CN101236333A - Liquid crystal orientating agent and liquid crystal display element - Google Patents

Liquid crystal orientating agent and liquid crystal display element Download PDF

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CN101236333A
CN101236333A CNA2008100094554A CN200810009455A CN101236333A CN 101236333 A CN101236333 A CN 101236333A CN A2008100094554 A CNA2008100094554 A CN A2008100094554A CN 200810009455 A CN200810009455 A CN 200810009455A CN 101236333 A CN101236333 A CN 101236333A
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liquid crystal
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aligning agent
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atom
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CN101236333B (en
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宫本佳和
阿部翼
林英治
西川通则
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

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Abstract

A liquid crystal orientation agent, comprising acrylic acid polymer containing pretilt angle presenting ingredient expressed by the following formula (1-1) or (1-2). With application of the liquid crystal orientation agent, a liquid orientation film with excellent coating performance can be obtained, capable of preventing voltage retention from reducing or prevent the screen from being burnt out even applying optical, thermal stress on the liquid crystal panel or driving the liquid crystal panel for a long time.

Description

Aligning agent for liquid crystal and liquid crystal display cells
Technical field
Liquid crystal orientation film that the present invention relates to the novel liquid crystal alignment agent, forms by this aligning agent for liquid crystal and liquid crystal display cells with this liquid crystal orientation film.More specifically, relate to and show that excellent coating, high voltage holding ratio and inhibition apply the stress that causes because of light and heat for a long time to liquid crystal panel or make the voltage retention under the long-time situation about driving of liquid crystal panel reduce, burn and shield aligning agent for liquid crystal that produces and the liquid crystal orientation film that is formed by this alignment agent, contain the liquid crystal display cells of this liquid crystal orientation film.
Background technology
From viewpoints such as save space, low power consumptions, the liquid crystal display cells that with the LCD is representative has quantized to produce since the liquid crystal desk-top computer first, constantly use, and continue active exploitation to many-sides such as clock, pocket game machine, spoken and written languages processor, laptop, auto navigation, field camera, PDA, digital camera, mobile phone, various watch-dog, LCD TV.As liquid crystal display cells, be extensive use of: use nematic crystal, TN (Twisted Nematic) the type liquid crystal display cells that the major axis of liquid crystal molecule obtains to continuous folding 90 degree of another substrate from a substrate with positive dielectric anisotropy always; Or compare STN (Super Twisted Nematic) the type liquid crystal display cells that forms high-contrast with TN type liquid crystal display cells.In addition, in recent years, in order further to improve the display quality of LCD, optical compensation curved (OCB) type liquid crystal display cells that develop the little VA of angle of visibility dependence (Vertical Alignment) type liquid crystal display cells, IPS (In Plane Switching) type liquid crystal display cells, the angle of visibility dependence is little and the high-speed responsive of image frame is also excellent etc.
In liquid crystal display cells, the parts of control liquid crystal aligning are liquid crystal orientation films.Liquid crystal orientation film forms by the following method: will contain the aligning agent for liquid crystal that polyamic acid maybe carries out this polyamic acid the imide amination polymer that imidizate forms by rolling method, spin-coating method, gentle version (flexo) print process, ink-jet method etc. and be applied on the substrate, then, with the coated face heat drying.At this, it is bad that the crawling of alignment films is directly connected to the orientation of liquid crystal, becomes the significantly reduced main cause of the display quality that makes liquid crystal panel.For the alignment agent that contains polyimide that used in the past, in the research of having carried out improving the imidizate rate of polyimide aspect the electrical characteristics such as improvement voltage retention, but there is the relation of compromise (trade off) in the coating of high imidizate rate and alignment agent, therefore wishes urgently to develop to have the excellent electrical characteristics and the aligning agent for liquid crystal of coating concurrently.In addition, the deterioration of liquid crystal orientation film and impurity can make voltage retention reduce to the absorption of this alignment films, think to cause that plate shows the reduction of display performances such as inequality, picture flickering, contrast reduction.In the past, method as the improvement voltage retention, report has: the example (spy opens flat 10-168455 communique) that adds the multi-functional epoxy compound in polyamic acid, attempt the example (specially permit No. 3572690 communique and Te Kai 2001-228481 communique) of the skeleton of the raw material-tetracarboxylic dianhydride of improvement polyamic acid and imide amination polymer and diamines, in polyamic acid, add the example (speciallyying permit the 3206169th communique) of acrylate copolymer etc.Yet, even the initial voltage conservation rate of these reports and to liquid crystal panel apply the stress of light and heat or make that liquid crystal panel drives for a long time, voltage retention also the improved effect of indeclinable reliability can not say so fully, and the coating aspect when improveing alignment films formation at the same time is not research also.In recent years, along with liquid crystal panel is applied in liquid crystal TV and the high-quality watch-dog, liquid crystal orientation film is in order to realize high-quality display performance, and except high voltage holding ratio, also urgent hope is reliability, the coating when alignment films forms of improvement voltage retention further.
Summary of the invention
The present invention is based on above situation and finishes, and therefore, the object of the present invention is to provide aligning agent for liquid crystal and this liquid crystal orientation film that can obtain following liquid crystal orientation film, and the liquid crystal display cells that can show beautiful image by this liquid crystal orientation film for a long time; Even described liquid crystal orientation film shows excellent coating and liquid crystal panel is applied the stress of light and heat or makes long-time driving of liquid crystal panel voltage retention can not take place yet reduce and burn screen.
Other purposes of the present invention and advantage can be clear and definite by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage are to realize by the aligning agent for liquid crystal that contains the polymkeric substance with the represented repetitive of following formula (1).
(in the formula, R 1It is hydrogen atom; Halogen atom; Can have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～30 alkyl; Or the polar group of 1 valency.A 1Be that singly-bound or carbon number are 1～10 alkylidene.A 2, A 3And A 4Independent separately, be singly-bound, ehter bond (O-), carbonyl (CO-), carbonyl oxygen base (COO-), the oxygen carbonyl (OCO-), amido link (NHCO-,-CONH-), thioether bond (S-) or carbon number be 1～10 alkylidene.B 1, B 2And B 3Independent separately, be singly-bound, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-cyclohexylidene, 1,3-cyclohexylidene, 1,4-cyclohexylidene or piperidines-1,4-two bases.R 2Be that hydrogen atom, carbon number are 1～50 alkyl or the group that contains fluorine atom.But, the A of adjacency 1～A 4And B 1～B 3Represent a singly-bound when all being singly-bound, and A 1～A 4And B 1～B 3When all representing a singly-bound, R 2It or not hydrogen atom.)
In addition, according to the present invention, above-mentioned purpose of the present invention is to reach by liquid crystal orientation film that is formed by above-mentioned aligning agent for liquid crystal and the liquid crystal display cells that possesses this liquid crystal orientation film.
Embodiment
" acrylate copolymer that the tilt angle representative element is arranged "
Below, the present invention is described in detail.Aligning agent for liquid crystal of the present invention contains polymkeric substance with the represented repetitive of above-mentioned formula (1) (below, be also referred to as " acrylate copolymer that the tilt angle representative element is arranged ").Electrical characteristics such as the tilt angle expression power that aligning agent for liquid crystal of the present invention can be controlled liquid crystal orientation film by the structure choice and the content thereof of the represented repetitive of above-mentioned formula (1), voltage retention.
In above-mentioned formula (1), R 1It is hydrogen atom; Halogen atom; Can have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～30 1 valency alkyl; Or the polar group of 1 valency.
As halogen atom, can enumerate for example fluorine atom, chlorine atom and bromine atoms.
As carbon number is 1～30 1 valency alkyl, can enumerate for example alkyl such as methyl, ethyl, propyl group; Naphthenic base such as cyclopentyl, cyclohexyl; Alkenyl such as vinyl, allyl; Alkylidene such as ethylidene, propylidene; Aromatic groups such as phenyl, naphthyl, anthryl, xenyl, fluorenyl etc.Hydrogen atom on the strong carbon atom that closes in these groups can be by replacements such as halogen atom such as for example fluorine, chlorine, bromine and cyano group.
In addition, above-mentioned replacement or the 1 valency alkyl that does not have a replacement can directly be good for and be closed on the main polymer chain skeleton, perhaps can be good for by linking group and close.As above-mentioned linking group, can enumerate linking group (for example, carbonyl (CO-), carbonyl oxygen base (COO-), oxygen carbonyl (OCO-), the sulfonyl (SO that for example contains oxygen atom, nitrogen-atoms, sulphur atom or silicon atom 2-), sulfonyloxy (SO 2-O-), oxygen sulfonyl (O-SO 2-), ehter bond (O-), thioether bond (S-), imino group (NH-), amido link (NHCO-), siloxane bond (Si (R) 2O-) (in the formula, R is alkyl such as methyl, ethyl); The perhaps group that these moiety combinations are formed by connecting more than 2 kinds.And then, when above-mentioned replacement or the 1 valency alkyl that does not have a replacement are naphthenic base or aromatic group, above-mentioned linking group can be carbon number be 1～10 divalent alkyl (for example-(CH 2) mThe represented alkylidene of-(in the formula, m is 1～10 integer)).
As 1 valency polar group, for example can enumerate hydroxyl, cyano group, nitro, acylamino-, imino group (=NH), three organic siloxies, three Organosilyls, amino, acyl group, alcoxyl silicyl, sulfonic group (SO 3H), sulfino (SO 2H) and carboxyl etc.
More specifically, as three organic siloxies, can enumerate for example trimethylsiloxy, silicohetane alcoxyl base etc.; As three Organosilyls, can enumerate for example trimethyl silyl, triethylsilyl etc.; As amino, can enumerate for example secondary amino group and uncle's amino etc.; As the alcoxyl silicyl, can enumerate for example trimethoxysilyl, triethoxysilyl etc.
In addition, R 2Be that hydrogen atom, carbon number are 1～50 alkyl or the group that contains fluorine atom.As carbon number is 1～50 alkyl or the group that contains fluorine atom, can enumerate for example branched-chain alkyl such as straight chained alkyl such as methyl, ethyl, propyl group, dodecyl, n-octadecane base and 2-ethylhexyl; Naphthenic base such as cyclopentyl, cyclohexyl; Group with aliphatics condensation polycyclic formula structures such as steroidal compounds skeletons; Alkenyl such as vinyl, allyl; Alkylidene such as ethylidene, propylidene; The group that hydrogen atom on aromatic group such as phenyl, naphthyl, anthryl, xenyl, fluorenyl and the strong carbon atom that closes in these groups can be replaced by halogen atom such as fluorine, chlorine, bromine or trifluoromethyl, trifluoromethoxy etc. etc.The selection of these groups can be selected by the necessary tilt angle expression power of liquid crystal orientation film.For example, when using as vertical-tropism agent, R 2The substituting group that preferred volume is big, for example preferably using carbon number is the group that is formed by connecting of straight chain shape more than 6 or branched-chain alkyl, a plurality of naphthenic base and aromatic group, the group with aliphatics condensation polycyclic formula structures such as steroidal compounds skeletons, from stably showing the viewpoint of high tilt angle, especially preferably has the group of steroidal compounds skeleton.
In the formula (1), A 1Be that singly-bound or carbon number are 1～10 alkylidene.A 2, A 3And A 4Independent separately, be from singly-bound, ehter bond (O-), carbonyl (CO-), carbonyl oxygen base (COO-), the oxygen carbonyl (OCO-), amido link (NHCO-,-CONH-), thioether bond (S-) or carbon number be the group of selecting 1～10 the alkylidene; B 1, B 2And B 3Independent separately, be singly-bound, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-cyclohexylidene, 1,3-cyclohexylidene, 1,4-cyclohexylidene or piperidines-1,4-two bases.
The represented preferred construction of formula (1) is represented with following formula (3).
(in the formula, R 6Definition and the R of formula (1) 1Definition identical.)
As the represented structure of formula (1), can enumerate the concrete example that goes out for example shown below.
Figure S2008100094554D00061
Figure S2008100094554D00071
Figure S2008100094554D00081
These are as in the cited structure of the concrete example of above-mentioned formula (1), from the viewpoint of the balance excellence of electrical characteristics such as the expression power of tilt angle and voltage retention, special preferred formula (1-3) and the represented structure of formula (1-4).
In addition, the acrylate copolymer with tilt angle representative element of the present invention preferably further contains the represented structure with cyclic ether structure of following formula (2).Cyclic ether structure in the represented structure of formula (2) can be carried out heat treated (afterwards baking and banking up with earth) after the alignment films and carry out the heat cross-linking reaction by forming, thereby thermotolerance, anti-liquid crystal liquid crystal property (solvent resistance), film density are improved, can give alignment films thus to reduce the effect of foreign ion diffusion.In addition, by these effects, liquid crystal panel is applied the stress of light and heat or makes liquid crystal panel drive, can not take place the reduction of voltage retention or the liquid crystal orientation film of burning screen for a long time even can obtain.
Figure S2008100094554D00091
(in the formula, R 3It is hydrogen atom; Halogen atom; Can have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～30 alkyl; Or the polar group of 1 valency.R 4It is the organic group of singly-bound or divalent.R 5Be that carbon number is 2～10 the group with cyclic ether structure.)
In above-mentioned formula (2), as R 3Concrete example, can illustration and above-mentioned formula (1) in R 1Same group.
R 4Be the organic group of singly-bound or divalent, preferred carbon number is 1～10 divalent alkyl, for example-and (CH 2) n-(in the formula, n is 1～10 integer).
As R 5The cyclic ether structure of expression, preferred carbon number be 2～10 have the reactive group of heat cross-linking, preference such as epoxy radicals, an oxa-cyclobutyl.Wherein, from reactive excellent viewpoint, preferred especially epoxy radicals.
Concrete example as the represented repetitive of above-mentioned formula (2), can enumerate the represented structural unit of following formula (4), for example with glycidyl acrylate, glycidyl methacrylate, acrylic acid-3,4-epoxy butyl ester, methacrylic acid-3,4-epoxy butyl ester, acrylic acid-6,7-epoxy heptyl ester, methacrylic acid-6,7-epoxy heptyl ester, α-Yi Jibingxisuan-6,7-epoxy heptyl ester etc. have the free-radical polymerised structural unit that contains ring-type ether unsaturated polymerizable compound and obtain.
Figure S2008100094554D00101
(in the formula, R 7Represent hydrogen atom independently of one another; Halogen atom; Can have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～30 alkyl; Or the polar group of 1 valency, and a is 1～10 integer.)
In formula (4), as R 7Concrete example, can illustration and above-mentioned formula (1) in R 1Same group.
Wherein, the film density height of alignment films after the heat curing, the viewpoint of the reliability of the excellent electrical characteristics of performance, electrical characteristics is set out, especially preferably the structural unit that glycidyl acrylate, glycidyl methacrylate polymerization are obtained.
And then, in order to promote the cross-linking reaction of the cyclic ether structure that above-mentioned formula (2) is represented, preferably in the acrylate copolymer with tilt angle representative element of the present invention, contain repetitive with hydroxy-acid group, as concrete example, preferably will have free-radical polymerised carboxy-containing acid group's compound polymerization and the structural unit that obtains.As structural unit with hydroxy-acid group, the repetitive that dicarboxylic acid precursor such as repetitive that can the represented monocarboxylic acid precursor polymeric of for example following formula of illustration (5) forms or maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid is polymerized.
Figure S2008100094554D00102
(in the formula, R 8Represent hydrogen atom independently of one another; Halogen atom; Can have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～30 alkyl; Or the polar group of 1 valency.)
In formula (5), as R 8Concrete example, can illustration and above-mentioned formula (1) in R 1Same group.
Wherein, the film density height of alignment films after the heat curing, the viewpoint of the reliability of the excellent electrical characteristics of performance, electrical characteristics is set out, especially preferably the structural unit that acrylic acid, methacrylic acid, crotonic acid polymerization are obtained.
In order to make the acrylate copolymer with tilt angle representative element of the present invention obtain thermotolerance, also preferably has the structure that following formula (6) and (7) are represented separately.
Figure S2008100094554D00111
(in the above-mentioned formula, R 9Be to have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～50 alkyl.R 10And R 11Independent separately, the expression hydrogen atom; Halogen atom; Can have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～30 alkyl; Or the polar group of 1 valency.)
In formula (6), R 9Be to have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, the carbon number that replaces or do not have a replacement is 1～50 alkyl, as its concrete example, aromatic group or naphthenic base such as cyclopentyl, cyclohexyl such as preferred phenyl, naphthyl, anthryl, fluorenyl, wherein, preferred especially phenyl, cyclohexyl.
In formula (7), R 10And R 11Independent separately, the expression hydrogen atom; Halogen atom; Can have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～30 alkyl; Or the polar group of 1 valency.As its concrete example, can illustration and above-mentioned formula (1) in R 1Same group.As the represented concrete example of formula (7), preferably with vinyl aromatic compounds polymerizations such as alpha-olefins such as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and styrene, 4-vinyl biphenyl, 2-vinyl biphenyl, 1-vinyl naphthalene, 2-vinyl naphthalene, α-Jia Jibenyixi and the structural unit that obtains.Wherein, the structural unit that especially preferably styrene polymerization is obtained.
As making the solvent that uses in the acrylate copolymer of tilt angle representative element that has of the present invention, can enumerate for example alcohol, ether, glycol ethers, ethylene glycol alkyl ether acetic acid esters, diethylene glycol alkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, aromatic hydrocarbon, ketone, ester etc.
As their concrete example, can enumerate respectively: as alcohol, for example methyl alcohol, ethanol, phenmethylol, 2-phenylethanol, 3-phenyl-1-propyl alcohol etc.; As ether tetrahydrofuran, two n-pentyl ethers etc. are arranged; As glycol ethers, for example glycol monoethyl ether, ethylene glycol monoethyl ether etc.; As ethylene glycol alkyl ether acetic acid esters, for example methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate etc.; As the diethylene glycol alkyl ether, for example diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether etc.; As propylene-glycol monoalky lether, for example propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether etc.; As propylene glycol alkyl ether propionic ester, for example methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester etc.; As propylene glycol alkyl ether acetic acid ester, for example methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters etc.; As aromatic hydrocarbon, for example toluene, dimethylbenzene etc.; As ketone, for example methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone, diisobutyl ketone etc.; As ester, methyl acetate for example, ethyl acetate, propyl acetate, butyl acetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid propyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid propyl ester, the ethoxyacetic acid butyl ester, the propoxyl group methyl acetate, propoxyl group ethyl acetate, the propoxyl group propyl acetate, the propoxyl group butyl acetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, esters such as 3-butoxy butyl propionate.
Wherein, preferred ethylene glycol alkyl ether acetic acid esters, diethylene glycol alkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, preferred especially diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether, methyl proxitol, propylene glycol ethylether, methyl proxitol acetate, 3-methoxypropionic acid methyl esters.
As making the polymerization initiator that uses in the acrylate copolymer of tilt angle representative element that has of the present invention, generally can use as the known polymerization initiator of radical polymerization initiator.For example can enumerate 2,2 '-azobis isobutyronitrile, 2,2 '-azo is two-(2, the 4-methyl pentane nitrile), 2, and 2 '-azo is two-azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, the peroxidating pivalic acid tert-butyl ester, 1,1 '-two-organic peroxides such as (tert-butyl hydroperoxide) cyclohexane; And hydrogen peroxide.When using superoxide as radical polymerization initiator, can with reductive agent-rise and use superoxide as the oxidation-reduction type initiating agent.
In the manufacturing of the acrylate copolymer with tilt angle representative element of the present invention, can use molecular weight to adjust agent in order to adjust molecular weight.As its concrete example, can enumerate halogenated hydrocarbons such as chloroform, carbon tetrabromide; Mercaptan such as positive hexyl mercaptan, n-octyl mercaptan, n-dodecane mercaptan, uncle's dodecyl mercaptans, thioglycol; Xanthates such as sulfuration dimethyl yellow ortho esters, dithiodiisopropyl xanthate; Terpinolene, α-Jia Jibenyixierjuwu etc.
Acrylate copolymer with tilt angle representative element of the present invention can control to desirable molecular weight by suitable adjustment polymerizing condition, and described polymerizing condition for example solvent species, solvent/monomer is packed into than the kind of (weight ratio), polymerization temperature, initiator type and addition thereof, chain-transferring agent and addition thereof etc.The weight-average molecular weight that is converted into polystyrene (hereinafter referred to as " Mw ") preferred 2 * 10 that the acrylate copolymer with tilt angle representative element that uses among the present invention is measured with gel permeation chromatography (GPC) 3～1 * 10 6, more preferably 5 * 10 3～5 * 10 5, preferred especially 1 * 10 4～4 * 10 5If Mw is less than 2 * 10 3Then can't form alignment films with desired thickness owing to can not get suitable viscosity when making alignment agent, and, following problem is arranged sometimes: the poor heat resistance of alignment films, thus voltage retention reduces, panel burns the main cause of shielding because of low molecular compound stripping panel characteristics variation becomes.On the other hand, if surpass 1 * 10 6, viscosity is too high when then making alignment agent, has problems aspect coating sometimes.In addition, molecular weight distribution (hereinafter referred to as " Mw/Mn ", Mn represents to be converted into the number-average molecular weight of polystyrene) is preferred below 20.0, and is more preferably below 15.0, preferred especially below 10.0.By Mw/Mn is reduced, the coating excellence of alignment agent can obtain can not to take place the alignment films of the panel characteristics variation problem that causes because of above-mentioned low molecular compound stripping etc.
Aligning agent for liquid crystal of the present invention can be used as the aligning agent for liquid crystal of variety of ways such as VA mode, TN mode, IPS mode, OCB mode, FFS mode, the alignment agent that can use as vertical orientated (VA) mode well.Preferred 4～60 moles of % of content of the repetitive that becomes the tilt angle representative element of above-mentioned formula (1) expression when using as the VA alignment agent, more preferably 5～40 moles of %, preferred especially 6～30 moles of %.If the content of the tilt angle representative element of formula (1) expression is less than 4 moles of %, then can't show sufficient liquid crystal vertical-tropism, if more than 60 moles of % then the printing variation, perhaps take place relevant sometimes easily and burning that discover is shielded with residual DC.
In the present invention, in order to give liquid crystal orientation film indeclinable high reliability of voltage retention and when making the long-time stress that drives or apply for a long time heat, light of liquid crystal panel, preferably make the repetitive that contains above-mentioned formula (2) expression in the acrylate copolymer with tilt angle representative element with cyclic ether structure with high initial voltage conservation rate.The content of the repetitive with cyclic ether structure of above-mentioned formula (2) expression can contain for example 5～50 moles of %, preferred 15～45 moles of %, preferred especially 20～40 moles of %.The content of the repetitive with cyclic ether structure of above-mentioned formula (2) expression is during less than 5 moles of %, can't fully obtain high reliability etc. and be the effect that the cross-linking reaction of purpose is brought with voltage retention, during greater than 50 moles of %, unreacted functional group is residual, becomes the reason that makes variation such as electrical characteristics sometimes.And then, for the cross-linking reaction of the cyclic ether structure that promotes above-mentioned formula (2) expression, in the acrylate copolymer with tilt angle representative element of the present invention, can suitably contain the repetitive with hydroxy-acid group of above-mentioned formula (5) expression.Preferably contain and the repetitive with cyclic ether structure of above-mentioned formula (2) the expression repetitive with hydroxy-acid group of above-mentioned formula (5) expression of equimolar amounts almost, can contain for example 5～50 moles of %, preferred 15～45 moles of %, preferred especially 20～40 moles of %.
In order to give the thermotolerance of the acrylate copolymer with tilt angle representative element, the structural unit that can suitably use above-mentioned formula (6) and above-mentioned formula (7) to represent separately, preferably contain the equimolar amounts degree separately, be suitable for the repetitive with hydroxy-acid group of the repetitive with cyclic ether structure of the repetitive that becomes the tilt angle representative element from the polymkeric substance total amount, deduct above-mentioned formula (1) expression, above-mentioned formula (2) expression and above-mentioned formula (5) expression and the part that obtains.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention, preferably in organic solvent, be dissolved with the structural unit with above-mentioned formula (1) expression polymkeric substance other adjuvants at least a above and interpolation as required and constitute.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate the illustrated identical solvent of organic solvent that uses in the synthetic reaction as the acrylate copolymer of representing in above-mentioned formula (1) with tilt angle representative element.And then, from the viewpoint of printing, preferably contain boiling point sometimes and be the solvent more than 160 ℃.As these solvents, can examples example such as N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, dimethyl sulfoxide, gamma-butyrolacton, tetramethylurea, 6-methyl phosphonic triamide, metacresol, xylenol, phenol, diacetone alcohol, ethylene glycol monobutyl ether (butyl cellosolve), propylene carbonate, diethylene glycol diethyl ether.Particularly preferred solvent composition is the composition that above-mentioned solvent is combined, and is that solid constituent is not separated out in aligning agent for liquid crystal and the surface tension of aligning agent for liquid crystal is the composition of 25～40mN/m scope.
Solid component concentration in the aligning agent for liquid crystal of the present invention is considered viscosity, volatility waits and selects, and for example is 1～50 weight %, preferred 2～40 weight %, the scope of preferred especially 3～30 weight %.That is, aligning agent for liquid crystal of the present invention is applied in substrate surface, thereby becomes filming of liquid crystal orientation film, but solid component concentration is difficult to obtain good liquid crystal orientation film during less than 1 weight % because of this thickness of filming is too small.When solid component concentration surpassed 50 weight %, the thickness of filming was excessive and be difficult to obtain good liquid crystal orientation film, and in addition, the viscosity of aligning agent for liquid crystal increases and coating characteristics is poor sometimes, thereby can not get the liquid crystal orientation film of inner evenness excellence.
It should be noted that, the coating process that the scope of particularly preferred solid component concentration is used when aligning agent for liquid crystal is applied to substrate and difference, more particularly, in order to obtain being suitable for the aligning agent for liquid crystal viscosity of various coating processes, must be adjusted to suitable solid component concentration.For example, when adopting spin-coating method, alignment agent viscosity is preferably adjusted to the scope of 3.0～10.0mPas.When adopting print process, preferably alignment agent viscosity is adjusted to the scope of 12～50mPas.When adopting ink-jet method, preferably alignment agent viscosity is adjusted to the scope of 3～15mPas.
In addition, the temperature when modulating aligning agent for liquid crystal of the present invention, preferred 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
Aligning agent for liquid crystal of the present invention is after freezing preservation, fully thaw after room temperature, the size of measuring with particle collector be the number (with the value of particle sensor mensuration in the liquid of RION (strain) system) of the particle foreign matter more than the 1.0 μ m be preferably 20/below the ml, more preferably 10/below the ml, be preferably especially 5/below the ml.Size be the above particle foreign matter of 1.0 μ m outnumber 20/ml the time, in aligning agent for liquid crystal, produce the agglutination body of this foreign matter, this agglutination body becomes the reason of the pin hole of liquid crystal orientation film or shrinkage cavity etc.
The adjuvant that can contain other in the aligning agent for liquid crystal of the present invention as required.As adjuvant, for example, can enumerate polyamic acid from the viewpoint of improvement residual DC, anti-burning screen property; From the viewpoint of improvement voltage retention, can enumerate imide amination polymer; From static characteristic, improve cohesiveness to substrate surface, and, can enumerate compound that contains functional silanes or the low molecular compound that in molecule, has 2 above epoxy radicals from improving the viewpoint of voltage retention.
As polyamic acid that in aligning agent for liquid crystal of the present invention, can add as required and imide amination polymer, can enumerate and make tetracarboxylic dianhydride and diamine compound generation polyaddition reaction and synthetic polyamic acid and above-mentioned polyamic acid carried out imidizate and the imide amination polymer that obtains.These materials can contain a kind of separately, also can contain more than 2 kinds.Here comprise the part imide polymer that above-mentioned polyamic acid part imidizate is formed in the said imide amination polymer and carry out the polymkeric substance that 100% imidizate forms, below, their general designations are made " imide amination polymer ".In addition, the preferred imidizate rate of imide amination polymer used herein is 10～100 moles of %, more preferably 20～95 moles of %, preferred especially 45～90 moles of %.At this, " imidizate rate " is meant, the acid imide number of repeating units is shared ratio in the sum of the amic acid repetitive of polymkeric substance and acid imide repetitive, represents with %.At this moment, a part that forms imide ring is that the material of different imide ring also is comprised in the acid imide number of repeating units.The concrete example of the imide amination polymer that carries out imidizate as the polyamic acid that can add with above-mentioned polyamic acid and obtain in aligning agent for liquid crystal of the present invention can enumerate making polyamic acid that at least a tetracarboxylic dianhydride who selects obtains with at least a diamine reactant of selecting and this polyamic acid is carried out the imide amination polymer that imidizate forms from following tetrabasic carboxylic acid acid dianhydride from following diamines; Described tetrabasic carboxylic acid acid dianhydride for example 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 5-(2,5-two oxa-s tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-two oxa-s-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-two oxa-s-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-two oxa-s-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 3,5,6-three carboxyls-2-carboxyl norbornane-2:3,5:6-dianhydride, dicyclo [3.3.0] octane-2,4,6, the 8-tetracarboxylic dianhydride, pyromellitic acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenylsulfone acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride; Described diamines is p-phenylenediamine (PPD) for example, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 9, two (4-aminophenyl) fluorenes of 9-, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-diamido-2,2 '-dimethyl diphenyl, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 1, two (amino methyl) cyclohexanes of 3-, 1, the 4-cyclohexane diamine, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexylamine), 3,3 '-(tetramethyl disiloxane-1,3-two bases) two (propylamine).Wherein, preferably make at least a tetracarboxylic dianhydride who is selected among the following tetracarboxylic dianhydride and be selected from polyamic acid that the diamine reactant in the following diamines forms and this polyamic acid carried out imidizate and the imide amination polymer that obtains; Described tetracarboxylic dianhydride is 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-two oxa-s-3-furyl)-naphtho-[1,2-c] furans-1,3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), pyromellitic acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride; Described diamines is a p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 2,7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 4,4 '-diamido-2,2 '-dimethyl diphenyl, 1, two (amino methyl) cyclohexanes of 3-.The cooperation ratio that these polyamic acids and imide amination polymer are represented with weight portion, preferably (the acrylate copolymer total amount with tilt angle representative element of the present invention): (total amount of polyamic acid and imide amination polymer)=10: 90～90: 10, more preferably 20: 80～80: 20, preferred especially 30: 70～70: 30.
As the compound that contains functional silanes, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, the 3-glycidoxy-propyltrimethoxy silane, two (oxidation the ethylidene)-3-TSL 8330s of N-, two (oxidation the ethylidene)-3-aminopropyltriethoxywerene werene of N-etc.When using these compounds that contain functional silanes, its cooperation ratio is with respect to polymkeric substance total amount 100 weight portions of the present invention, below preferred 2 weight portions, more preferably below 0.2 weight portion.
As the low molecular compound that in molecule, has 2 above epoxy radicals, can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, the glycerine diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, the two (N of 3-, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N, N ', N '-four glycidyl group-p-phenylenediamine (PPD) etc. are as preferred compound.When using these low molecular compounds that have 2 above epoxy radicals in molecule, its cooperation ratio is with respect to polymkeric substance total amount 100 weight portions of the present invention, preferred 1～60 weight portion, more preferably 5～40 weight portions, preferred especially 10～30 weight portions.
＜liquid crystal display cells 〉
Liquid crystal display cells of the present invention for example can be made by the following method.
(1) in the one side of the substrate that is provided with the nesa coating that forms pattern, is coated with aligning agent for liquid crystal of the present invention, follows, form by the heating coated face and film by for example methods such as rolling method, spin-coating method, print process, ink-jet method.At this,, can use for example glass such as sheet glass, soda-lime glass as substrate; The transparency carrier that constitutes by plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, ester ring type polyolefin.Nesa coating as being arranged on the substrate one side can use by tin oxide (SnO 2) constitute NESA film (U.S. PPG register of company trade mark), by indium oxide-tin oxide (In 2O 3-SnO 2) the ITO film that constitutes etc.The pattern of these nesa coatings forms can adopt photo-engraving process, use the method for mask in advance.In reflecting electrode, can use metals such as Al, Ag, perhaps contain the alloy of these metals etc., as long as but have sufficient reflectivity, just be not limited to these.During the coating of liquid crystalline alignment agent, in order further to improve the adhesiveness of substrate surface and nesa coating, reflecting electrode and liquid crystal orientation film, can be in advance on this surface of substrate coating contain functional silanes compound, contain the compound of functionality titanium etc.Behind the coating of liquid crystalline alignment agent, the vertical liquid of the alignment agent that is coated with in order to prevent etc. impose usually and preheat (baking and banking up with earth in advance).Bake and bank up with earth preferred 30～300 ℃ of temperature in advance, more preferably 40～200 ℃, preferred especially 50～150 ℃., solvent fully removed, when polymkeric substance contains the cyclic ether structure,, implement to burn till (afterwards baking and banking up with earth) operation in order to promote the heat cross-linking reaction of this functional group thereafter.This burns till preferred 80～300 ℃ of (afterwards baking and banking up with earth) temperature, more preferably 120～250 ℃.Like this, aligning agent for liquid crystal of the present invention is removed organic solvent after by coating and can be formed and become filming of liquid crystal orientation film.Preferred 0.001～1 μ m of the thickness of formed liquid crystal orientation film, more preferably 0.005～0.5 μ m.
(2) for the film coated surface that forms as required, with circumvolution the roller of the cloth that is made of for example fibers such as nylon, regenerated fiber, cotton thread is arranged, carry out friction treatment in the certain orientation wiping.Thus, can obtain the alignment capability and the controlled liquid crystal orientation film of tilt angle of liquid crystal molecule.In addition, except the method for carrying out friction treatment, can also be applied in the method that film coated surface irradiation polarized ultraviolet is controlled alignment capability.Moreover the micropowder (foreign matter) that produces when removing friction treatment etc. and make film coated surface form clean state is preferably with formed liquid crystal orientation films of washing such as isopropyl alcohol and/or pure water.In addition, by to imposing following processing, can improve the visual field characteristic of liquid crystal display cells by the film formed liquid crystal orientation film of liquid crystal aligning of the present invention; Described processing is for example opened flat 6-222366 communique, spy the spy and is opened and disclose processing such, that tilt angle is changed by the part irradiation ultraviolet radiation in the flat 6-281937 communique, perhaps the spy open disclose in the flat 5-107544 communique such, form etchant resist on ground, liquid crystal orientation film top through friction treatment, with direction that formerly friction treatment is different on carry out friction treatment after, remove above-mentioned etchant resist, make the processing of the alignment capability variation of liquid crystal orientation film.
(3) as above make 2 substrates that form liquid crystal orientation film like that, 2 plate bases are situated between by gap (cell gap) configuration relatively, make the frictional direction of each liquid crystal orientation film form quadrature or antiparallel, with the fit periphery of 2 plate bases of sealant, in the cell gap that marks off by substrate surface and sealant, inject filling liquid crystal, filling orifice is sealed constitute liquid crystal cells.So, at the outside surface of liquid crystal cells, promptly constitute the outside surface side configuration polaroid of each substrate of liquid crystal cells, obtain liquid crystal display cells thus.
At this,, can use and for example contain hardening agent and as epoxy resin of the alumina balls of sept etc. as sealant.
As liquid crystal, can enumerate nematic crystal and smectic crystal.Wherein, preferred nematic crystal, for example azomethine class liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, two  alkanes liquid crystal, bicyclooctane class liquid crystal, cube alkanes liquid crystal etc.In addition, for example can also add the chirality agent of selling as cholesteric crystals such as courage steroid chloride, cholesteryl pelargonate, cholesteryl carbonic esters, with trade name " C-15 ", " CB-15 " (MERCK corporate system) in these liquid crystal waits and uses.And then, can also use taking off siloxy benzal base-strong dielectricity liquid crystal such as amino-2-methyl butyl cinnamic ester.
In addition, as the polaroid that is fitted in the liquid crystal cells outside surface, make the polyvinyl alcohol (PVA) stretch orientation, the polarizing coating that is called the H film that will be absorbed with iodine simultaneously is with the polaroid of cellulose acetate diaphragm clamping or the polaroid that itself is made of the H film.
As above, according to liquid crystal orientation film of the present invention, can obtain to obtain the aligning agent for liquid crystal of following liquid crystal orientation film, even described liquid crystal orientation film shows good coating and liquid crystal panel is applied the stress of light, heat or makes long-time reduction and the burning screen that voltage retention also can not take place that drive of liquid crystal panel.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not limited to these embodiment.The molecular weight determination of the polymkeric substance in embodiment and the comparative example, the coating of aligning agent for liquid crystal, granule number are measured, the reliability determination of tilt angle, voltage retention and the voltage retention of the liquid crystal display cells of made is estimated by the following method.
[weight-average molecular weight and molecular weight distribution]
Use gel permeation chromatography (GPC, eastern Cao (strain) system, trade name: 3 of HLC-8020/ chromatographic columns: eastern Cao (strain) system, trade name: TSK guardcolum α, TSK gel α-M, TSK gel α-2500), use dimethyl formamide (DMF: in the DMF of 3L, be added with the material that lithium bromide monohydrate 9.4g, phosphatase 11 .7g form) as solvent, measure the weight-average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) that are converted into polystyrene.Mn is a number-average molecular weight.
[coating of aligning agent for liquid crystal]
Use JET-CM continuous ink jet printing machine (discipline state skill is ground industry (strain) system), on the ito substrate of ITO film of thickness 200nm, wide 20 μ m, carry out the coating of aligning agent for liquid crystal with the liquid measure that forms dry film thickness 60nm with the interval formation striated of 100 μ m.The aligning agent for liquid crystal coated substrates of gained was baked and banked up with earth (on hot plate) 1 minute in advance under 80 ℃, under 200 ℃, burn till 60 minutes then (in cleaning oven, under the nitrogen environment) after, periphery, central portion with 20 times microscopic examination liquid crystal orientation films, do not have the situation of crawling to be judged as " well ", the situation that observes pin hole, crawling (thickness is unequal) is judged as " bad ".The result who estimates coating for each alignment agent is summarised in the table 1.
[granule number]
(RION (strain) system, KL-20A), measuring size for the 10ml aligning agent for liquid crystal is granule number 2 times more than the 1.0 μ m, is granule number more than the 1.0 μ m with its mean value as size to use particle sensor in the liquid.Under the condition of optical source wavelength 780nm, sample pumping velocity 10ml/min, measure.
[tilt angle]
Use the strong strength detection device OMS-J3 that closes of central smart machine (strain), carry out the mensuration of the tilt angle of liquid crystal display cells.
[voltage retention]
Liquid crystal display cells is applied after the voltage of 5V with the interval of the application time of 60 microseconds, 167 microseconds, in the voltage retention of measuring under 60 ℃ the environment after impressed voltage is removed 167 microseconds.Determinator uses the VHR-1 of (strain) Toyo Technica system.Voltage retention is in being judged as more than 99.9% " well ", other be judged as " bad ".
[reliability of voltage retention]
The liquid crystal display cells of made was preserved 7 days in 100 ℃ baking oven, imposed thermal stress.Measure the voltage retention before and after the thermal stress, the absolute value of voltage retention variable quantity is 0.5% with interior being judged as " well ", other be judged as " bad ".
Synthesis example 1 (synthesizing of tilt angle representative element precursor)
β-cholesterol 80g is dissolved in the dehydration tetrahydrofuran (THF) of 800ml, adds after the triethylamine 27.2g, drip methacrylic chloride 35.6g lentamente, stirred 3 hours down in room temperature (r.t.).After reaction finishes,, add chloroform 400ml after removing THF by decompression distillation by removing by filter triethylamine hydrochloride.Wash this solution, behind the dried over mgso organic layer, remove chloroform by decompression distillation.Then, utilize ethanol to carry out recrystallization, obtain the methacrylic acid courage steroid ester 54g (yield: 57.4%) of the white solid represented in the above-mentioned reaction equation.
Synthesis example 2 (synthesizing of polymer A)
Stirring rod is being installed, three keratotic plugs, pack in the four-hole boiling flask of thermometer as the methacrylic acid courage steroid ester 15.16g (0.0332 mole) that in synthesis example 1, obtains of monomer, glycidyl methacrylate 12.8g (0.09 mole), methacrylic acid 7.2g (0.0836 mole), styrene 7.2g (0.0691 mole), N-cyclohexyl maleimide 7.2g (0.0402 mole), and then interpolation is as the diethylene glycol ethyl-methyl ether 52.8g of solvent, as 2 of polymerization initiator, two (2, the 4-methyl pentane nitrile) 2.24g of 2 '-azo, α-Jia Jibenyixierjuwu 0.96g as chain-transferring agent.It was flowed down bubbling about 10 minutes at nitrogen, after carrying out the nitrogen displacement in the system, under nitrogen environment, reacted 5 hours down, obtain having the polymer A of tilt angle representative element at 70 ℃.By the molecular weight of GPC mensuration polymer A, the result is Mw=96,000, and Mw/Mn=7.87 does not see the peak that causes because of residual monomer.The monomer hypothesis of packing in this polymer solution all changes into polymer A, and directly dilution is used to make aligning agent for liquid crystal of the present invention.
Synthesis example 3 (synthesizing of polymer B)
Except using N-phenylmaleimide 7.2g (0.0416 mole) to replace the N-cyclohexyl maleimide, fully similarly operate with synthesis example 2, obtain having the polymer B of tilt angle representative element.By the molecular weight of GPC mensuration polymer B, the result is Mw=108,000, and Mw/Mn=6.51 does not see the peak that causes because of residual monomer.The monomer hypothesis of packing in this polymer solution all changes into polymer B, and directly dilution is used to make aligning agent for liquid crystal of the present invention.
Synthesis example 4 (polymkeric substance C's is synthetic)
Methacrylic acid courage steroid ester 30.0g (0.0657 mole) packs into, glycidyl methacrylate 12.0g (0.0844 mole), methacrylic acid 7.0g (0.0813 mole), styrene 4.5g (0.0432 mole), N-cyclohexyl maleimide 7.2g (0.0402 mole), and then interpolation is as the diethylene glycol ethyl-methyl ether 65.0g of solvent, as 2 of polymerization initiator, 2 '-azo two (2, the 4-methyl pentane nitrile) 2.74g, α-Jia Jibenyixierjuwu 1.18g as chain-transferring agent, in addition, fully similarly operate with synthesis example 2, obtain having the polymkeric substance C of tilt angle representative element.By the molecular weight of GPC mensuration polymkeric substance C, the result is Mw=79,000, and Mw/Mn=7.31 does not see the peak that causes because of residual monomer.The monomer hypothesis of packing in this polymer solution all changes into polymkeric substance C, and directly dilution is used to make aligning agent for liquid crystal of the present invention.
Synthesis example 5 (polymkeric substance D's is synthetic)
Methacrylic acid courage steroid ester 10.0g (0.0219 mole) packs into, glycidyl methacrylate 15.0g (0.1055 mole), methacrylic acid 9.0g (0.1045 mole), styrene 2.5g (0.0240 mole), N-cyclohexyl maleimide 4.0g (0.0223 mole), and then interpolation is as the diethylene glycol ethyl-methyl ether 43.0g of solvent, as 2 of polymerization initiator, 2 '-azo two (2, the 4-methyl pentane nitrile) 1.83g, α-Jia Jibenyixierjuwu 0.78g as chain-transferring agent, in addition, fully similarly operate with synthesis example 2, obtain having the polymkeric substance D of tilt angle representative element.By the molecular weight of GPC mensuration polymkeric substance D, the result is Mw=125,000, and Mw/Mn=9.54 does not see the peak that causes because of residual monomer.The monomer hypothesis of packing in this polymer solution all changes into polymkeric substance D, and directly dilution is used to make aligning agent for liquid crystal of the present invention.
Compare synthesis example 1 (polymkeric substance E's is synthetic)
In the four-hole boiling flask that stirring rod, three keratotic plugs, thermometer are installed, pack into as glycidyl methacrylate 40.0g (0.2814 mole), methacrylic acid 20.0g (0.2323 mole), styrene 20.0g (0.192 mole), the N-cyclohexyl maleimide 20.0g (0.1116 mole) of monomer, and then add as the diethylene glycol ethyl-methyl ether 132.0g of solvent, as 2 of initiating agent, two (2, the 4-methyl pentane nitrile) 7.00g of 2 '-azo, as the α-Jia Jibenyixierjuwu 3.00g of chain-transferring agent.It was flowed down bubbling about 10 minutes at nitrogen, after carrying out the nitrogen displacement in the system, under nitrogen environment, reacted 5 hours down, obtain polymkeric substance E at 70 ℃.By the molecular weight of GPC mensuration polymkeric substance E, the result is Mw=91,000, and Mw/Mn=11.86 does not see the peak that causes because of residual monomer.The monomer hypothesis of packing in this polymer solution all changes into polymkeric substance E, and directly dilution is used to make aligning agent for liquid crystal of the present invention.
Compare synthesis example 2 (polymerization F's is synthetic)
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride 20.8381g (0.0930 mole), be dissolved among the N-N-methyl-2-2-pyrrolidone N-140g, 60 ℃ of reactions 5 hours down as the p-phenylenediamine (PPD) 9.2129g (0.0852 mole) and the represented diamines 4.9490g (0.0095 mole) of above-mentioned formula (a) of diamine compound.Then, reaction solution is injected in the excessive methyl alcohol, makes reaction produce the thing precipitation.Then, use methanol wash, under reduced pressure, obtain polyamic acid 31g thus in 40 ℃ of dryings 24 hours.The polyamic acid 30g of gained is dissolved among the N-N-methyl-2-2-pyrrolidone N-400g, add pyridine 6.3g and acetic anhydride 8.1g, 110 ℃ of following dehydration closed-loops 4 hours, with above-mentionedly similarly precipitate, washing, drying under reduced pressure, obtain Mw=111,000, Mw/Mn=5.23, the imidizate rate is 51% imide amination polymer F 26g.
Compare synthesis example 3 (polymerization G's is synthetic)
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride 19.8781g (0.0887 mole), the p-phenylenediamine (PPD) 6.8285g (0.0631 mole) as diamine compound, diaminodiphenyl-methane 3.5771g (0.0180 mole) and the represented diamines 4.7162g (0.0090 mole) of above-mentioned formula (a) are dissolved among the N-N-methyl-2-2-pyrrolidone N-140g, react 4 hours down at 60 ℃.Then, reaction solution is injected in the excessive methyl alcohol, makes reaction produce the thing precipitation.Then, use methanol wash, under reduced pressure, obtain polyamic acid 32.8g thus in 40 ℃ of dryings 24 hours.The polyamic acid 30g of gained is dissolved among the N-N-methyl-2-2-pyrrolidone N-400g, add pyridine 12.0g and acetic anhydride 15.5g, 110 ℃ of following dehydration closed-loops 4 hours, with above-mentionedly similarly precipitate, washing, drying under reduced pressure, obtain Mw=92,000, Mw/Mn=4.19, the imidizate rate is 79% imide amination polymer G 25g.
Embodiment 1
In the polymer A solution that synthesis example 2 obtains, further add diethylene glycol methyl ethyl ether, make the aligning agent for liquid crystal that the total solid constituent concentration is 3.5 weight %.After it is fully stirred, use the filtrator of aperture 0.2 μ m to filter, obtain aligning agent for liquid crystal of the present invention.The gained aligning agent for liquid crystal preserved 7 days in-15 ℃ freezer after, this alignment agent is thawed to room temperature, implement mensuration, the coating test of granule number.The results are shown in table 1.In addition, following making VA type liquid crystal display cells carries out the reliability evaluation of tilt angle, voltage retention and voltage retention.Use spinner with aligning agent for liquid crystal of the present invention be applied to be located at the glass substrate one side by on the film formed nesa coating of ITO, on hot plate, under 80 ℃, carry out 1 minute preparation drying, then in cleaning oven (nitrogen environment), under 200 ℃, burnt till 1 hour, and made the transparent electrode substrate of thickness 60nm thus with liquid crystal orientation film.Then, each outer rim at the liquid crystal orientation film of the above-mentioned liquid crystal orientation film coated substrates of having of a pair of transparency electrode/transparent electrode substrate, after coating was mixed with the epoxy adhesive of diameter 5.5 μ m alumina balls, overlapping pressing made that the liquid crystal aligning face is relative, makes adhesive cures.Then, by liquid crystal injecting port between substrate, fill negative type liquid crystal (the MERCK corporate system, MLC-2038) after, with the acrylic acid light-curing adhesive liquid crystal injecting port is sealed, the two sides applying polaroid in the substrate outside is made VA type liquid crystal display cells.Estimate the reliability of tilt angle, voltage retention and voltage retention for the VA type liquid crystal display cells of gained, the results are shown in table 1.
Embodiment 2
Except using the polymer B solution that in synthesis example 3, obtains to replace the polymer A solution, obtain aligning agent for liquid crystal of the present invention and VA type liquid crystal display cells similarly to Example 1.Estimate the reliability of granule number, coating, tilt angle, voltage retention and voltage retention, the results are shown in table 1.
Embodiment 3
Except using the polymkeric substance C solution that in synthesis example 4, obtains to replace the polymer A solution, obtain aligning agent for liquid crystal of the present invention and VA type liquid crystal display cells similarly to Example 1.Estimate the reliability of granule number, coating, tilt angle, voltage retention and voltage retention, the results are shown in table 1.
Embodiment 4
Except using the polymkeric substance D solution that in synthesis example 5, obtains to replace the polymer A solution, obtain aligning agent for liquid crystal of the present invention and VA type liquid crystal display cells similarly to Example 1.Estimate the reliability of granule number, coating, tilt angle, voltage retention and voltage retention, the results are shown in table 1.
Comparative example 1
Except using the polymkeric substance E solution that in comparing synthesis example 1, obtains to replace obtaining aligning agent for liquid crystal of the present invention and liquid crystal display cells similarly to Example 1 the polymer A solution.Estimate the reliability of granule number, coating, tilt angle, voltage retention and voltage retention, the results are shown in table 1.
Comparative example 2
In the polymkeric substance F that relatively synthesis example 2 obtains, add N-N-methyl-2-2-pyrrolidone N-and ethylene glycol monobutyl ether, make the mixed weight of N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether compare=50/50, and then interpolation is the N of 20 weight % with respect to polymkeric substance F, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane is made the aligning agent for liquid crystal that the total solid constituent concentration is 3.5 weight %.In addition, obtain aligning agent for liquid crystal of the present invention and VA type liquid crystal display cells similarly to Example 1.Estimate the reliability of granule number, coating, tilt angle, voltage retention and voltage retention, the results are shown in table 1.
Comparative example 3
In the polymkeric substance G that relatively synthesis example 3 obtains, add gamma-butyrolacton, N-N-methyl-2-2-pyrrolidone N-and ethylene glycol monobutyl ether, make the mixed weight of gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether compare=40/30/30, and then interpolation is the N of 20 weight % with respect to polymkeric substance G, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane is made the aligning agent for liquid crystal that the total solid constituent concentration is 3.5 weight %.In addition, obtain aligning agent for liquid crystal of the present invention and VA type liquid crystal display cells similarly to Example 1.Estimate the reliability of granule number, coating, tilt angle, voltage retention and voltage retention, the results are shown in table 1.
Table 1
Polymkeric substance Coating Granule number Tilt angle Voltage retention
Initial value Initial value is judged Reliability (VHR variable quantity) Reliability decision
Embodiment 1 A Well 1 90.0° 99.3％ Well -0.3 5％ Well
Embodiment 2 B Well 0 90.0° 99.1％ Well -0.4 4％ Well
Embodiment 3 C Well 1 90.0° 99.5％ Well -0.3 2％ Well
Embodiment 4 D Well 3 89.9° 99.2％ Well -0.2 8％ Well
Comparative example 1 E Well 1 Can't measure 96.1％ Bad -0.4 9％ Well
Comparative example 2 F Well 4 89.8° 98.8％ Bad -0.7 7％ Bad
Comparative example 3 G Bad 5 89.8° 99.4％ Well -0.4 1％ Well
By above-mentioned table 1 as can be known, by the liquid crystal orientation film that obtains by the liquid crystal orientation film of the present invention that obtains among the embodiment 1～4, can all realize the excellent reliability of excellent alignment films coating, high voltage holding ratio and voltage retention simultaneously.On the other hand, by comparative example as can be known, alignment agent in the past can't satisfy whole above-mentioned characteristics simultaneously.As can be known, the structure choice and the content optimization thereof of the repetitive that becomes the tilt angle representative element of through type (1) expression, and the structure choice of other copolymer compositions and content optimization thereof can be adjusted the above-mentioned characteristic of aligning agent for liquid crystal of the present invention.As above, by the present invention, the aligning agent for liquid crystal that can obtain following liquid crystal orientation film can be provided and have this liquid crystal orientation film, have the liquid crystal display cells of beautiful image; Described liquid crystal orientation film can realize simultaneously that the excellent reliability of excellent alignment agent coating, high voltage holding ratio and voltage retention is whole.

Claims (10)

1, a kind of aligning agent for liquid crystal is characterized in that, contains the polymkeric substance with the represented repetitive of following formula (1),
Figure S2008100094554C00011
In the formula, R 1It is hydrogen atom; Halogen atom; Can have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～30 alkyl; Or the polar group of 1 valency; A 1Be that singly-bound or carbon number are 1～10 alkylidene; A 2, A 3And A 4Independent separately, be singly-bound, ehter bond (O-), carbonyl (CO-), carbonyl oxygen base (COO-), the oxygen carbonyl (OCO-), amido link (NHCO-,-CONH-), thioether bond (S-) or carbon number be 1～10 alkylidene; B 1, B 2And B 3Independent separately, be singly-bound, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-cyclohexylidene, 1,3-cyclohexylidene, 1,4-cyclohexylidene or piperidines-1,4-two bases; R 2Be that hydrogen atom, carbon number are 1～50 alkyl or the group that contains fluorine atom; But, the A of adjacency 1～A 4And B 1～B 3Represent a singly-bound when all being singly-bound, and A 1～A 4And B 1～B 3When all representing a singly-bound, R 2It or not hydrogen atom.
2, aligning agent for liquid crystal according to claim 1, wherein, polymkeric substance further has the represented repetitive of following formula (2),
In the formula, R 3It is hydrogen atom; Halogen atom; Can have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～30 alkyl; Or the polar group of 1 valency; R 4Be singly-bound or divalent organic group; A 5Be that carbon number is 2～10 the group with cyclic ether structure.
3, aligning agent for liquid crystal according to claim 1 and 2, in the formula (1), R 2Be that carbon number is 3～30 straight or branched alkyl or the group with steroidal compounds skeleton.
4, according to claim 2 or 3 described aligning agent for liquid crystal, in the formula (2), R 5It is group with epoxy construction or oxetanes structure.
5, aligning agent for liquid crystal according to claim 1, wherein, the represented repetitive of described formula (1) is the repetitive of following formula (3) expression,
Figure S2008100094554C00022
In the formula, R 6Definition and the R of formula (1) 1Definition identical.
6, aligning agent for liquid crystal according to claim 2, wherein, the represented repetitive of described formula (2) is the repetitive of following formula (4) expression,
Figure S2008100094554C00031
In the formula, R 7Definition and the R of described formula (1) 1Definition identical, a is 1～10 integer.
7, according to claim 5 or 6 described aligning agent for liquid crystal, wherein, polymkeric substance further contains the represented repetitive of following formula (5),
Figure S2008100094554C00032
In the formula, R 8Definition and the R of described formula (1) 1Definition identical.
8, according to each described aligning agent for liquid crystal in the claim 5～7, wherein, polymkeric substance further contains at least a of the represented separately repetitive in following formula (6) and (7),
Figure S2008100094554C00033
In the formula, R 9Be to have the linking group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or the carbon number that do not have a replacement is 1～50 alkyl; R 10And R 11Independent separately, with the R of described formula (1) 1Definition identical.
9, a kind of liquid crystal orientation film, it is formed by the described aligning agent for liquid crystal of claim 1～8.
10, a kind of liquid crystal display cells, it contains the described liquid crystal orientation film of claim 9.
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