, two (acetopyruvic acid) two (ethyl acetoacetic acid) titanium, three (acetopyruvic acid) single (ethyl acetoacetic acid) titanium etc. comprises the titanium chelates such as the titanium compound of two or more chelating ligands,
Tri-alkoxy list (acetopyruvic acid) zirconiums such as triethoxy list (acetopyruvic acid) zirconium, two (acetopyruvic acid) zirconiums of dialkoxy such as two (acetopyruvic acid) zirconiums of diethoxy, monoalkoxy three (acetopyruvic acid) zirconiums such as monosubstituted ethoxy three (acetopyruvic acid) zirconium, four (acetopyruvic acid) zirconium, tri-alkoxy list (ethyl acetoacetic acid) zirconiums such as triethoxy list (ethyl acetoacetic acid) zirconium, two (ethyl acetoacetic acid) zirconiums of dialkoxy such as two (ethyl acetoacetic acid) zirconiums of diethoxy, monoalkoxy three (ethyl acetoacetic acid) zirconiums such as monosubstituted ethoxy three (ethyl acetoacetic acid) zirconium, four (ethyl acetoacetic acid) zirconium, single (acetopyruvic acid) three (ethyl acetoacetic acid) zirconium, two (acetopyruvic acid) two (ethyl acetoacetic acid) zirconium, three (acetopyruvic acid) single (ethyl acetoacetic acid) zirconium etc. comprises the zirconium chelates such as the zirconium compounds of two or more chelating ligands,
The aluminum chelates etc. such as three (acetopyruvic acid) aluminium, three (ethyl acetoacetic acid) aluminium.
As above-mentioned organic acid, such as list the aliphatics saturated carboxylic acids such as formic acid, acetic acid, propionic acid, the aliphatics such as propanedioic acid, fumaric acid unsaturated carboxylic acid, the aromatic carboxylic acids such as Whitfield's ointment, phenylformic acid, phthalic acid, the aromatic sulphonic acid such as tosic acid, Phenylsulfonic acid, the halogen-containing carboxylic acids such as Monochloro Acetic Acid, trichoroacetic acid(TCA), trifluoroacetic acid, citric acid, tartrate etc.
As above-mentioned mineral acid, such as, list hydrochloric acid, nitric acid, sulfuric acid, hydrogen fluoride, phosphoric acid etc.
As above-mentioned organic bases, such as list pyridine, pyrroles, piperazine, tetramethyleneimine, piperidines, picoline, Trimethylamine 99, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, trolamine, diazabicyclo octane, diazabicyclo nonane, diazabicyclo undecylene, Tetramethylammonium hydroxide etc.
As above-mentioned alkali metal compound, such as, list sodium hydroxide, potassium hydroxide, hydrated barta, calcium hydroxide etc.These catalyzer can be used alone or use two or more.
Among these catalyzer, preferable alloy inner complex, organic acid, mineral acid.As metallo-chelate, be more preferably titanium chelate.
With regard to the consumption of catalyzer, be preferably 0.001 ~ 10 mass parts relative to raw silicon hydride compounds 100 mass parts, be more preferably 0.001 ~ 1 mass parts.
Catalyzer can make an addition in advance using in the silane compound of raw material or in solution silane compound being dissolved in organic solvent and obtaining, or also solubilized or be scattered in added water.
The water added when the synthesis of other organopolysiloxane, can intermittently or continuously make an addition in the silane compound as raw material or in solution silane compound being dissolved in organic solvent and obtaining.
Temperature of reaction during synthesis as other organopolysiloxane, is preferably 0 ~ 100 DEG C, is more preferably 15 ~ 80 DEG C.Reaction times is preferably 0.5 ~ 24 hour, is more preferably 1 ~ 8 hour.
This liquid crystal aligning agent, when containing when containing other polymkeric substance while [A] compound, as the content of other polymkeric substance, is preferably 10, below 000 mass parts relative to [A] compound 100 mass parts.The preferred content of other polymkeric substance is different because of the kind of other polymkeric substance.
This liquid crystal aligning agent is when containing [A] compound and [B] polymkeric substance, with regard to both preferred usage ratios, the total amount of [B] polymkeric substance is preferably 100 ~ 5 relative to [A] compound 100 mass parts, 000 mass parts, be more preferably 200 ~ 3,000 mass parts.
On the other hand, when this liquid crystal aligning agent contains [A] compound and other organopolysiloxane, with regard to both preferred usage ratios, be 100 ~ 2,000 mass parts relative to the amount of other organopolysiloxane of [A] compound 100 mass parts.
This liquid crystal aligning agent contains other polymkeric substance while containing [A] compound, as other polymkeric substance, preferably [B] polymkeric substance or other organopolysiloxane.
[solidifying agent, curing catalysts and curing catalyst]
For the crosslinking reaction more firmly object making [A] compound, solidifying agent and curing catalysts can be made to be contained in this liquid crystal aligning agent.For the object promoting the curing reaction that solidifying agent is administered, curing catalyst can be made to be contained in this liquid crystal aligning agent.
As solidifying agent, can use: have epoxy group(ing) solidified nature compound or containing have epoxy group(ing) compound solidification compound solidification in normally used solidifying agent.As such solidifying agent, such as, list polyamine, polybasic acid anhydride, polycarboxylic acid.
As polybasic acid anhydride, such as, list acid anhydrides and other the polybasic acid anhydride of cyclohexanetricarboxylic acid.
As cyclohexanetricarboxylic acid's acid anhydride, such as, list hexanaphthene-1,3,4-tricarboxylic acid-3,4-acid anhydrides, hexanaphthene-1,3,5-tricarboxylic acid-3,5-acid anhydrides, hexanaphthene-1,2,3-tricarboxylic acid-2,3-acid anhydrides etc.As other polybasic acid anhydride, such as list normally used tetracarboxylic dianhydride in the synthesis of 4-methyl tetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, succinyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, the compound represented by following formula (6), polyamic acid, list α-terpinene, alloocimene etc. in addition and there is the ester ring type compound of conjugated double bond and the diels-alder reaction product (Diels-Alderreactionproduct) of maleic anhydride and their hydrogenation thing etc.
In formula (6), x is the integer of 1 ~ 20.
As curing catalysts, such as, can use antimony hexafluoride compound, phosphorus hexafluoride compound, praseodynium acid aluminium etc.These catalyzer can carry out catalysis to the cationoid polymerisation of epoxy group(ing) under the effect of heating.
As above-mentioned curing catalyst, such as list imidazolium compounds, quaternary phosphonium compound, quaternary ammonium compound, 1, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene, the Diazabicycloalkenes such as its organic acid salt, zinc octoate, stannous octoate, the organometallic compounds such as acetopyruvic acid aluminium coordination compound, boron trifluoride, the boron compounds such as triphenyl borate, zinc chloride, the metal halide compounds such as tin chloride, Dyhard RU 100, the high-melting-point decentralized potentiality curing catalysts such as amine add-on type promotor such as the affixture of amine and epoxy resin, by the surface coverage microcapsule-type potentiality curing catalyst that obtain of polymkeric substance by season squama salt etc., amine salt type potentiality curing catalyst, lewis acid, the hot cationic polymerization type potentiality curing catalyst etc. of Bronsted hydrochlorate contour temperature dissociative type.
[epoxy compounds]
From the viewpoint of the cementability improved for the substrate surface of formed liquid crystal orientation film, above-mentioned epoxy compounds can be made to be contained in this liquid crystal aligning agent.
As epoxy compounds, preferred ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2, 2-bis-bromo neopentylglycol diglycidyl ether, 1, 3, 5, 6-four glycidyl group-2, 4-hexylene glycol, N, N, N ', N '-four glycidyl group m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl benzylamine, N, N-diglycidyl-aminomethyl cyclohexane.
When this liquid crystal aligning agent contains epoxy compounds, with regard to it containing with regard to proportional, relative to above-mentioned [A] polyorganosiloxane compounds and other total 100 mass parts of polymkeric substance arbitrarily used, be preferably below 0.01 ~ 40 mass parts, be more preferably 0.1 ~ 30 mass parts.
Again, when this liquid crystal aligning agent contains epoxy compounds, also can share the alkaline catalystss such as 1 benzyl 2 methyl imidazole for efficiently causing the object of its crosslinking reaction.
[functional silanes compound]
Functional silanes compound can be used for the object of the cementability of the substrate of the liquid crystal orientation film improved and obtain.As functional silanes compound, such as, list 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-urea propyl trimethoxy silicane, 3-urea propyl-triethoxysilicane, 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, two (oxo the ethylidene)-3-TSL 8330 of N-, two (oxo the ethylidene)-APTES of N-, 3-glycydoxy Trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silanes etc., list tetracarboxylic dianhydride described in Japanese Laid-Open Patent Publication 63-291922 publication and the reactant etc. with amino silane compound further.
When this liquid crystal aligning agent contains functional silanes compound, with regard to it containing with regard to proportional, be preferably below 50 mass parts relative to above-mentioned [A] compound and other total 100 mass parts of polymkeric substance arbitrarily used, be more preferably below 20 mass parts.
[tensio-active agent]
As tensio-active agent, such as, list nonionogenic tenside, anion surfactant, cats product, amphoterics, (gathering) silicone surfactant, polyalkylene oxide tensio-active agent, fluorochemical surfactant etc.
When this liquid crystal aligning agent contains tensio-active agent, with regard to it containing with regard to proportional, relative to entirety 100 mass parts of liquid crystal aligning agent, be preferably below 10 mass parts, be more preferably below 1 mass parts.
The preparation method > of < liquid crystal aligning agent
As mentioned above, this liquid crystal aligning agent with [A] compound for must composition and containing, can as required containing other optional member, but prepared by the mode of the composition of the solution shape preferably obtained in organic solvent with each component dissolves.
As may be used for the organic solvent preparing this liquid crystal aligning agent, preferred solubilized [A] compound and other composition arbitrarily used and the organic solvent do not reacted with them.The organic solvent that can be preferred for this liquid crystal aligning agent is different from the kind of other polymkeric substance of adding arbitrarily.
When this liquid crystal aligning agent contains [A] compound and [B] polymkeric substance, as preferred organic solvent, list: as the organic solvent used in the synthesis of polyamic acid in above-mentioned illustrative organic solvent.Now, the poor solvent and illustrative poor solvent that use in the synthesis as polyamic acid of the present invention can also be share.These organic solvents can be used alone or use two or more.
On the other hand, when this liquid crystal aligning agent only contains [A] compound as polymkeric substance, or containing [A] compound and other organopolysiloxane as polymkeric substance when, as preferred organic solvent, such as, list 1-oxyethyl group-2-propyl alcohol, 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, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether (ethylene glycol butyl ether), ethylene glycol list amyl 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.Among them, be preferably n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate.
Can be used for the preferred solvent preparing this liquid crystal aligning agent, can according to the presence or absence of the use of other polymkeric substance and its kind, combine above-mentioned organic solvent more than one and obtain.Such solvent is, not to separate out in liquid crystal aligning agent contained each composition and make the surface tension of liquid crystal aligning agent be the solvent of the scope of 25 ~ 40mN/m under following preferred solid component concentration.
The ratio of weight shared by the gross weight of liquid crystal aligning agent of the whole compositions except solvent in the solid component concentration of this liquid crystal aligning agent, i.e. liquid crystal aligning agent, although consider viscosity, volatility etc. and select, be preferably the scope of 1 ~ 10 quality %.This liquid crystal aligning agent coats substrate surface, form the film that will become liquid crystal orientation film, but when solid component concentration is more than 1 quality %, the thickness of this film not easily becomes too small and can obtain good liquid crystal orientation film.On the other hand, when solid component concentration is below 10 quality %, suppress the thickness of film become excessive and good liquid crystal orientation film can be obtained, in addition, prevent the viscosity of liquid crystal aligning agent from increasing and making coating characteristics be good.The scope of particularly preferred solid component concentration is different because of the method adopted during coating of liquid crystalline alignment agent on substrate.Such as, based on the scope being particularly preferably 1.5 ~ 4.5 quality % when rotational method.When based on print process, particularly preferably solid component concentration is set to the scope of 3 ~ 9 quality %, thus soltion viscosity is set to the scope of 12 ~ 50mPas.When based on ink jet method, particularly preferably solid component concentration is set to the scope of 1 ~ 5 quality %, thus soltion viscosity is set to the scope of 3 ~ 15mPas.Temperature when preparing this liquid crystal aligning agent is preferably 0 DEG C ~ 200 DEG C, is more preferably 0 DEG C ~ 40 DEG C.
< liquid crystal display device >
Liquid crystal display device of the present invention is the liquid crystal display device of the PSA mode possessing the liquid crystal orientation film formed by this liquid crystal aligning agent.According to this liquid crystal display device, by forming liquid crystal orientation film by above-mentioned liquid crystal aligning agent, thus make liquid crystal aligning high, and excellent high-speed response can be played.Below, see figures.1.and.2, the embodiment of liquid crystal display device is described.
[the first embodiment]
The liquid crystal display device 1 of Fig. 1 is: possess a pair substrate 2 of subtend configuration, be laminated in a pair liquid crystal orientation film 3 of the inner surface side of this pair substrate 2 respectively, be filled in the liquid crystal display device of the PSA mode of the liquid crystal layer 4 formed between above-mentioned liquid crystal orientation film 3 and by polymerizable liquid crystal compound.
As a pair substrate 2, such as, can use the glass such as float glass, soda glass, the transparency carrier formed by plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, ester ring type polyolefine.
The internal surface of above-mentioned a pair substrate 2 is provided with transparency electrode 5a and 5b.Transparency electrode 5a becomes common electrode (commonelectrode), and transparency electrode 5b becomes pixel electrode.As this transparency electrode 5, such as, can use and comprise stannic oxide (SnO 2) NESA film (PPG register of company of U.S. trade mark), comprise indium oxide-tin oxide (In 2o 3-SnO 2) ito film etc.Again, this transparency electrode is same with known liquid crystal display device, is connected with not shown TFT, bus (busline) etc.
On the surface (side, face of subtend) of two transparency electrode 5a and 5b, be formed with wire projection (dykes and dams shape tropism control works) 6.As the size of this wire projection, such as, be highly 1.5 μm, width is 10 μm; Be such as 25 μm as interval.Liquid crystal molecule is made to carry out orientation segmentation by this wire projection 6.
In the inner surface side of a pair substrate 2, be formed with liquid crystal orientation film 3 via transparency electrode 5a, 5b and wire projection 6.This liquid crystal orientation film 3 is vertical alignment layer, is formed by this above-mentioned liquid crystal aligning agent.The process such as friction treatment, light orientation process can be implemented to the surface of this liquid crystal orientation film 3, also can not implement.According to this liquid crystal display device, by forming liquid crystal orientation film by above-mentioned liquid crystal aligning agent, thus make liquid crystal aligning excellent and excellent high-speed response can be played.
The liquid crystal layer 4 formed by polymerizable liquid crystal compound is filled with between this liquid crystal orientation film 3.This liquid crystal layer 4 has negative dielectric constant anisotropy.As such liquid crystal, such as, can use dicyano benzene series liquid crystal, pyridazine system liquid crystal, Schiff's base system liquid crystal, azoxy system liquid crystal, biphenyl system liquid crystal, Santosol 360 system liquid crystal etc.In addition; as above-mentioned polymerizable liquid crystal compound; be not particularly limited, known thing can be used, such as, can use and the monomer and polymerization starter with acryl and liquid crystal skeleton together be made an addition to negative (negative dielectric constant anisotropy) type liquid crystal and the material that obtains.As the addition of above-mentioned monomer, such as below more than 0.1 quality % 1 quality %.As the thickness of liquid crystal layer 4, such as, it is about about 4 μm.
In this liquid crystal display device 1, owing to forming liquid crystal layer 4 by polymerizable liquid crystal compound, thus in liquid crystal layer 4, be formed with polymer layer 7 at the interface with liquid crystal orientation film 3.This polymer layer 7 gives liquid crystal molecule 4a in liquid crystal layer 4 with tilt angle with the angle θ p of regulation.
In this liquid crystal display device 1, same with known liquid crystal display device, at the stacked not shown Polarizer of two outside surfaces of substrate 2.As this Polarizer; be not particularly limited; but list: make PVA (PVOH) FILM stretch orientation absorb iodine and the Polarizer that clips via rhodia protective membrane of the light polarizing film being referred to as " H film " obtained, or the Polarizer etc. formed by H film itself.
According to this liquid crystal display device 1, by forming liquid crystal orientation film 3 by above-mentioned liquid crystal aligning agent, thus liquid crystal aligning is improved, and excellent high-speed response can be played.
[the second embodiment]
The liquid crystal display device 11 of Fig. 2 (a) is: possess a pair substrate 2 of subtend configuration, be laminated in a pair liquid crystal orientation film 3 of the inner surface side of this pair substrate 2 respectively, be filled in the liquid crystal display device of the PSA mode of the liquid crystal layer 4 formed between above-mentioned liquid crystal orientation film 3 and by polymerizable liquid crystal compound.In this liquid crystal display device 11, also same with liquid crystal display device 1, at the stacked not shown Polarizer of two outside surfaces of substrate 2.
Liquid crystal display device 11 is, replace the wire projection 6 of liquid crystal display device 1 by the transparency electrode 15 of patterning and carry out liquid crystal molecule orientation segmentation liquid crystal display device.The transparency electrode 5a (common electrode) of the substrate 2 in liquid crystal display device 11, liquid crystal orientation film 3, liquid crystal layer 4 and side is owing to being that thus the material same with the liquid crystal display device 1 of Fig. 1 omit the description.
At the internal surface of the side of aforesaid substrate 2, be equipped with the transparency electrode 15 (pixel electrode) of herring-bone form pattern.Use the transparency electrode 15 of such patterning, thus liquid crystal molecule 4a in liquid crystal layer 4 can be made along this transparency electrode 15 orientation, just can realize orientation segmentation (with reference to Fig. 2 (b)).Again, this transparency electrode is same with known liquid crystal display device, is connected with not shown TFT, bus etc.
In this liquid crystal display device 11, also by making curable liquid crystal layer under the state being applied with voltage, thus the vergence direction of the liquid crystal molecule in liquid crystal layer can be remembered, as PSA mode liquid crystal display device and work.
Even if by this liquid crystal display device 11, also by forming liquid crystal orientation film by above-mentioned liquid crystal aligning agent, thus make liquid crystal aligning excellent and excellent high-speed response can be played.
[other embodiment]
Again, for this liquid crystal display device, in liquid crystal layer, the cured portion manifesting PSA can be formed in the mode of polymer layer 4 as the liquid crystal display device 1 of Fig. 1, also can be partial or formed universally in liquid crystal layer.In addition, also carry out the electrode of alternative above-mentioned wire projection or patterning by slit (slit), partition wall etc. and carry out orientation segmentation.In any one embodiment, also according to this liquid crystal display device, such as liquid crystal molecule relative to substrate interface minimum tilt after state under supported, liquid crystal orientation film is formed by this liquid crystal aligning agent, therefore, when applying voltage, liquid crystal molecule can be made positively to swing to this vergence direction and responsiveness now can be improved.
The manufacture method > of < liquid crystal display device
An example of the manufacture method of this liquid crystal display device is described for the situation of the liquid crystal display device 1 of Fig. 1.
As the manufacture method of liquid crystal display device 1, the method with following operation can be listed:
Formed the operation of liquid crystal orientation film 3 by above-mentioned liquid crystal aligning agent at each internal surface of a pair substrate 2 with transparency electrode 5a or 5b and wire projection 6,
The mode subtend configuration that above-mentioned a pair substrate 2 is faced each other according to internal surface, to the operation of filling polymerizable liquid crystal compound between this substrate, and
The operation that above-mentioned polymerizable liquid crystal compound solidifies is made under the state being applied with voltage.
With regard to the formation of above-mentioned liquid crystal orientation film, by after coating of liquid crystalline alignment agent, solidify under the effect of heating thus formed.
As the curing of above-mentioned polymerizable liquid crystal compound, can list: the thermofixation of use the photocuring of ultraviolet etc., giving based on heat.As irradiation dose when photocuring, be not particularly limited, but be such as 1,000 ~ 5,000mJ/cm as ultraviolet irradiation amount 2left and right.In addition, applying voltage during polymerization is also not particularly limited, but is about 0 ~ 20V.
By applying voltage in this wise while solidify (polymerization), form liquid crystal layer, thus state lower support liquid crystal molecule after tilting, effectively can control the orientation of liquid crystal molecule.In addition, according to this manufacture method, by forming liquid crystal orientation film by above-mentioned liquid crystal aligning agent, thus it is high and have the liquid crystal display device of the PSA mode of excellent high-speed response to manufacture liquid crystal aligning.
Embodiment
Below, further describe the present invention by synthesis example and embodiment, but the present invention is not limited to these embodiments.
The weight-average molecular weight (Mw) of the organopolysiloxane with epoxy group(ing) obtained below in an example and [A] compound is the polystyrene conversion value measured by the GPC of following specification.
Chromatographic column: East ソ mono-commercial firm, TSKgelGRCXLII
Solvent: tetrahydrofuran (THF)
Temperature: 40 DEG C
Pressure: 68kgf/cm 2
Again, the starting compound used below in an example and the necessary amounts of polymkeric substance, by repeatedly carrying out the synthesis of starting compound under the synthetic route shown in following synthesis example and polymkeric substance as required and guaranteeing.
< has the synthesis > of the organopolysiloxane of epoxy group(ing)
[synthesis example 1]
To in the reaction vessel having agitator, thermometer, dropping funnel and reflux condensing tube, add 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (ECETS) 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, at room temperature mix.Then, spend 30 minutes after dropping funnel dropping deionized water 100g, mix under reflux and reacted 6 hours at 80 DEG C.After reaction terminating, take out organic layer, washed by 0.2 quality % aqueous ammonium nitrate solution until after water after washing becomes neutrality, under reduced pressure solvent and water are distillated, thus obtain the organopolysiloxane with epoxy group(ing) in the mode of the transparent liquid of thickness.
The organopolysiloxane that this has epoxy group(ing) has been carried out 1h-NMR analyzes, and confirms: can obtain the peak based on epoxy group(ing) near chemical shift (δ)=3.2ppm, do not cause the side reaction of epoxy group(ing) in the reaction as theoretical strength.
[synthesis example 2 ~ 3]
Raw material setting will be added as described in Table 1, in addition, operate in the same manner as synthesis example 1 and obtain the organopolysiloxane with epoxy group(ing) respectively in the mode of the transparent liquid of thickness.The Mw with the organopolysiloxane of epoxy group(ing) obtained by synthesis example 1 ~ 3 and epoxy equivalent (weight) are shown in table 1 in the lump.Again, the abbreviation of the raw silicon hydride compounds in table 1 represents following meaning.
ECETS:2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane
MTMS: methyltrimethoxy silane
PTMS: phenyltrimethoxysila,e
Table 1
The synthesis > of the specific carboxylic acid of <
[synthesis of specific carboxylic acid 1]
Specific carboxylic acid 1 has been synthesized according to following reaction scheme.
[synthesis example 4]
To have prolong 500mL there-necked flask in add 4-cyano group-4 '-xenol 6.3g, 11-bromoundecane acid methyl esters 10g, salt of wormwood 14.2g, DMF 200mL, 160 DEG C of heated and stirred 5 hours.After utilizing TLC to confirm that reaction terminates, reaction soln is cooled to room temperature.Reaction soln is devoted water 500mL, carried out mix and blend.By the white solid filtering separation separated out, wash further with water.By at 80 DEG C by obtained solid vacuum-drying, thus obtain 11g compound 1.
[synthesis example 5]
Then, in the there-necked flask of 200mL having prolong, 10g compound 1,1.6g lithium hydroxide monohydrate, 30mL methyl alcohol, 15mL water is added, 80 DEG C of heated and stirred 4 hours.After utilizing TLC to confirm that reaction terminates, reaction soln is cooled to room temperature.Under the state stirring reaction soln, dilute hydrochloric acid is slowly dripped in reaction soln.Solid filtering will be separated out, by the sequential purge of water, ethanol.By at 80 DEG C by obtained solid vacuum-drying, thus obtain the specific carboxylic acid 1 of 8g.
[synthesis of specific carboxylic acid 2]
Specific carboxylic acid 2 has been synthesized according to following reaction scheme.
[synthesis example 6]
To have prolong 500mL there-necked flask in add 4-cyano group-4 '-xenol 15g, ethylene carbonate 13.5g, Tetrabutyl amonium bromide (TBAB) 2.5g, DMF 300mL, 150 DEG C of heated and stirred 9 hours.After utilizing TLC to confirm that reaction terminates, reaction soln is cooled to room temperature.Reaction soln has been washed with the mixing solutions separatory of ethyl acetate 300mL, 1N-aqueous sodium hydroxide solution 100mL.Extract organic layer, then carry out separatory washing according to the order of 1N-aqueous sodium hydroxide solution 100mL, water 100mL further.With magnesium sulfate by after organic layer drying, organic solvent is distillated.After obtained solid vacuum-drying, carry out recrystallize with ethanol 100mL/ hexane 250mL, thus obtain 13.1g compound 2.
[synthesis example 7]
To have prolong, dropping funnel 200mL there-necked flask in add 12g compound 2, the 4-chlorobenzene sulfonyl chloride of 12.7g, 60mL dewater methylene dichloride and mix.Under the state being cooled with an ice bath reaction soln, spend 10 minutes and drip the dehydration methylene dichloride 10mL solution of triethylamine 6.6g.Under ice bath state, stir 30 minutes, turn back to room temperature and stir 6 hours further.In reaction soln, add chloroform 150mL, carry out 4 separatory washings with water 100mL.With the organic layer that dried over mgso extracts, organic solvent is distillated.With ethanol, obtained solids wash is obtained 16.1g compound 3.
[synthesis example 8]
To have prolong 300mL there-necked flask in add the DMF of 15g compound 3, the 4-HBA methyl esters of 11g, 12.5g salt of wormwood, 180mL, 80 DEG C of heated and stirred 9 hours.After utilizing TLC to confirm that reaction terminates, reaction soln is cooled to room temperature.Reaction soln is devoted 500mL water, carried out mix and blend.By the white solid filtering separation separated out, wash further with ethanol.By at 80 DEG C by obtained solid vacuum-drying, thus obtain 10g compound 4.
[synthesis example 9]
To have prolong 100mL there-necked flask in add 9.5g compound 4,1.6g lithium hydroxide monohydrate, 30mL methyl alcohol, 15mL tetrahydrofuran (THF), 15mL water, 80 DEG C of heated and stirred 4 hours.After utilizing TLC to confirm that reaction terminates, reaction soln is cooled to room temperature.Under the state stirring reaction soln, dilute hydrochloric acid is slowly dripped in reaction soln.Solid filtering will be separated out, by the sequential purge of water, ethanol.By at 80 DEG C by obtained solid vacuum-drying, thus obtain the specific carboxylic acid 2 of 9g.
[synthesis of specific carboxylic acid 3]
Specific carboxylic acid 3 has been synthesized according to following reaction scheme.
[synthesis example 10]
In synthesis example 4,2,3,5,6-tetra-fluoro-4-(pentafluorophenyl group) phenol of 10.7g are used to carry out alternative 4-cyano group-4 '-xenol thus obtain 13.7g compound 5.
[synthesis example 11]
In synthesis example 5, use 13.5g compound 5 to carry out alternative compounds 1, thus obtain the specific carboxylic acid 3 of 11.2g.
[synthesis of specific carboxylic acid 4]
Specific carboxylic acid 4 has been synthesized according to following reaction scheme.
[synthesis example 12]
In synthesis example 6,2,3,5,6-tetra-fluoro-4-(pentafluorophenyl group) phenol of 25.5g are used to carry out alternative 4-cyano group-4 '-xenol, thus obtain 23.1g compound 6.
[synthesis example 13]
In synthesis example 7, use 18.9g compound 6 to carry out alternative compounds 2, thus obtain 24.1g compound 7.
[synthesis example 14]
In synthesis example 8, use 20g compound 7 to carry out alternative compounds 3, thus obtain 15.4g compound 8.
[synthesis example 15]
In synthesis example 9, use 13g compound 8 to carry out alternative compounds 4, thus obtain the specific carboxylic acid 4 of 11.4g.
[synthesis of specific carboxylic acid 5]
Specific carboxylic acid 5 has been synthesized according to following reaction scheme.
[synthesis example 16]
Operate in the same manner as the synthesis of specific carboxylic acid 1, obtain 15g and the number of methylene radical is changed to 5 and the specific carboxylic acid 5 obtained from 10.
[synthesis of specific carboxylic acid 6]
Specific carboxylic acid 6 has been synthesized according to following reaction scheme.
[synthesis example 17]
To have prolong 500mL there-necked flask in add 2,2 ', 3,3 '-four fluoro-4 '-propyl group-4-xenol 10.1g, 11-bromoundecane acid methyl esters 10g, salt of wormwood 14.2g, N, dinethylformamide 200mL, 160 DEG C of heated and stirred 5 hours.After utilizing TLC to confirm that reaction terminates, reaction soln is cooled to room temperature.Reaction soln is devoted water 500mL, carried out mix and blend.By the white solid filtering separation separated out, wash further with water.By at 80 DEG C by obtained solid vacuum-drying, thus obtain 10.8g compound 9.
[synthesis example 18]
Then, in the there-necked flask of 200mL having prolong, 10g compound 9,1.6g lithium hydroxide monohydrate, 30mL methyl alcohol, 15mL water is added, 80 DEG C of heated and stirred 4 hours.After utilizing TLC to confirm that reaction terminates, reaction soln is cooled to room temperature.Under the state stirring reaction soln, dilute hydrochloric acid is slowly dripped in reaction soln.Solid filtering will be separated out, by the sequential purge of water, ethanol.By at 80 DEG C by obtained solid vacuum-drying, thus obtain the specific carboxylic acid 6 of 6g.
[synthesis of specific carboxylic acid 7]
Specific carboxylic acid 7 has been synthesized according to following reaction scheme.
[synthesis example 19]
By initial compounds (2,2 ', 3,3 '-four fluoro-4 '-propyl group-4-xenol) 10.1g becomes the compound (2 recorded in above-mentioned reaction scheme, the fluoro-4-of 3-bis-(4-propyl-cyclohexyl base) phenol) 9.1g, in addition, operate in the same manner as the synthesis of above-mentioned specific carboxylic acid 6, obtain the specific carboxylic acid 7 of 5.9g.
[synthesis of specific carboxylic acid 8]
Specific carboxylic acid 8 has been synthesized according to following reaction scheme.
[synthesis example 20]
By initial compounds (2,2 ', 3,3 '-four fluoro-4 '-propyl group-4-xenol) 10.1g becomes the compound (2,2 ', 3 recorded in above-mentioned reaction scheme, 3 '-four fluoro-4-propyl group-4 "-hydroxyl terphenyl) 12.9g; in addition, operate in the same manner as the synthesis of above-mentioned specific carboxylic acid 6, obtain the specific carboxylic acid 8 of 7.1g.
[synthesis of specific carboxylic acid 9]
Specific carboxylic acid 9 has been synthesized according to following reaction scheme.
[synthesis example 21]
By initial compounds (2,2 ', 3,3 '-four fluoro-4 '-propyl group-4-xenol) 10.1g becomes the compound (2 recorded in above-mentioned reaction scheme, the fluoro-4-of 3-bis-(4-cyclohexyl ylmethoxy) phenol) 10.2g, in addition, operate in the same manner as the synthesis of above-mentioned specific carboxylic acid 6, obtain the specific carboxylic acid 9 of 6.5g.
[synthesis of specific carboxylic acid 10]
Specific carboxylic acid 10 has been synthesized according to following reaction scheme.
[synthesis example 22]
By initial compounds (2,2 ', 3,3 '-four fluoro-4 '-propyl group-4-xenol) 10.1g becomes the compound (2 recorded in above-mentioned reaction scheme, fluoro-4 '-(the 4-propyl group phenylethyl) biphenyl of 3-bis-) 12.6g, in addition, operate in the same manner as the synthesis of above-mentioned specific carboxylic acid 6, obtain the specific carboxylic acid 10 of 7.2g.
[synthesis of specific carboxylic acid 11]
Specific carboxylic acid 11 has been synthesized according to following reaction scheme.
[synthesis example 23]
By initial compounds (2,2 ', 3,3 '-four fluoro-4 '-propyl group-4-xenol) 10.1g becomes the compound 14.2g recorded in above-mentioned reaction scheme, in addition, operate in the same manner as the synthesis of above-mentioned specific carboxylic acid 6, obtain the specific carboxylic acid 11 of 7.6g.
[synthesis of specific carboxylic acid 12]
According to following reaction scheme, synthesize specific carboxylic acid 12.
[synthesis example 24]
To in the there-necked flask of 500mL having prolong, add 4-[difluoro (4-pentylcyclohexyl) methoxyl group]-2,3-difluorophenol 12.5g, 11-bromoundecane acid methyl esters 10g, salt of wormwood 14.2g, N, dinethylformamide 200mL, 160 DEG C of heated and stirred 5 hours.After utilizing TLC to confirm that reaction terminates, reaction soln is cooled to room temperature.Reaction soln is devoted 500mL water, carried out mix and blend.By the white solid filtering separation separated out, wash further with water.By at 80 DEG C by obtained solid vacuum-drying, thus obtain 14.8g compound 10.
[synthesis example 25]
Then, in the there-necked flask of 200mL having prolong, 10g compound 10,1.6g lithium hydroxide monohydrate, 30mL methyl alcohol, 15mL water is added, 80 DEG C of heated and stirred 4 hours.After utilizing TLC to confirm that reaction terminates, reaction soln is cooled to room temperature.Under the state stirring reaction soln, dilute hydrochloric acid is slowly dripped in reaction soln.Solid filtering will be separated out, by the sequential purge of water, ethanol.By at 80 DEG C by obtained solid vacuum-drying, thus obtain the specific carboxylic acid 12 of 6g.
The synthesis > of < [A] compound
[synthesis example 26]
To in the there-necked flask of 100mL, add the organopolysiloxane with epoxy group(ing) that 9.8g obtains by above-mentioned synthesis example 1, specific carboxylic acid 1, the 4-octyloxy phenylformic acid of 3.3g as one of compound represented by above-mentioned formula (4) represented by illustrative formula (4-11) and the UCAT18X (quaternary amine of サ Application ア プ ロ commercial firm) of 0.20g that 28g methyl iso-butyl ketone (MIBK), 5.0g are obtained by above-mentioned synthesis example 5, stir 12 hours at 80 DEG C.After reaction terminating, carry out redeposition with methyl alcohol, precipitate dissolves is obtained solution in ethyl acetate, 3 washings are carried out to this solution, then solvent is distillated, thus obtain [A] compd A-1 of 14.5g in white powder mode.The Mw of [A] compd A-1 is 6,500.
[synthesis example 27]
The specific carboxylic acid 2 using 4g to be obtained by synthesis example 9 carrys out alternative specific carboxylic acid 1, operates in addition, thus obtain the white powder of [A] compd A-2 of 12.8g in the same manner as synthesis example 26.The Mw of [A] compd A-2 is 6,000.
[synthesis example 28]
The specific carboxylic acid 3 using 6.8/g to be obtained by synthesis example 11 carrys out alternative specific carboxylic acid 1, operates in addition, thus obtain the white powder of [A] compd A-3 of 14.7g in the same manner as synthesis example 26.The Mw of [A] compd A-3 is 8,100.
[synthesis example 29]
The specific carboxylic acid 4 using 5.6g to be obtained by synthesis example 15 carrys out alternative specific carboxylic acid 1, has carried out the synthesis of [A] compound in addition in the same manner as synthesis example 26.Its result, obtains the white powder of [A] compd A-4 of 15.0g.The Mw of [A] compd A-4 is 7,500.
[synthesis example 30]
To in the there-necked flask of 100mL, add the UCAT18X (quaternary amine of サ Application ア プ ロ commercial firm) of the organopolysiloxane with epoxy group(ing) that 9.8g obtains by above-mentioned synthesis example 1,28g methyl iso-butyl ketone (MIBK), specific carboxylic acid 1 that 10g is obtained by above-mentioned synthesis example 5 and 0.20g, stir 12 hours at 80 DEG C.After reaction terminating, carry out redeposition with methyl alcohol, by precipitate dissolves in ethyl acetate, 3 washings are carried out to this solution, then solvent is distillated, thus obtain [A] compd A-5 of 16.0g in white powder mode.The Mw of [A] compd A-5 is 8,500.
[synthesis example 31]
Use the specific carboxylic acid 5 that obtained by synthesis example 16 of 4.1g to carry out alternative specific carboxylic acid 1, operate in the same manner as synthesis example 26 in addition and obtain the white powder of [A] compd A-6 of 12.4g.The Mw of [A] compd A-6 is 6,200.
[synthesis example 32]
4-(4-pentylcyclohexyl) phenylformic acid of 3.6g as one of compound represented by above-mentioned formula (4) represented by illustrative formula (4-13) is used to carry out alternative 4-octyloxy phenylformic acid, operate in the same manner as synthesis example 26 in addition, thus obtain the white powder of [A] compd A-7 of 13.4g.The Mw of [A] compd A-7 is 7,900.
[synthesis example 33]
To in the there-necked flask of 100mL, add the UCAT18X (quaternary amine of サ Application ア プ ロ commercial firm) of the organopolysiloxane with epoxy group(ing) that 9.8g obtains by above-mentioned synthesis example 1,28g methyl iso-butyl ketone (MIBK), specific carboxylic acid 1 that 8.0g is obtained by above-mentioned synthesis example 5,4-(4-pentylcyclohexyl) phenylformic acid that 1.4g is represented by above-mentioned formula (4-13) and 0.20g, stir 12 hours at 80 DEG C.After reaction terminating, carry out redeposition with methyl alcohol, by precipitate dissolves in ethyl acetate, 3 washings are carried out to this solution, then solvent is distillated, thus obtain [A] compd A-8 of 13.9g in white powder mode.The Mw of [A] compd A-8 is 8,900.
[synthesis example 34]
To in the there-necked flask of 100mL, add the UCAT18X (quaternary amine of サ Application ア プ ロ commercial firm) of the organopolysiloxane with epoxy group(ing) that 9.8g obtains by above-mentioned synthesis example 1,28g methyl iso-butyl ketone (MIBK), specific carboxylic acid 1 that 2.0g is obtained by above-mentioned synthesis example 5,4-(4-pentylcyclohexyl) phenylformic acid that 5.8g is represented by above-mentioned formula (4-13) and 0.20g, stir 12 hours at 80 DEG C.After reaction terminating, carry out redeposition with methyl alcohol, precipitate dissolves is obtained solution in ethyl acetate, 3 washings are carried out to this solution, then solvent is distillated, thus obtain [A] compd A-9 of 13.4g in white powder mode.The Mw of [A] compd A-9 is 7,600.
[synthesis example 35]
To in the there-necked flask of 100mL, add the UCAT18X (quaternary amine of サ Application ア プ ロ commercial firm) of the organopolysiloxane with epoxy group(ing) that 9.8g obtains by above-mentioned synthesis example 1,28g methyl iso-butyl ketone (MIBK), specific carboxylic acid 1 that 8.0g is obtained by above-mentioned synthesis example 5, carboxylic acid derivative that 2.6g is represented by above-mentioned formula (4-12) and 0.20g, stir 12 hours at 80 DEG C.After reaction terminating, carry out redeposition with methyl alcohol, by precipitate dissolves in ethyl acetate, 3 washings are carried out to this solution, then solvent is distillated, thus obtain [A] compd A-10 of 15.5g in white powder mode.The Mw of [A] compd A-10 is 9,200.
[synthesis example 36]
Use the specific carboxylic acid 6 that obtained by synthesis example 18 of 6.1g to carry out alternative specific carboxylic acid 1, operate in the same manner as synthesis example 26 in addition and obtain the white powder of [A] compd A-11 of 18.4g.The Mw of [A] compd A-11 is 7,300.
[synthesis example 37]
Use the specific carboxylic acid 7 that obtained by synthesis example 19 of 5.7g to carry out alternative specific carboxylic acid 1, operate in the same manner as synthesis example 26 in addition and obtain the white powder of [A] compd A-12 of 17.5g.The Mw of [A] compd A-12 is 7,600.
[synthesis example 38]
Use the specific carboxylic acid 8 that obtained by synthesis example 20 of 7.2g to carry out alternative specific carboxylic acid 1, operate in the same manner as synthesis example 26 in addition and obtain the white powder of [A] compd A-13 of 19.1g.The Mw of [A] compd A-13 is 7,000.
[synthesis example 39]
Use the specific carboxylic acid 9 that obtained by synthesis example 21 of 6.2g to carry out alternative specific carboxylic acid 1, operate in the same manner as synthesis example 26 in addition and obtain the white powder of [A] compd A-14 of 18.1g.The Mw of [A] compd A-14 is 6,900.
[synthesis example 40]
Use the specific carboxylic acid 10 that obtained by synthesis example 22 of 7.0g to carry out alternative specific carboxylic acid 1, operate in the same manner as synthesis example 26 in addition and obtain the white powder of [A] compd A-15 of 19.4g.The Mw of [A] compd A-15 is 7,500.
[synthesis example 41]
Use the specific carboxylic acid 11 that obtained by synthesis example 23 of 8.4g to carry out alternative specific carboxylic acid 1, operate in the same manner as synthesis example 26 in addition and obtain the white powder of [A] compd A-16 of 20.1g.The Mw of [A] compd A-16 is 7,300.
[synthesis example 42]
Use the specific carboxylic acid 12 that obtained by synthesis example 25 of 7.2g to carry out alternative specific carboxylic acid 1, operate in the same manner as synthesis example 26 in addition and obtain the white powder of [A] compd A-17 of 19.5g.The Mw of [A] compd A-17 is 7,300.
[comparing synthesis example 1]
To in the there-necked flask of 100mL, add the organopolysiloxane with epoxy group(ing), 28g methyl iso-butyl ketone (MIBK), the 4-octyloxy phenylformic acid of 3.3g and the UCAT18X (quaternary amine of サ Application ア プ ロ commercial firm) of 0.10g that 9.8g is obtained by above-mentioned synthesis example 1, stir 12 hours at 80 DEG C.After reaction terminating, carry out redeposition with methyl alcohol, by precipitate dissolves in ethyl acetate, 3 washings are carried out to this solution, then solvent is distillated, thus obtain [A] Compound C A-1 of 9.6g in white powder mode.The Mw of Compound C A-1 is 6,000.
The synthesis > of < polyamic acid
[synthesis example 43]
1,2,3,4-cyclobutanetetracarboxylic dianhydride 19.61g (0.1 mole) and 4,4 '-diamino-2,2 '-dimethyl diphenyl 21.23g (0.1 mole) are dissolved in METHYLPYRROLIDONE 367.6g, at room temperature react 6 hours.Then, reaction mixture is injected excessive methyl alcohol, reaction product is precipitated.Use methanol wash throw out, by under reduced pressure 40 DEG C of dryings 15 hours, thus obtain 35g polyamic acid PA-1.
[synthesis example 44]
2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 22.4g (0.1 mole) and two (methylamine) 14.23g (0.1 mole) of hexanaphthene are dissolved in METHYLPYRROLIDONE 329.3g, react 6 hours at 60 DEG C.Then, reactant is injected excessive methyl alcohol, reaction product is precipitated.Use methanol wash throw out, under reduced pressure 40 DEG C of dryings 15 hours, thus obtain 32g polyamic acid PA-2.
The synthesis > of < polyimide
[synthesis example 45]
Take the polyamic acid PA-2 that 17.5g is obtained by above-mentioned synthesis example 44, add METHYLPYRROLIDONE 232.5g, pyridine 3.8g and diacetyl oxide 4.9g wherein, carry out imidization 120 DEG C of reactions 4 hours.Then, reaction mixture is injected excessive methyl alcohol, reaction product is precipitated.Use methanol wash throw out, drying under reduced pressure 15 hours, thus obtain 15g polyimide PI-1.
[synthesis example 46]
Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 19.88g, be dissolved in METHYLPYRROLIDONE 140g as Ursol D 6.83g, the diaminodiphenyl-methane 3.58g of diamine compound and the diamines 4.72g that represented by above-mentioned formula (G-4), reacted 4 hours at 60 DEG C.Then, reaction soln is flow in excessive methyl alcohol and reaction product is precipitated.Thereafter, by methanol wash, under reduced pressure obtain polyamic acid 32.8g 40 DEG C of dryings 24 hours.Obtained polyamic acid 30g is dissolved in METHYLPYRROLIDONE 400g, add pyridine 12.0g and diacetyl oxide 15.5g and 110 DEG C of dehydration closed-loops 4 hours, operate as described above, carry out precipitating, wash, drying under reduced pressure, obtain the Mw=92 of 25g, 000, Mw/Mn=4.19, imide rate 79% polyimide PI-2.
The preparation > of < liquid crystal aligning agent
[embodiment 1]
Take the solution containing the polyamic acid PA-1 obtained by synthesis example 43, the amount of taking is be scaled wherein contained polyamic acid PA-1 to be equivalent to 1, the amount of 000 mass parts, add [A] compd A-1 (100 mass parts), add METHYLPYRROLIDONE and ethylene glycol butyl ether further, thus to make solvent composition be METHYLPYRROLIDONE: ethylene glycol butyl ether=50: 50 (mass ratioes), solid component concentration are the solution of 3.0 quality %.By this solution of metre filter in 10.2 μm, aperture, thus prepare liquid crystal aligning agent S-1.
[embodiment 2 ~ 21 and comparative example 1]
Set as the polyamic acid of [B] polymkeric substance or polyimide, combination as the polyorganosiloxane compounds of [A] composition as recorded in table 2, in addition, operate similarly to Example 1, thus prepared liquid crystal aligning agent S-2 ~ S-21 and CS-1.
[comparative example 2]
To in the polyimide PI-2 obtained by above-mentioned synthesis example 46, be METHYLPYRROLIDONE according to solvent composition: ethylene glycol butyl ether=70: the mode of 30 (mass ratioes) adds METHYLPYRROLIDONE and ethylene glycol butyl ether respectively, thus make the solution that solid component concentration is 3.0 quality %.Liquid crystal aligning agent CS-2 has been prepared by this solution of metre filter in 0.2 μm, aperture.Again, "-" in table represents the composition not using correspondence.
The manufacture > of < liquid crystal display device
As the liquid crystal display device of liquid crystal aligning agent S-1 employing embodiment 1,15 type XGA panels (pel spacing: 297 μm, pixel count: 1024 × 768) are made.Figure 3 shows that the mode chart of a pixel of this panel (liquid crystal display device).The substrate of side defines the transparency electrode 21 of patterning.Further in order to make transparency electrode 21 work as pixel electrode, be provided with TFT22 and bus 23 on the substrate.The transparency electrode 21 of patterning extends from pixel central part to 4 orientation (upper right, bottom right, upper left, lower-left) as shown in Figure 3.Herein, the electrode width of the transparency electrode 21 of the patterning near boundary portion (spine) is 2 μm, the width of interval (space) is 4 μm, and the electrode width away from the region of boundary portion is 4 μm, interval wide is 2 μm.From boundary portion end to the distance x of pattern width change section be 5 μm.At the substrate of another side, define transparency electrode (common electrode).Baseplate material employs the glass substrate OA-2 (NEG Inc.) of thickness of slab 0.7mm.
On these substrates, use liquid crystal aligning agent S-1 to form liquid crystal orientation film by print process, carried out the thermal treatment of 60 minutes at 180 DEG C.Further, the spacer (Plot water Off ア イ Application ケ ミ カ Le commercial firm system) via diameter 4 μm, by these baseplate-laminatings, has made the sylphon not injecting liquid crystal.In this box, be filled with the dielectric constant anisotropy that trace with the addition of photopolymerization monomer (large Japanese ink Inc.) is negative liquid crystal (メ ルク commercial firm system).The addition of photopolymerization monomer is 2.4 quality %.Then, the irradiation ultraviolet radiation to this groove applying voltage, the polymerization by monomer polymerization.Further, on the two sides, outside of substrate, Polarizer is fitted according to the mode that the polarization direction of 2 Polarizers is mutually orthogonal, thus made the liquid crystal display device of embodiment 1.Applying voltage during polymerization is 10V, UV irradiation dose is 2,000mJ/cm 2(λ=365nm).
Use the liquid crystal aligning agent represented by table 2 to carry out alternative liquid crystal aligning agent S-1, in addition, carry out operation similar to the above, thus make the liquid crystal display device of the liquid crystal aligning agent employing embodiment 2 ~ 20 and comparative example 1 and 2.
< evaluates >
Following evaluation has been carried out to the liquid crystal display device manufactured.Table 2 will be the results are shown in.
[orientation]
For the liquid crystal display device by above-mentioned manufacture, the light do not applied under voltage status by visual observation under backlight irradiates leaks orientation presence or absence at random, the situation that light does not leak orientation at random is "○", there is light in a part and leak orientation situation at random for " △ ", the situation that cannot obtain vertical orientated state is completely "×".
[response speed (electrooptics responsiveness during beginning)]
Utilize the device comprising polarizing microscope, photodetector and pulses generation machine to determine the time of the beginning of liquid crystal response.Liquid crystal response speed refers to herein: from not applying voltage status to made liquid crystal display device to when applying the voltage of 5V of maximum 1 second, be changed to the time (msec.) required for transmissivity 90% from transmissivity 10%.
Table 2
Liquid crystal aligning agent [A] composition [B] composition Orientation Response speed (msec.)
Embodiment 1 S-1 A-1 PA-1 ○ 30
Embodiment 2 S-2 A-2 PA-1 ○ 32
Embodiment 3 S-3 A-3 PA-1 ○ 28
Embodiment 4 S-4 A-4 PA-1 ○ 31
Embodiment 5 S-5 A-5 PI-2 ○ 38
Embodiment 6 S-6 A-6 PA-1 ○ 27
Embodiment 7 S-7 A-7 PA-1 ○ 27
Embodiment 8 S-8 A-8 PA-1 △ 30
Embodiment 9 S-9 A-9 PA-1 ○ 32
Embodiment 10 S-10 A-10 PA-1 ○ 33
Embodiment 11 S-11 A-7 PA-2 ○ 32
Embodiment 12 S-12 A-7 PI-1 ○ 31
Embodiment 13 S-13 A-7 PI-2 ○ 38
Embodiment 14 S-14 A-8 PI-2 ○ 34
Embodiment 15 S-15 A-11 PA-1 ○ 27
Embodiment 16 S-16 A-12 PA-1 ○ 27
Embodiment 17 S-17 A-13 PA-1 ○ 27
Embodiment 18 S-18 A-14 PA-1 ○ 27
Embodiment 19 S-19 A-15 PA-1 ○ 27
Embodiment 20 S-20 A-16 PA-1 ○ 27
Embodiment 21 S-21 A-17 PA-1 ○ 27
Comparative example 1 CS-1 CA-1 PA-1 ○ 53
Comparative example 2 CS-2 - PI-2 ○ 56
According to the result of table 2, the orientation possessing the liquid crystal display device of the liquid crystal orientation film using the liquid crystal aligning agent of embodiment 1 ~ 21 to make is excellent, and in the response speed of liquid crystal, high speed reaches about more than about 2/3 compared with the liquid crystal display device of comparative example.
Utilizability in industry
Liquid crystal aligning agent of the present invention can be preferred for the liquid crystal display device of the PSA mode manufacturing high-speed response excellence.
Description of reference numerals
1,11 liquid crystal display device
2 substrates
3 liquid crystal orientation films
4 liquid crystal layers
4a liquid crystal molecule
5,5a, 5b transparency electrode
6 wire projections
The transparency electrode of 15 patternings
21 transparency electrodes
22TFT
23 buses

Claims (5)

1. a manufacture method for the liquid crystal display device of PSA mode, it has following operation:
The operation of liquid crystal orientation film is formed by liquid crystal aligning agent at each internal surface of a pair substrate with transparency electrode,
The mode subtend configuration that above-mentioned a pair substrate is faced each other according to internal surface, to the operation of filling polymerizable liquid crystal compound between this substrate, and
The operation that above-mentioned polymerizable liquid crystal compound solidifies is made under the state being applied with voltage;
It is characterized in that, described liquid crystal aligning agent contains the compound that [A] has the group represented by following formula (1),
In formula (1), R 1for the group that following formula (D-1) ~ (D-123) represents, R 2for comprising the link group of double bond, triple bond, ehter bond, ester bond or Sauerstoffatom, a is the integer of 0 ~ 1,
In formula (D-1) ~ (D-123), R is the alkyl of carbonatoms 1 to 20 or the alkoxyl group of carbonatoms 1 ~ 20; X is hydrogen atom or fluorine atom independently of one another.
2. the manufacture method of the liquid crystal display device of PSA mode according to claim 1, wherein, above-mentioned liquid crystal aligning agent is the liquid crystal aligning agent containing [A] compound, should have by [A] compound: be derived from the part of the organopolysiloxane with epoxy group(ing), be derived from the part of the compound represented by following formula (2)
In formula (2), R 1, R 2and a is same with above-mentioned formula (1) defines, R 3for the alkylidene group of methylene radical, carbonatoms 2 ~ 30, phenylene or cyclohexylidene, these groups can have substituting group further.
3. the manufacture method of the liquid crystal display device of PSA mode according to claim 2, wherein, by being by following formula (X containing above-mentioned epoxy group(ing) 1-1) or (X 1-2) liquid crystal aligning agent of above-mentioned [A] compound of the group represented and form liquid crystal orientation film,
Formula (X 1-1) in, A is Sauerstoffatom or singly-bound, and h is the integer of 1 ~ 3, and i is the integer of 0 ~ 6, and wherein, when i is 0, A is singly-bound,
Formula (X 1-2), in, j is the integer of 0 ~ 6.
4. the manufacture method of the liquid crystal display device of PSA mode according to claim 1 and 2, wherein, above-mentioned liquid crystal aligning agent is the liquid crystal aligning agent of at least one polymkeric substance selected in the group be made up of polyamic acid and polyimide containing [B] further.
5. a liquid crystal display device for PSA mode, its manufacture method by the liquid crystal display device of the PSA mode according to any one of claim 1 ~ claim 4 and manufacturing.
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