CN103980911A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element and manufacture method thereof - Google Patents

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element and manufacture method thereof Download PDF

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CN103980911A
CN103980911A CN201410025139.1A CN201410025139A CN103980911A CN 103980911 A CN103980911 A CN 103980911A CN 201410025139 A CN201410025139 A CN 201410025139A CN 103980911 A CN103980911 A CN 103980911A
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liquid crystal
polymkeric substance
film
crystal aligning
aligning agent
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CN103980911B (en
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樫下幸志
平野哲
吉泽满代
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JSR Corp
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

Abstract

The invention provides a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element and a manufacture method thereof. The invention provides the liquid crystal alignment agent which provides a liquid crystal alignment film which is good in washing-resistance (solvent resistance) in condition that an organic solvent is used as a cleaning fluid. The liquid crystal alignment agent comprises a polymer (S), the polymer (S) is obtained by polymerizing an alkoxy silane compound (A) having one alkoxy and one silylation in one molecule and an alkoxy silane compound (B) having more than 2 alkoxy silylations in one molecule. Compared with the alkoxy silane compound (A), the alkoxy silane compound (B) used in the polymerization of the polymer (S) is 3 Moore% to 30 Moore%.

Description

Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device and manufacture method thereof
Technical field
The present invention relates to a kind of liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device and manufacture method thereof.
Background technology
As liquid crystal display device, except twisted nematic (Twisted Nematic, TN) type, STN Super TN (Super Twisted Nematic, STN) use of the representative such as type has beyond the liquid crystal display device of horizontal alignment pattern of the nematic liquid crystal (nematic liquid crystal) of positive dielectric anisotropy, also known use has vertical orientated (the Vertical Alignment of vertical (homeotropic) alignment mode of the nematic liquid crystal of negative dielectric anisotropic, VA) the various liquid crystal display device such as type liquid crystal display device.These liquid crystal display device possess and have the liquid crystal orientation film that makes the function that liquid crystal molecule is orientated on certain orientation.The material that forms this liquid crystal orientation film is known polyamic acid, polyimide, polymeric amide, polyester, organopolysiloxane etc., the liquid crystal orientation film that particularly comprises polyamic acid or polyimide is due to thermotolerance, physical strength, with the affinity excellence of liquid crystal molecule etc., so just preferably use for a long time (with reference to patent documentation 1～patent documentation 3).While manufacturing liquid crystal display device, liquid crystal orientation film is to be dissolved in these component of polymer the liquid crystal aligning agent forming in organic solvent to form.
In addition, disclose the liquid crystal aligning agent that contains following organopolysiloxane in patent documentation 4, this organopolysiloxane is to make the mixture of the water-disintegrable silane compound of 3 officials' energy and 4 officials energy under the existence of oxalic acid and alcohol, react and obtain.Explanation in this patent documentation 4: vertical orientated property and the excellent heat resistance of the liquid crystal orientation film being formed by described liquid crystal aligning agent.
In addition, propose in recent years to have the liquid crystal display device of polymer stabilizing orientation (Polymer Sustained Alignment, PSA) pattern.PSA pattern is following technology: comprising at least 1 gap with a pair of substrate of the substrate of pattern-like conducting film, the liquid-crystal composition that clamping contains polymerizable compound, between to conducting film, execute irradiation ultraviolet radiation under alive state, make polymerizable compound carry out polymerization, show thus tilt angle characteristic and control the differently-oriented directivity of liquid crystal.According to this technology, can realize by conducting film being made as to specific formation the high speed of amplification and the liquid crystal molecule response at visual angle, in multidomain vertical orientation (Multi-domain Vertical Alignment, MVA) profile plate, the problem of inevitable transmissivity and contrast gradient deficiency is also eliminated.
In addition, recently, proposed to relate to the technology (patent documentation 5) of the more novel display format that replaces PSA pattern.This technology anticipation: the Kapton that comprises the laurate structure with light functionality is irradiated to the ultraviolet ray without polarisation, utilize and rotate to give required tilt angle expression power by the caused molecule of photoisomerization of laurate structure.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese patent laid-open 4-153622 communique
The clear 56-91277 communique of [patent documentation 2] Japanese Patent Laid-Open
[patent documentation 3] Japanese patent laid-open 11-258605 communique
[patent documentation 4] Japanese patent laid-open 9-281502 communique
No. 2009/0325453 specification sheets of [patent documentation 5] U.S. Patent Application Publication
Summary of the invention
For being attached to the objects such as the foreign matter removal of film coated surface, the film forming with liquid crystal aligning agent in described the whole bag of tricks with an organic solvent cleans sometimes.In this cleaning step, conventionally use the poor solvent of component of polymer contained in liquid crystal aligning agent as scavenging solution.On the other hand, in the time that described step is cleaned, by film coated surface is contacted with scavenging solution, and in scavenging solution dissolve polymer composition.In this situation, the thickness of film reduces, and in the liquid crystal orientation film that worry forms, cannot show required liquid crystal aligning or electrical characteristic.
The present invention forms in view of described situation, and one of its object is to provide a kind of liquid crystal aligning agent, and this liquid crystal aligning agent provides the resistance to cleaning (solvent resistance) with an organic solvent as scavenging solution in the situation that good liquid crystal orientation film.
According to the present invention, described problem is to be reached by following liquid crystal aligning agent, described liquid crystal aligning agent contains polymkeric substance (S), this polymkeric substance (S) is the alkoxysilane compound containing trialkylsilyl group in molecular structure (A) in 1 molecule by comprising in monomer composition with 1 alkoxysilane group, with in 1 molecule, have more than 2 alkoxysilane group alkoxysilane compound containing trialkylsilyl group in molecular structure (B) polymerization and obtain, and with respect to described alkoxysilane compound containing trialkylsilyl group in molecular structure (A), the described alkoxysilane compound containing trialkylsilyl group in molecular structure (B) using in the polymerization of described polymkeric substance (S) is 3 % by mole～30 % by mole.Described polymkeric substance (S) also can be through under the existence of for example alkali metal compound or organic bases, organoalkoxysilane (A) and organoalkoxysilane (B) is hydrolyzed or the step of hydrolytic condensation is synthesized.
[effect of invention]
Liquid crystal aligning agent of the present invention can provide in the case of utilizing the resistance to cleaning good liquid crystal orientation film of organic solvent formed film is cleaned.Therefore, the liquid crystal orientation film being obtained by liquid crystal aligning agent of the present invention still has sufficient thickness after cleaning, even if the liquid crystal display device of the display format of known VA type liquid crystal display device, PSA pattern or renewal, also can realize desired display quality before being for example applied to.In addition, also favourable with regard to the viewpoint of goods yield.
Brief description of the drawings
Fig. 1 is the figure that represents the electrode pattern of the patterned transparency electrode for slit-shaped.
Fig. 2 is the summary pie graph of FFS type liquid crystal display device.
Fig. 3 (a) and Fig. 3 (b) are the floor map of top electrode.Fig. 3 (a) is the vertical view of top electrode, and Fig. 3 (b) is the part enlarged view of top electrode.
[explanation of symbol]
10: liquid crystal display device
11a, 11b: glass substrate
12: bottom electrode
13: silicon nitride film
14: top electrode
15a, 15b: liquid crystal orientation film
Embodiment
Liquid crystal aligning agent of the present invention contains the polymkeric substance (S) that the polymerization by comprising alkoxysilane compound containing trialkylsilyl group in molecular structure in monomer composition obtains.Below, other compositions of each composition contained in liquid crystal aligning agent of the present invention and allotment optionally and arbitrarily are described.
< polymkeric substance (S) >
Polymkeric substance (S) be use there is the alkoxysilane compound containing trialkylsilyl group in molecular structure (A) of 1 alkoxysilane group in 1 molecule, with 1 molecule in there is more than 2 alkoxysilane group alkoxysilane compound containing trialkylsilyl group in molecular structure (B) be used as monomer and the polymkeric substance that obtains.
(alkoxysilane compound containing trialkylsilyl group in molecular structure (A))
Described alkoxysilane compound containing trialkylsilyl group in molecular structure (A), as long as have 1 alkoxysilane group, is not particularly limited, and can be any in monoalkoxy silane, dialkoxy silicane, trialkoxy silane, tetraalkoxysilane.In addition, alkoxysilane compound containing trialkylsilyl group in molecular structure (A) for example can have the functional groups such as epoxy group(ing), vinyl, allyl group, styryl, (methyl) acryl, amino, isocyanato, sulfydryl.
As alkoxysilane compound containing trialkylsilyl group in molecular structure (A), particularly, for example, the concrete example of monoalkoxy silane, dialkoxy silicane and trialkoxy silane for example can be enumerated:
3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxypropyl dimethyl methyl TMOS, 3-glycidoxypropyl dimethylethoxysilane, 2-glycidoxypropyl ethyl trimethoxy silane, 2-glycidoxypropyl ethyl triethoxysilane, 2-glycidoxypropyl ethyl-methyl dimethoxy silane, 2-glycidoxypropyl ethyl-methyl diethoxy silane, 2-glycidoxypropyl ethyl dimethyl methyl TMOS, 2-glycidoxypropyl ethyl dimethylethoxysilane, 4-glycidoxypropyl butyl trimethoxy silane, 4-glycidoxypropyl butyl triethoxyl silane, 4-glycidoxypropyl butyl methyl dimethoxy silane, 4-glycidoxypropyl butyl methyl diethoxy silane, 4-glycidoxypropyl butyl dimethyl methyl TMOS, 4-glycidoxypropyl butyl dimethylethoxysilane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl triethoxysilane, 3-(3,4-epoxy group(ing) cyclohexyl) propyl trimethoxy silicane, 3-(3,4-epoxy group(ing) cyclohexyl) propyl-triethoxysilicanes etc. are containing the silane compound of epoxy group(ing),
3-(methyl) acryloxy propyltrichlorosilan, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 2-(methyl) acryloxy ethyl trichlorosilane, 2-(methyl) acryloxy ethyl trimethoxy silane, 2-(methyl) acryloxy ethyl triethoxysilane, 4-(methyl) acryloxy butyl trichlorosilane, 4-(methyl) acryloxy butyl trimethoxy silane, 4-(methyl) acryloxy butyl triethoxyl silane, 3-(methyl) acryloxy butyl trimethoxy silane, 3-(methyl) acryloxy amyltrimethoxysilane, 3-(methyl) acryloxy hexyl Trimethoxy silane, 3-(methyl) acryloxy heptyl Trimethoxy silane, 3-(methyl) acryloxy octyl group Trimethoxy silane, 3-(methyl) acryloxy nonyl Trimethoxy silane, 3-(methyl) acryloxy decyl Trimethoxy silane, 3-(methyl) acryloxy undecyl Trimethoxy silane, 3-(methyl) acryloxy dodecyltrimethoxysilanes etc. are containing the silane compound of (methyl) acryl,
METHYL TRICHLORO SILANE, methyltrimethoxy silane, Union carbide A-162, phenyl-trichloro-silicane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyl dichlorosilane (DMCS), methyl dimethoxysilane, methyldiethoxysilane, dimethyldichlorosilane(DMCS), dimethyldimethoxysil,ne, dimethyldiethoxysilane, diphenyl dichlorosilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, Chlorodimethyl silane, methoxyl group dimethylsilane, oxyethyl group dimethylsilane, chlorine trimethyl silane, trimethylammonium bromide silane, iodine trimethyl silane, methoxytrimethylsilane, trimethylethoxysilane, dodecyl triethoxyl silane, octadecyl trichlorosilane alkane, octadecyl Trimethoxy silane, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilanis, other the silane compound etc. such as allyltriethoxysilane.In addition, the concrete example of tetraalkoxysilane for example can be enumerated: four butoxy silanes, tetraethoxysilane, tetraisopropoxysilan, tetramethoxy-silicane, tetrapropoxysilane etc.In addition, in this specification sheets, " (methyl) acryloxy " is the implication that comprises " acryloxy " and " methacryloxy ".Described alkoxysilane compound containing trialkylsilyl group in molecular structure (A) can use separately or two or more is used in combination a kind in described compound.
With regard to improving the aspect etc. of molecular weight of polymkeric substance (S), alkoxysilane compound containing trialkylsilyl group in molecular structure (A) is preferably and comprises trialkoxy silane.The total amount of the alkoxysilane compound containing trialkylsilyl group in molecular structure (A) using with respect to reaction, the usage ratio of trialkoxy silane is preferably and is made as more than 80 % by mole, is more preferably made as more than 90 % by mole, is especially preferably and is made as more than 95 % by mole.
In the situation that uses tetraalkoxysilane as alkoxysilane compound containing trialkylsilyl group in molecular structure (A), total mole number with respect to alkoxysilane compound containing trialkylsilyl group in molecular structure (A) with alkoxysilane compound containing trialkylsilyl group in molecular structure (B), the usage ratio of described tetraalkoxysilane is preferably below 30 % by mole.By being made as described scope, can will be made as preferred scope by the molecular weight of the synthetic polymkeric substance (S) obtaining.In addition, can suppress the gelation of polymkeric substance (S) or separate out, can obtain the polymers soln of excellent storage stability.More preferably, below 20 % by mole, be especially preferably 15 % by mole.
(alkoxysilane compound containing trialkylsilyl group in molecular structure (B))
Described alkoxysilane compound containing trialkylsilyl group in molecular structure (B), as long as have 2 above alkoxysilane groups, is not particularly limited, for example, can enumerate the represented compound of following formula (B ') etc.
[changing 1]
(in formula (B '), R 11and R 12be the alkyl of carbon number 1～6 independently respectively, X 11for the organic radical of h valency; H is 2～4 integer, the integer that i is 1～3.)
R in described formula (B ') 11and R 12for example can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, these groups can be straight chain shapes, can be also branch-like.Be preferably carbon number 1～3, more preferably methyl or ethyl.
X 11organic radical for example can enumerate: the alkyl such as chain alkyl, ester ring type alkyl and aromatic hydrocarbyl, or methylene radical warp-O-,-CO-in chain alkyl ,-COO-,-NH-,-group that CONH-etc. replaces, have the group of heterocycle etc.X 11carbon number be preferably 1～20, more preferably 2～15.
H is 2～4, more preferably 2 or 3.
The preferred concrete example of alkoxysilane compound containing trialkylsilyl group in molecular structure (B) for example can be enumerated the represented compound of following formula (B-1)～formula (B-3) difference etc.
[changing 2]
(in formula (B-1)～formula (B-3), R is the alkyl of carbon number 1～6, can be identical in 1 molecule, and also can be different; X nfor thering is the divalent group of nitrogen-atoms; J1 is 1～20 integer, and j2 is respectively 1～6 integer independently, and j3 is respectively 1～6 integer independently.)
R in described formula (B-1)～formula (B-3) is preferably methyl or ethyl, more preferably methyl.The X of described formula (B-3) nfor example can enumerate :-NH-, piperidine ring, piperazine ring etc.In addition, alkoxysilane compound containing trialkylsilyl group in molecular structure (B) can be used alone a kind or two or more is used in combination.
With respect to the total mole number of alkoxysilane compound containing trialkylsilyl group in molecular structure (A), be preferably 3 % by mole～30 % by mole for the synthesis of the usage ratio of the alkoxysilane compound containing trialkylsilyl group in molecular structure (B) of polymkeric substance (S).If be less than 3 % by mole, the molecular weight of the polymkeric substance of gained is little, has the tendency of poor solvent resistance.In addition, if more than 30 % by mole, easily produce the gelation of polymkeric substance or separate out, being wanting at storage stability.The scope of more preferably 3 % by mole～20 % by mole, is especially preferably the scope of 5 % by mole～20 % by mole.In making liquid crystal aligning agent, contain in the situation of organopolysiloxane by using polymkeric substance (S), the polymer that can realize component of polymer quantizes, and can make the solvent resistance of liquid crystal orientation film good.
Polymkeric substance (S) is preferably has epoxy group(ing).In polymkeric substance (S), for having in the situation of organopolysiloxane (below also referred to as " containing the organopolysiloxane of epoxy group(ing) ") of epoxy group(ing), epoxy group(ing) is preferably oxa-cyclopropyl.Oxa-cyclopropyl can be that one of them that only form in the carbon atom of oxa-cyclopropyl rings has associative key, to the direct bond of the Siliciumatom of organopolysiloxane or via the bond in conjunction with base, or can be also to form in the carbon atom of oxa-cyclopropyl rings two to become the ring-type oxa-cyclopropyl structure of the carbon atom that forms alicyclic ring by this associative key.The organopolysiloxane containing epoxy group(ing) as polymkeric substance (S) for example can obtain by the polymerization that comprises the illustrated described silane compound containing epoxy group(ing) in alkoxysilane compound containing trialkylsilyl group in molecular structure (A) in monomer composition.
Polymkeric substance (S) is preferably according to the purposes of liquid crystal aligning agent has specific functional group.For example, in the situation for the manufacture of VA type liquid crystal display device by liquid crystal aligning agent of the present invention, polymkeric substance (S) is preferably and comprises the group (below also referred to as " liquid crystal aligning base ") with the function that makes liquid crystal molecular orientation as specific functional group.In addition, be applied to and constructing after the liquid crystal cells of PSA pattern etc., improve the situation of pattern of the orientation limitations power of liquid crystal molecule by carry out rayed from the outside of this liquid crystal cells, polymkeric substance (S) is preferably has the group that comprises the two keys of polymerizability as specific functional group.In utilizing optical alignment method the macromolecule membrane being formed by liquid crystal aligning agent to be given in the situation of liquid crystal aligning ability, polymkeric substance (S) is preferably to be had and can give anisotropic functional group (below also referred to as " light orientation base ") as specific functional group to film by utilizing light-struck photoisomerization reaction or photodimerization to react.
[liquid crystal aligning base]
Described liquid crystal aligning base is the group that can give to the macromolecule membrane being formed by liquid crystal aligning agent tilt angle, for example, can enumerate the represented group of following formula (D ') etc.
[changing 3]
(in formula (D '), R ifor the alkyl of carbon number 1～40, fluoroalkyl, cyano group or the fluorine atom of carbon number 1～40, or there is the alkyl of the carbon number 17～51 of steroid (steroid) skeleton; Z ifor singly-bound, *-O-, *-COO-or *(wherein, to have the associative key of " * " be R to mark to-OCO- iside); R iIfor cyclohexylidene or phenylene, being binding on ring hydrogen atom can replace through the alkyl of cyano group, fluorine atom, trifluoromethyl or carbon number 1～3; N1 is 1 or 2, wherein in the time that n1 is 2, and 2 R iIcan be mutually identical, also can be different; N2 is 0 or 1; Z iIfor singly-bound, *-O-, *-COO-or *(wherein, to have the associative key of " * " be R to mark to-OCO- iside); N3 is 0～2 integer, and n4 is 0 or 1)
Have the represented group of this described formula (D ') by polymkeric substance (S), the film being formed by the liquid crystal aligning agent that contains described polymkeric substance (S) is brought into play good liquid crystal aligning ability, therefore preferred.
About the R of described formula (D ') i, the alkyl of carbon number 1～40 is preferably the alkyl of straight chain shape, particularly, for example, can enumerate: methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-octyl, positive decyl, dodecyl, n-hexadecyl, stearyl etc.; The fluoroalkyl of carbon number 1～40 is preferably the fluoroalkyl of straight chain shape, particularly, for example, can enumerate: 3-trifluoromethyl propyl group, 4-trifluoromethyl butyl, 6-trifluoromethyl hexyl, 10-trifluoromethyl decyl, 3-pentafluoroethyl group propyl group, 4-pentafluoroethyl group butyl, 8-pentafluoroethyl group octyl group, 3,3,4,4,5,5,5-, seven fluorine amyl groups, 3,3,4,4,5,5,6,6,7,7,8,8,8-, ten trifluoro octyl groups, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-, 17 fluorine decyls etc.; The alkyl of the described carbon number 17～51 with steroid skeleton for example can be enumerated: 3-cholestane base (3-cholestanyl), 3-cholesteryl (3-cholestenyl), 3-lanostane base (3-lanostanyl), 3-cholane base (3-cholanyl), 3-pregnane base (3-pregnyl), 3-androstane alkyl (3-androstanyl), 3-female steroid alkyl (3-estranyl) etc.
Work as R ifor alkyl or fluoroalkyl and n2 and n4, the two is 0 o'clock, R ialkyl or fluoroalkyl be preferably the straight chain shape of carbon number 4～40.
R in described formula (D ') iIcyclohexylidene and phenylene be preferably respectively Isosorbide-5-Nitrae-cyclohexylidene and Isosorbide-5-Nitrae-phenylene.As " (R in described formula (D ') iI) n1-" represented divalent group, the situation that n1 is 1 for example can be enumerated: Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene etc.; N1 is that 2 situation for example can be enumerated: 4,4 '-biphenylene, 4,4 '-bis-cyclohexylidenes, following formula
[changing 4]
(in formula, mark has associative key and the Z of " * " ibond)
The groups that difference is represented etc., are used as preferred group.
N3 in described formula (D ') is preferably 2.In addition, a preferably example of the represented group of described formula (D ') can be enumerated: n2 be 1 or n2 be 0 and R ifor thering is the group of alkyl of carbon number 17～51 of steroid skeleton.
In the situation for the manufacture of VA type liquid crystal display device by liquid crystal aligning agent of the present invention, with respect to 1 mole of Siliciumatom contained in polymkeric substance (S), the ratio that exists of the liquid crystal aligning base in polymkeric substance (S) is preferably 0.7 mole of following ratio, more preferably 0.5 mole of following ratio, is especially preferably the ratio of 0.1 mole～0.5 mole.
[group that comprises the two keys of polymerizability]
The described group that comprises the two keys of polymerizability for example can be enumerated the represented group of following formula (A) etc.
[changing 5]
(in formula (A), R is hydrogen atom or methyl, X iand X iIbe respectively alkane two bases of Isosorbide-5-Nitrae-phenylene, carbon number 1～8, Z is Sauerstoffatom ,-COO- *or-OCO- *(wherein, mark has associative key and the X of " * " iIbond), a, b, c and d are respectively 0 or 1.Wherein, when c is 0 and d while being 1, X iIfor Isosorbide-5-Nitrae-phenylene, in the time that b is 0, d is 0.)
Group Z in described formula (A) is preferably Sauerstoffatom.
The concrete example of the represented group of described formula (A) for example can be enumerated: vinyl, allyl group, to styryl, (methyl) acryloyl-oxy ylmethyl, 2-((methyl) acryloxy) ethyl, 3-((methyl) acryloxy) propyl group, 4-((methyl) acryloxy) butyl, 5-((methyl) acryloxy) amyl group, 6-((methyl) acryloxy) hexyl, 7-((methyl) acryloxy) heptyl, 8-((methyl) acryloxy) octyl group, 9-((methyl) acryloxy) nonyl, 10-((methyl) acryloxy) decyl, 4-(2-((methyl) acryloxy) ethyl) phenyl, 2-((4-(methyl) acryloxy) phenyl) ethyl, 4-((methyl) acryloyl-oxy ylmethyl) phenyl, 4-(methyl) acryloxy phenyl methyl, 4-(3-((methyl) acryloxy) propyl group) phenyl, 3-(4-(methyl) acryloxy phenyl) propyl group, 4-((methyl) acryloyl-oxy ylmethoxy) phenyl, 4-(2-((methyl) acryloxy) oxyethyl group) phenyl, 4-(3-((methyl) acryloxy) propoxy-) phenyl, (methyl) acryloxy methoxymethyl, 2-((methyl) acryloyl-oxy ylmethoxy) ethyl, 2-(2-((methyl) acryloyl-oxy base oxethyl) ethyl, 2-(2-(2-((methyl) acryloxy) oxyethyl group) oxyethyl group) ethyl, 3-(3-((methyl) acryloxy) propoxy-) propyl group, acryloyl-oxy ylmethyl, 6-{[6-(acryl oxygen base) caproyl] oxygen base } hexyl etc.In these groups, can enumerate vinyl, allyl group, to styryl, (methyl) acryloyl-oxy ylmethyl, 2-((methyl) acryloxy) ethyl, 3-((methyl) acryloxy) propyl group and 6-{[6-(acryl oxygen base) caproyl] oxygen base hexyl is as preferred group.
The described group that comprises the two keys of polymerizability is preferably the represented group of described formula (A), is more preferably selected from a kind of above group in above-mentioned illustrated concrete group.With regard to the aspect of orientation limitations power that fully improves liquid crystal molecule with regard to the rayed after constructing by liquid crystal cells, with respect to 1 mole of Siliciumatom contained in polymkeric substance (S), polymkeric substance (S) is preferably with the ratio of 0.01 mole～0.80 mole and contains the group that comprises the two keys of polymerizability, more preferably contain with the ratio of 0.02 mole～0.70 mole, be especially preferably with the ratio of 0.2 mole～0.60 mole and contain.In addition, contain in the situation of the polymkeric substance with the group that comprises the two keys of polymerizability as polymkeric substance (S) in liquid crystal aligning agent of the present invention, the heat treated with regard to can form by film time further promotes with regard to intermolecular crosslinked aspect preferably.
[light orientation base]
With regard to the sensitive aspect to light or be easily directed into regard to the aspect in polymkeric substance, described smooth orientation base is preferably has the represented structure of following formula (B1).In addition, by not only comprising the represented structure of following formula (B1), and make also to comprise the represented group of following formula (A1) in the contained polymkeric substance of liquid crystal aligning agent (S), can improve high-speed response.
[changing 6]
(in formula (B1), R is fluorine atom or cyano group; A ' is 0～4 integer; Be in more than 2 situations in a ', multiple R can be identical, also can be different; " * " represents associative key.)
[changing 7]
(in formula (A1), R afor alkane two bases, phenylene or the cyclohexylidene of carbon number 1～30; Wherein, part or all of the hydrogen atom that these groups have can be substituted; R bfor comprising any the concatenating group in two keys, triple bond, ehter bond and ester bond; R cfor thering is the group of at least 2 single ring architectures; A is 0 or 1; " * " represents associative key.)
R in described formula (A1) cbe preferably by following formula (A2) represented.
[changing 8]
(in formula (A2), R dfor phenylene, biphenylene, naphthylidene, cyclohexylidene, two cyclohexylidene, cyclohexylidene phenylene or divalent heterocyclic radical; Part or all of the hydrogen atom that these groups have can be substituted; R efor thering is any one the concatenating group in the substituent alkane that comprises carbon number 1～10 two bases, two key, triple bond, ehter bond, ester bond and heterocyclic radical; R ffor remove (c+1) valency group that (c+1) individual hydrogen atom obtains in benzene, biphenyl, naphthalene, hexanaphthene, bis cyclohexane, phenylcyclohexane or heterogeneous ring compound; R gfor hydrogen atom, cyano group, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxyl group, trifluoromethoxy or alkyl-carbonyl oxygen base; B is 0 or 1; C is 1～9 integer; D is 1 or 2; In R d, R e, R gand b is respectively in multiple situation, multiple R d, R e, R gand b respectively can be identical, also can be different; * represent associative key.)
In addition, have in the multiple situation in described particular functional base in polymkeric substance (S), each functional group can all be contained in the polymkeric substance (S) in single kind, also can be used as to have the polymkeric substance (S) of the part in required functional group, use with the mixture of polymkeric substance (S) with all the other functional groups.Certainly, 3 kinds of above organopolysiloxane can be mixed and use, also the organopolysiloxane of more than two kinds with identical functional group can be mixed and uses, be used as polymkeric substance (S).Can be any embodiment, is therefore organopolysiloxane as long as have as a whole described each functional group in described scope as the polymkeric substance (S) of single thing or mixture.Therefore, use polymkeric substance (S) in the form of the mixture with multiple organopolysiloxane, described each functional group's preferable range can be regarded as respectively the mole number using the total amount of polyorganosiloxane mixtures as benchmark.
(synthesizing of polymkeric substance (S))
As mentioned above, polymkeric substance (S) can, by making alkoxysilane compound containing trialkylsilyl group in molecular structure (A) and alkoxysilane compound containing trialkylsilyl group in molecular structure (B) and water, be preferably under the existence of suitable catalyzer and organic solvent and react and synthesize.When this hydrolysis-condensation reaction, with respect to 1 mole of the synthetic silane compound (total amount) using, the usage ratio of water is preferably 0.5 mole～100 moles, more preferably 1 mole～30 moles.
When hydrolysis-condensation reaction, spendable catalyzer for example can be enumerated: acid, alkali metal compound, organic bases, titanium compound, zirconium compounds etc., be preferably acid, alkali metal compound or organic bases.As the concrete example of these catalyzer, acid for example can be enumerated: oxalic acid, phosphoric acid, acetic acid, hydrochloric acid, tosic acid etc.; Alkali metal compound for example can be enumerated: sodium hydroxide, potassium hydroxide, sodium ethylate etc.; Described organic bases for example can be enumerated 1 grade～2 grades organic amines, 3 grades of organic amines, 4 grades of organic amines etc.
As described catalyzer, with regard to can suppressing aspect of the aspect of the side reactions such as the open loop of epoxy group(ing), the aspect that maybe can accelerate hydrolytic condensation speed, excellent storage stability etc., be preferably alkali metal compound or organic bases in described these catalyzer, be particularly preferably organic bases.Organic bases is preferably the organic amine of 3 grades or the organic amine of 4 grades, for example, can enumerate respectively: as 3 of triethylamine, three-Tri N-Propyl Amine, three-n-Butyl Amine 99, pyridine, 4-dimethylaminopyridine and so on grades of organic amines: as 4 of Tetramethylammonium hydroxide and so on grades of organic amines etc.The usage quantity of organic bases according to reaction conditions such as kind, temperature of organic bases etc. and different, can suitably be set, and for example, with respect to whole silane compounds, is preferably 0.01 times mole～3 times moles, more preferably 0.05 times mole～1 times mole.
When described hydrolysis-condensation reaction, spendable organic solvent for example can be enumerated: hydrocarbon, ketone, ester, ether, alcohol etc.As the concrete example of these organic solvents, hydrocarbon for example can be enumerated: toluene, dimethylbenzene etc.; Ketone for example can be enumerated: methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, metacetone, pimelinketone etc.; Ester for example can be enumerated: ethyl acetate, butylacetate, Isoamyl Acetate FCC, propylene glycol methyl ether acetate, acetic acid 3-methoxyl group butyl ester, ethyl lactate etc.; Ether for example can be enumerated: glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF) etc.; Alcohol for example can be enumerated: 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether etc.In these organic solvents, be preferably and use non-water-soluble organic solvent.In addition, these organic solvents can be used alone a kind or by two or more mix use.
With respect to whole silane compounds 100 weight parts that use in reaction, the usage ratio of the organic solvent in hydrolysis-condensation reaction is preferably 10 weight part～10,000 weight part, more preferably 50 weight part～1,000 weight part.
Described hydrolysis-condensation reaction is preferably as mentioned above, and silane compound is dissolved in organic solvent, and this solution is mixed with organic bases and water, for example, utilize oil bath etc. to heat to implement.When hydrolysis-condensation reaction, be preferably Heating temperature is made as below 130 DEG C, be more preferably made as 40 DEG C～100 DEG C.Be preferably heat-up time and be made as 0.5 hour～12 hours, be more preferably made as 1 hour～8 hours.Add and hanker, mixed solution can be stirred, also can be placed under backflow.In addition, after reaction finishes, be preferably and utilize water to clean a point organic solvent layer of getting from reaction solution.When this cleaning, the water (for example, the aqueous ammonium nitrate solution of 0.2 % by weight left and right etc.) that comprises a small amount of salt by use cleans, preferred with regard to cleaning operation becomes easy aspect.Can, by till cleaning and becoming neutrality to the water layer after cleaning, then, after optionally utilizing the siccative such as anhydrous calciumsulphate, molecular sieve that organic solvent layer is dry, remove solvent, thereby obtain polymkeric substance (S).
In situation in described polymkeric substance (S) for the organopolysiloxane containing epoxy group(ing), with respect to this containing Siliciumatom contained in the organopolysiloxane of epoxy group(ing) 1 mole, the ratio that exists of this epoxy group(ing) is preferably the ratio of 0.05 mole～1 mole, the ratio of more preferably 0.10 mole～1 mole.
In polymkeric substance (S), for having in the situation of organopolysiloxane (below also referred to as " containing the organopolysiloxane of specific base ") of described particular functional base, this polymkeric substance can be by synthesizing appropriately combined vitochemical well-established law.For example, can carry out synthetic method by the polymerization that comprises the water-disintegrable silane compound with described particular functional base in monomer composition by (i); (ii) by making to there is the functional groups' such as epoxy group(ing) organopolysiloxane, react the compound that forms functional group's (such as carboxyl etc.) of key and there is described particular functional base with the functional group that can have with this organopolysiloxane and react and synthesize.In addition; in the method for described (ii); be not limited to the situation of reacting to import described particular functional base with carboxyl by epoxy group(ing), for example, also can utilize reacting or (methyl) acryl and amino reacting of (methyl) acryl and sulfydryl.In described reaction, just easy and can improve with regard to the aspect of importing rate of particular functional base, be preferably and utilize containing the organopolysiloxane of epoxy group(ing) and reacting of carboxylic acid.The usage ratio that has the water-disintegrable silane compound of described particular functional base and have a compound of described particular functional base is preferably the mode that becomes respectively described preferred value scope with the concentration of the described particular functional base in resulting polymers (S) and adjusts.
< is containing the organopolysiloxane of epoxy group(ing) and the > that reacts of carboxylic acid
In by containing the organopolysiloxane of epoxy group(ing) and carboxylic acid react to synthesize in the situation as the organopolysiloxane that contains specific base of polymkeric substance (S), this reaction is preferably under the existence of suitable catalyzer and suitable organic solvent to be carried out.
As the catalyzer containing using in the reacting of the organopolysiloxane of epoxy group(ing) and carboxylic acid, for example, except can suitable use organic bases, can also use the so-called hardening accelerator reacting of promotion epoxy compounds and acid anhydrides.
Described organic bases for example can be enumerated: 1 grade or 2 grades of organic amines, 3 grades of organic amines, 4 grades of organic amine salts etc.; Described hardening accelerator for example can be enumerated: 3 grades of amine (wherein, as 3 grades of organic amines of organic bases except), imdazole derivatives, organo phosphorous compounds, 4 phosphonium salts, Diazabicycloalkene, organometallic compound, 4 grades of ammoniums of halogenation, metal halogen compound, potentiality hardening accelerator etc.Described potentiality hardening accelerators etc. for example can be enumerated: the hot cationic polymerization type potentiality hardening accelerator of high-melting-point decentralized potentiality hardening accelerator (such as amine add-on type promotor etc.), microcapsule-type potentiality hardening accelerator, amine salt type potentiality stiffening agent promotor, high temperature dissociative type etc.In these hardening accelerators, be preferably and use 4 grades of organic amine salts or 4 grades of ammoniums of halogenation.
As the concrete example of described catalyzer, described 4 grades of organic amine salts for example can be enumerated: Tetramethylammonium hydroxide etc.; 4 grades of ammoniums of described halogenation for example can be enumerated: tetraethylammonium bromide, four-normal-butyl bromination ammonium, etamon chloride, four-normal-butyl chlorination ammonium etc.Described catalyzer can use be selected from these catalyzer more than a kind.With respect to organopolysiloxane 100 weight parts containing epoxy group(ing), the usage ratio of catalyzer is preferably 0.01 weight part～100 weight part, more preferably 0.1 weight part～20 weight part.
For example can enumerate containing the organic solvent using in the reacting of the organopolysiloxane of epoxy group(ing) and carboxylic acid: ketone, ether, ester, acid amides, alcohol etc.As the concrete example of described organic solvent, described ketone for example can be enumerated: methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl n-butyl ketone, methyl-n-amyl ketone, metacetone, pimelinketone, cyclopentanone etc.; Described ether for example can be enumerated: glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), dioxan etc.;
Described ester for example can be enumerated: ethyl acetate, n-butyl acetate, Isoamyl Acetate FCC, propylene glycol methyl ether acetate, acetic acid 3-methoxyl group butyl ester, ethyl lactate etc.; Described acid amides for example can be enumerated: 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-ethanoyl morpholine, N-ethanoyl piperidines, N-acetyl-pyrrolidine etc.;
Described alcohol for example can be enumerated: 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol list-positive propyl ether, ethylene glycol list-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list-positive propyl ether etc., can use be selected from these organic solvents more than a kind.
As the total weight of the composition beyond the organic solvent in reaction soln shared ratio in the total amount of reaction soln, the usage ratio of organic solvent is preferably the ratio that becomes 0.1 % by weight～50 % by weight that is made as, and is more preferably made as the ratio that becomes 5 % by weight～50 % by weight.
About described polymkeric substance (S), utilize the weight average molecular weight of the polystyrene conversion that gel permeation chromatography measures to be preferably 500～1,000,000, more preferably 5,000～200,000, be especially preferably 5,000～150,000.Wherein, in polymkeric substance (S), for using the compound with described particular functional base to carry out in the situation of the upgrading polymkeric substance that upgrading obtains, the weight average molecular weight that is preferably the polymkeric substance before this upgrading is described scope.In the situation of the mixture that comprises two or more organopolysiloxane in liquid crystal aligning agent as described polymkeric substance (S), as long as the entirety of mixture meets described molecular weight, meet respectively described molecular weight but be preferably each organopolysiloxane.
Other polymkeric substance of < >
Liquid crystal aligning agent of the present invention also can contain described polymkeric substance (S) polymkeric substance (being sometimes referred to as below " other polymkeric substance ") in addition as component of polymer.These other polymkeric substance can be used in the electrical specification of the solution properties and the gained liquid crystal display device that improve liquid crystal aligning agent.Other polymkeric substance for example can be enumerated: polymkeric substance (below also referred to as " other organopolysiloxane ") by only using alkoxysilane compound containing trialkylsilyl group in molecular structure (A) to obtain as the polymerization of monomer, polyamic acid, poly amic acid ester, polyimide, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc.Other polymkeric substance are preferably the mixture of at least a kind (below also referred to as " polymkeric substance (P) ") selecting in the cohort that free polyamic acid, poly amic acid ester and polyimide form or other organopolysiloxane or polymkeric substance (P) and other organopolysiloxane, more preferably comprise the polymkeric substance of polymkeric substance (P).
[polymkeric substance (P): polyamic acid]
By making tetracarboxylic dianhydride react and obtain with diamine compound as the polyamic acid of polymkeric substance (P).
Tetracarboxylic dianhydride for example can enumerate: aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.These tetracarboxylic dianhydrides can be used alone, or two or more is used in combination.As their concrete example, aliphatics tetracarboxylic dianhydride for example can enumerate butane tetracarboxylic acid dianhydride etc.Ester ring type tetracarboxylic dianhydride for example can enumerate: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic base NSC 60134 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-volution-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyls-2-carboxyl methyl 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 encircles [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone etc.Aromatic tetracarboxylic acid's dianhydride for example can be enumerated: pyromellitic acid anhydride etc.In addition, can enumerate the tetracarboxylic dianhydride who records in No. 2010-97188, Japanese Patent Patent.
In these tetracarboxylic dianhydrides, be preferably and use ester ring type tetracarboxylic dianhydride, more preferably comprise 2,3,5-tricarboxylic base NSC 60134 dianhydride or 1,2,3,4-tetramethylene tetracarboxylic dianhydride, be particularly preferably and comprise 2,3,5-tricarboxylic base NSC 60134 dianhydride.
In comprising 2,3,5-tricarboxylic base NSC 60134 dianhydride and 1, in 2,3,4-tetramethylene tetracarboxylic dianhydride's at least any one situation, with respect to the synthetic middle whole tetracarboxylic dianhydrides that use of polyamic acid, the usage quantity of its total is preferably and is made as more than 10 % by mole, is more preferably made as more than 20 % by mole, is especially preferably and is made as more than 50 % by mole.
The synthetic middle diamine compound using of polyamic acid for example can be enumerated: aliphatie diamine, ester ring type diamines, diamino organo-siloxane, aromatic diamine etc.These diamine compounds can be used alone, or two or more is used in combination.As their concrete example, aliphatie diamine for example can be enumerated: m-xylene diamine (m-xylylenediamine), 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine etc.Ester ring type diamines for example can be enumerated: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (cyclo-hexylamine), 1, two (amino methyl) hexanaphthenes of 3-etc.Diamino organo-siloxane for example can be enumerated: two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc.
Aromatic diamine for example can be enumerated: Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 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 phenylene two isopropylidenes) dianiline, 4,4 '-(metaphenylene two isopropylidenes) dianiline, 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-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, 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, 3,5-diaminobenzoic acid cholestene, 3,5-diaminobenzoic acid lanostane, two (the 4-amino benzoyl 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 '-trifluoromethyl benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexanes of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptyl hexanaphthenes of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptyl hexanaphthenes of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthenes of 1,1-, 2,4-diamino-N, N-diallyl aniline, 4-aminobenzyl amine, the diamine compound that 3-aminobenzyl amine and following formula (A-1) are represented etc.
[changing 9]
(in formula (A-1), X bfor alkane two bases of carbon number 1～3 ,-O-,-COO-or-OCO-; R is 0 or 1; S is 0～2 integer; T is 1～20 integer.)
In addition, also can enumerate the diamine compound of recording in No. 2009-97188, Japanese Patent Patent.
The tetracarboxylic dianhydride of building-up reactions and the usage ratio of diamine compound that offer polyamic acid are preferably, with respect to amino contained in diamine compound 1 equivalent, tetracarboxylic dianhydride's anhydride group is 0.2 equivalent～2 equivalent, more preferably 0.3 equivalent～1.2 equivalent.This building-up reactions is preferably in organic solvent carries out.Temperature of reaction is preferably-20 DEG C～150 DEG C, more preferably 0 DEG C～100 DEG C.Reaction times is preferably 0.5 hour～and 24 hours, more preferably 2 hours～12 hours.
The solvent of organic solvent as long as the polyamic acid of synthesized being dissolved, there is no particular restriction, for example can enumerate: METHYLPYRROLIDONE (N-methyl-2-pyrrolidone, NMP), N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N, N-methylimidazole alkane ketone (N, N-dimethyl imidazolidinone), dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA (hexamethylphosphoric triamide) etc. are non-proton is polar solvent; The phenol series solvents such as meta-cresol, xylenol, phenol, halogenation phenol etc.In addition, in the scope that the synthetic middle organic solvent using for example can not be separated out at the polyamic acid of synthesized, by the poor solvent of the polyamic acids such as alcohol, ketone, ester, ether, hydrocarbon, halon use.
With respect to the total (a+b) of the total amount (b) of tetracarboxylic dianhydride and diamine compound and the usage quantity (a) of organic solvent, the usage quantity (a) of organic solvent is preferably and is made as 0.1 % by weight～50 % by weight, is more preferably made as 5 % by weight～30 % by weight.
The polyamic acid solution obtaining by described reaction can directly offer the preparation of liquid crystal aligning agent, also can, by offering again the preparation of liquid crystal aligning agent after polyamic acid segregation contained in reaction soln, also can the preparation of liquid crystal aligning agent will be offered after emanate polyamic acid purifying again.The isolation process of polyamic acid for example can be enumerated: to reaction soln being injected in a large amount of poor solvents and the method for the precipitate drying under reduced pressure obtaining; The method etc. of utilizing vaporizer that reaction soln underpressure distillation is removed.The purification process of polyamic acid can be enumerated: emanated polyamic acid is dissolved in organic solvent again to the method for utilizing poor solvent that it is separated out; Carry out 1 time or repeatedly utilize vaporizer by the method for the step of the underpressure distillation removals such as organic solvent.
[polymkeric substance (P): poly amic acid ester]
For example can utilize following methods to obtain as the poly amic acid ester of described polymkeric substance (P): [I] compound by the polyamic acid that makes to be obtained by described building-up reactions and hydroxyl or halogenide, react synthetic method containing the compound of epoxy group(ing) etc.; The method that [II] makes tetracarboxylic acid diester react with diamines; [III] makes method that tetracarboxylic acid diester dihalide reacts with diamines etc.
The compound of the hydroxyl herein, using in method [I] for example can be enumerated: the alcohols such as methyl alcohol, ethanol, propyl alcohol; The phenols such as phenol, cresols etc.In addition, halogenide for example can be enumerated: monobromethane, monobromethane, bromo-octadecane, methyl chloride, chlorooctadecane, 1,1, the fluoro-2-iodoethane of 1-tri-etc., for example can enumerate propylene oxide etc. containing the compound of epoxy group(ing).
The tetracarboxylic acid diester using in method [II] for example can be by using described alcohols, and illustrative tetracarboxylic dianhydride's open loop in described polyamic acid synthetic is obtained.The reaction of method [II] is preferably under the existence of suitable dehydration catalyst to be carried out.Dehydration catalyst for example can be enumerated: 4-(4,6-dimethoxy-1,3,5-triazines-2-yl)-4-methylmorpholine halogenide, carbonylic imidazole, phosphorus are condensing agent etc.The tetracarboxylic acid diester dihalide using in method [III] for example can be reacted and be obtained by the suitable chlorizating agent such as the tetracarboxylic acid diester that makes to obtain in mode as above and thionyl chloride.
The diamines using in method [II] and method [III] can be enumerated illustrated diamines in synthesizing of polyamic acid.In addition, poly amic acid ester can only have amic acid esters structure, can be also amido acid structure and amic acid esters structure the partial esterification thing deposited.
[polymkeric substance (P): polyimide]
Polyimide as the polymkeric substance in the present invention (P) can, by the amido acid structure dehydration closed-loop that described polyamic acid is had, carry out imidization and manufacture.Polyimide can be using the amido acid structure having as the polyamic acid of its precursor all carry out dehydration closed-loop and complete imide compound, can be also only a part for amido acid structure to be carried out to dehydration closed-loop and the part imide compound that makes amido acid structure and imide ring structure and deposit.
The synthetic method of polyimide for example can be enumerated: the method (i) polyamic acid being heated; (ii) polyamic acid is dissolved in organic solvent, in this solution, adds dewatering agent and dehydration closed-loop catalyzer, the method optionally heating etc.
Temperature of reaction in method (i) is preferably 50 DEG C～200 DEG C, more preferably 60 DEG C～170 DEG C.If temperature of reaction is less than 50 DEG C, dehydration closed-loop reaction insufficient carrying out, if temperature of reaction exceedes 200 DEG C, the molecular weight of the polyimide of gained can decline.Reaction times is preferably 0.5 hour～and 48 hours, more preferably 2 hours～20 hours.
In method (i), the polyimide of gained can directly offer the preparation of liquid crystal aligning agent, also can will after polyimide segregation, offer again the preparation of liquid crystal aligning agent, or can will after the polyimide purifying of gained, offer again the preparation of liquid crystal aligning agent.
In method (ii), dewatering agent for example can be enumerated: the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.The usage quantity of dewatering agent is suitably selected according to required imide rate, with respect to 1 mole, the amido acid structure of polyamic acid, is preferably and is made as 0.01 mole～20 moles.In addition, dehydration closed-loop catalyzer for example can be enumerated: pyridine, collidine (collidine), two picolins (lutidine), triethylamine etc.With respect to 1 mole of dewatering agent, the usage quantity of dehydration closed-loop catalyzer is preferably 0.01 mole～10 moles.In addition, the content of described dewatering agent and dehydration closed-loop agent is more, and imide rate more can improve.
The organic solvent using in method (ii) for example can be enumerated with organic solvent as illustrative organic solvent is identical for the synthesis of the organic solvent of polyamic acid etc.Temperature of reaction in method (ii) is preferably 0 DEG C～180 DEG C, more preferably 10 DEG C～150 DEG C.Reaction times is preferably 0.5 hour～and 20 hours, more preferably 1 hour～8 hours.By reaction conditions being made as to described scope, dehydration closed-loop sufficient reacting carries out, and in addition, the molecular weight of gained polyimide can be made as to suitable molecular weight.
In method (ii), obtain the reaction soln that contains polyimide.This reaction soln can directly offer the preparation of liquid crystal aligning agent, also in can autoreaction solution, remove the preparation that offers again liquid crystal aligning agent after dewatering agent and dehydration closed-loop catalyzer, also can will after polyimide segregation, offer again the preparation of liquid crystal aligning agent, or will after emanate polyimide purifying, offer again the preparation of liquid crystal aligning agent.In autoreaction solution, remove the method for dewatering agent and dehydration closed-loop catalyzer and for example can enumerate method of solvent exchange etc.The isolation process of polyimide and purification process for example can be enumerated with isolation process as polyamic acid and purification process and identical method of illustrative method etc.
Polymkeric substance (P) is preferably in the time being made into concentration and being the solution of 10 % by weight, has the polymkeric substance of the soltion viscosity of 10mPas～800mPas, more preferably has the polymkeric substance of the soltion viscosity of 15mPas～500mPas.In addition, the soltion viscosity (mPas) of polymkeric substance (P) is that concentration prepared by the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) to using this polymkeric substance is the polymers soln of 10 % by weight, use E type rotational viscosimeter at 25 DEG C, measures and must value.
The weight average molecular weight (Mw) of utilizing the polystyrene conversion that gel permeation chromatography (gel permeation chromatography, GPC) measures in polymkeric substance (P) is preferably 5,000～350,000, more preferably 10,000～250,000.
[other organopolysiloxane]
Described other organopolysiloxane can obtain by the hydrolysis-condensation reaction of described alkoxysilane compound containing trialkylsilyl group in molecular structure (A).The concrete example of the synthetic middle alkoxysilane compound containing trialkylsilyl group in molecular structure (A) using of described other organopolysiloxane can be applied the illustration of the alkoxysilane compound containing trialkylsilyl group in molecular structure (A) that can be used for synthetic described polymkeric substance (S).Other organopolysiloxane for example can be enumerated: have the organopolysiloxane of the represented structural unit of following formula (a1) and hydrolyzate thereof, with and the condenses of hydrolyzate etc.
[changing 10]
(in formula (a1), X afor alkyl, the alkoxyl group of carbon number 1～6 or the aryl of carbon number 6～20 of hydroxyl, halogen atom, carbon number 1～20; Y afor the alkoxyl group of hydroxyl or carbon number 1～10.)
The major part of described other organopolysiloxane can have an independent existence with polymkeric substance (S), or its part also can be used as with the condenses of polymkeric substance (S) and exists.
About described other organopolysiloxane, utilize the weight average molecular weight of the polystyrene conversion that gel permeation chromatography measures to be preferably 500～1,000,000, more preferably 1,000～150,000, be especially preferably 1,000～100,000.
Not only contain polymkeric substance (S) in liquid crystal aligning agent of the present invention, and contain in the situation of polymkeric substance (P) as other polymkeric substance, both preferred usage ratios are: with respect to polymkeric substance (S) 100 weight parts, the usage quantity of the total of polymkeric substance (P) is preferably 100 weight part～100,000 weight part, more preferably 100 weight part～5,000 weight part, especially be preferably 200 weight part～3,000 weight part.
On the other hand, contain in the situation of other organopolysiloxane as other polymkeric substance in liquid crystal aligning agent of the present invention, can be with respect to polymkeric substance (S) 100 weight parts, and the usage quantity of the total of other organopolysiloxane is made as below 2000 weight parts.Be preferably below 1,000 weight part, more preferably below 500 weight parts.
With respect to entire amount 100 weight parts of component of polymer, suitably the setting in can the scope below 100 weight parts containing the proportional of polymkeric substance (S) in liquid crystal aligning agent.With regard to making the good viewpoint of the solvent resistance of formed film, with respect to whole polymkeric substance 100 weight parts contained in liquid crystal aligning agent, polymkeric substance (S) containing proportional be preferably 0.1 weight part more than, more preferably more than 0.5 weight part, more than being especially preferably 1 weight part.In addition, just utilize other polymkeric substance to improve with regard to the viewpoint of electrical specification of liquid crystal display device, with respect to whole polymkeric substance 100 weight parts contained in liquid crystal aligning agent, polymkeric substance (S) containing proportional being preferably below 50 weight parts, more preferably, below 25 weight parts, be especially preferably below 20 weight parts.
Other compositions of < >
Only otherwise undermine effect of the present invention, liquid crystal aligning agent of the present invention, except containing component of polymer, also can contain other compositions such as the compound (below also referred to as " epoxy compounds ") in such as stiffening agent, hardening catalyst, hardening accelerator, molecule with at least one epoxy group(ing), functional silanes compound, tensio-active agent.
[stiffening agent, hardening catalyst and hardening accelerator]
Have in the situation of epoxy group(ing) in the polymkeric substance of allocating in liquid crystal aligning agent, stiffening agent and hardening catalyst can be for further promoting the object of the crosslinking reaction between epoxy construction to use.Hardening accelerator can use for the object that promotes the responsible sclerous reaction of stiffening agent.
As stiffening agent, for example, except hexanaphthene-1,3,4-tricarboxylic acid-3,4-acid anhydride, hexanaphthene-1,3,5-tricarboxylic acid-3,5-acid anhydride, 4-methyl tetrahydrophthalic anhydride, methyl carbic anhydride, dodecenylsuccinic acid acid anhydride, Succinic anhydried, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, trimellitic anhydride, following formula (6)
[changing 11]
(in formula (6), the integer that x is 1～20)
Represented compound, be generally used for, beyond the tetracarboxylic dianhydride of synthesizing polyamides acid, also can enumerating: α-terpinene (α-terpinene), alloocimene (alloocimene) etc. have the ester ring type compound of conjugated double bond and the Diels-Alder reaction of MALEIC ANHYDRIDE (Diels-Alder reaction) product and their hydride etc.
Described hardening catalyst for example can use antimony hexafluoride compound, phosphorus hexafluoride compound, triacetyl pyruvic acid aluminium etc.These catalyzer can carry out by heating the cationoid polymerisation of catalysis epoxy group(ing).Described hardening accelerator for example can be enumerated: imidazolium compounds; 4 grades of phosphorus compounds; 4 grades of amine compound; The Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] hendecene-7 or its organic acid salt; The organometallic compounds such as zinc octoate, stannous octoate, aluminium Acetyl Acetone complex compound; The boron compound such as boron trifluoride, triphenyl borate; The metal halogen compound such as zinc chloride, tin chloride; The high-melting-point decentralized potentiality hardening accelerators such as amine add-on type promotor such as the affixture of Dyhard RU 100 (dicyandiamide), amine and epoxy resin; 4 Ji phosphonium salts etc. are the microcapsule-type potentiality hardening accelerator by polymer overmold by surface; Amine salt type potentiality hardening accelerator; Lewis acid (Lewis acid salt), cloth are born the hot cationic polymerization type potentiality hardening accelerator of the high temperature dissociative types such as this special hydrochlorate (Bronsted acid salt) etc.
In making liquid crystal aligning agent, contain in the situation of stiffening agent, hardening catalyst or hardening accelerator, total 100 weight parts with respect to described polymkeric substance (S) with other polymkeric substance, it is containing proportional being preferably below 20 weight parts, more preferably below 10 weight parts.
[epoxy compounds]
Epoxy compounds can be contained in liquid crystal aligning agent for improving the object of the cementability of the liquid crystal orientation film forming to substrate surface.The concrete example of epoxy compounds for example can be enumerated: ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidylether, 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-benzyl amine, N, N-diglycidyl-amino methyl hexanaphthene etc.In addition, in the situation that contains epoxy compounds in liquid crystal aligning agent, cause well the object of its crosslinking reaction for efficiency, also can and use alkaline catalystss such as 1 benzyl 2 methyl imidazoles.
In making liquid crystal aligning agent, contain in the situation of epoxy compounds, total 100 weight parts with respect to described polymkeric substance (S) with arbitrarily used other polymkeric substance, described epoxy compounds containing proportional 0.01 weight part～40 weight part that is preferably, more preferably 0.1 weight part～30 weight part.
[functional silanes compound]
Functional silanes compound can use for the object that improves the liquid crystal orientation film of gained and the cementability of substrate.The concrete example of functional silanes compound for example can be enumerated: 3-TSL 8330, APTES, 2-TSL 8330, 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-tri-ethoxy silylpropyl diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-phenyl-3-TSL 8330, glycidoxypropyl methyltrimethoxy silane, 2-glycidoxypropyl ethyl trimethoxy silane, 3-glycidoxypropyltrimewasxysilane etc.
In making liquid crystal aligning agent, contain in the situation of functional silanes compound, total 100 weight parts with respect to described polymkeric substance (S) with arbitrarily used other polymkeric substance, being made as below 50 weight parts containing proportional being preferably of described functional silanes compound, is more preferably made as below 20 weight parts.
[tensio-active agent]
Tensio-active agent for example can be enumerated: nonionogenic tenside, anion surfactant, cats product, amphoterics, silicone surfactant, polyalkylene oxide (polyalkylene oxide) tensio-active agent, fluorochemical surfactant etc.In making liquid crystal aligning agent, contain in the situation of tensio-active agent, with respect to entire amount 100 weight parts of liquid crystal aligning agent, described tensio-active agent containing proportional being preferably below 10 weight parts, more preferably below 1 weight part.
The preparation > of < liquid crystal aligning agent
Liquid crystal aligning agent of the present invention be prepared into component of polymer and other compositions of optionally allocating be arbitrarily preferably dissolve or be scattered in organic solvent and molten liquid composition.
The organic solvent that can be used in preparation liquid crystal aligning agent of the present invention be preferably by polymkeric substance (S) and arbitrarily used other polymkeric substance and other compositions dissolve and not with the organic solvent of these polymer reactions.This organic solvent is according to the kind of other polymkeric substance that add arbitrarily and difference.Particularly, the preferred organic solvent in the situation that contains polymkeric substance (S) and polymkeric substance (P) in liquid crystal aligning agent of the present invention can enumerate as for the synthesis of the organic solvent of polyamic acid in illustrative organic solvent above.Now, can also using as also can for the synthesis of polyamic acid of the present invention poor solvent and illustrative solvent and use.
On the other hand, only contain in the situation of polymkeric substance (S) as component of polymer in liquid crystal aligning agent, or containing polymkeric substance (S) and other organopolysiloxane for example can enumerate as the preferred organic solvent in the situation of component of polymer: 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 ether, dipropylene glycol propyl ether, dipropylene glycol dme, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether (ethylene glycol butyl ether), ethylene glycol monopentyl ether, ethylene glycol ether, Diethylene Glycol, methylcellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetic ester, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl group Trivalin SF, diethylene glycol monobutyl ether, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, acetic acid 3-methoxyl group butyl ester, methyl amyl acetate, acetic acid 2-ethyl butyl ester, acetic acid 2-ethylhexyl, acetic acid benzyl ester, n-hexyl acetate, hexalin acetate, octyl acetate, pentyl acetate, Isoamyl Acetate FCC etc.
Described organic solvent can be according to the having or not and kind of the use of other polymkeric substance, and a kind of described organic solvent is used in combination above.In addition, described organic solvent is preferably under following preferred solid component concentration, and each composition contained in liquid crystal aligning agent can not be separated out, and the surface tension of liquid crystal aligning agent becomes the organic solvent of the scope of 25mN/m～40mN/m.
The solid component concentration of liquid crystal aligning agent, weight shared ratio in the gross weight of liquid crystal aligning agent of the whole compositions beyond the solvent in liquid crystal aligning agent is to consider that viscosity, volatility etc. select, and is preferably the scope of 1 % by weight～10 % by weight.Liquid crystal aligning agent is applied forms in substrate surface the film that becomes liquid crystal orientation film, more than solid component concentration is made as to 1 % by weight, forms the sufficient film of thickness, can obtain the liquid crystal orientation film that various characteristics is good.On the other hand, by solid component concentration is made as below 10 % by weight, the thickness that suppresses film becomes excessive, can obtain good liquid crystal orientation film.In addition, can prevent that the viscosity of liquid crystal aligning agent from increasing, and make coating characteristics good.
The scope of particularly preferred solid component concentration is according to the method adopting in the time of coating of liquid crystalline alignment agent on substrate and difference.For example, in utilizing in the situation of turner method, be preferably the scope of 1.5 % by weight～4.5 % by weight.In utilizing in the situation of print process, be preferably the scope that solid component concentration is made as to 3 % by weight～9 % by weight, thus soltion viscosity is made as to the scope of 12mPas～50mPas.In utilizing in the situation of ink jet method, be preferably the scope that solid component concentration is made as to 1 % by weight～5 % by weight, thus soltion viscosity is made as to the scope of 3mPas～15mPas.Temperature while preparing liquid crystal aligning agent is preferably 0 DEG C～200 DEG C, more preferably 0 DEG C～40 DEG C.
The manufacture method > of < liquid crystal display device
Liquid crystal display device of the present invention possesses the liquid crystal orientation film forming with liquid crystal aligning agent of the present invention as above.The drive pattern of liquid crystal display device of the present invention is not particularly limited, and can be applicable to multiple drive modes.
For example TN type, STN type, VA type (comprises vertical orientated-multidomain vertical orientation (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, vertical orientated (the Vertical Alignment-Patterned Vertical Alignment of vertical orientated-pattern, VA-PVA) type etc.), coplanar switching (In Plane Switching, IPS) type, fringing field switches (Fringe Field Switching, FFS) liquid crystal display device such as type can utilize the 1st manufacture method that comprises for example following step (1)～step (3) to manufacture.
(1) use liquid crystal aligning agent of the present invention on substrate, to form the step of film;
(2) optionally coated surface is implemented to give the step of processing of orientation; And
(3) make mode that film is relative a pair of substrate subtend that is formed with film be configured to form the step of liquid crystal cells with the layer across liquid crystal molecule.
In addition, can enumerate from described the 2nd different manufacture method the method that comprises for example following step (1 ')～step (3 ').
(1 ') is coated with respectively liquid crystal aligning agent of the present invention and forms the step of film on this conducting film of a pair of substrate with conducting film;
(2 ') make mode that film is relative a pair of substrate subtend that is formed with film be configured to form the step of liquid crystal cells with the layer across liquid crystal molecule; And
(3 ') are being executed under alive state liquid crystal cells are being carried out to light-struck step between the conducting film that a pair of substrate is had.
Below, described each manufacture method is described successively.
[the 1st manufacture method]
Step (1) in described the 1st manufacture method is used different substrates according to required operating mode.Step (3) shares with each operating mode.
[step (1): the formation of film]
First on substrate, be coated with liquid crystal aligning agent of the present invention, then, coated face heated, on substrate, form thus film.
(1-1) for example, in manufacturing in the situation of TN type, STN type or VA type liquid crystal display device, first, using two substrates that are provided with patterned nesa coating as a pair of, in its each transparent conducting film forming surface, be preferably and utilize offset printing method (offset printing method), method of spin coating (spin coating method), roll-coater method (roll coater method) or ink jet printing method (inkjet printing method) to be coated with respectively liquid crystal aligning agent of the present invention.Substrate for example can use: the glass such as float glass (float glass), soda glass (soda glass); The transparency carrier that comprises the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).The wherein nesa coating of one side that is arranged at substrate can use: comprise stannic oxide (SnO 2) NESA film (PPG register of company of U.S. trade mark), comprise Indium sesquioxide-stannic oxide (In 2o 3-SnO 2) tin indium oxide (indium tin oxide, ITO) film etc.In order to obtain patterned nesa coating, for example, can utilize following methods: form after patternless nesa coating, form the method for pattern by photoetch (photo etching); While forming nesa coating, use the method for the shade with required pattern etc.When coating of liquid crystalline alignment agent, in order to make the cementability of substrate surface and nesa coating and film better, also can implement to be coated with in advance to forming the face of film in substrate surface the pre-treatment of functional silanes compound, functionality titanium compound etc.
After coating of liquid crystalline alignment agent, for the object of sagging etc. that prevents be coated with liquid crystal aligning agent, be preferably and implement to preheat (prebake conditions).Prebake conditions temperature is preferably 30 DEG C～200 DEG C, more preferably 40 DEG C～150 DEG C, is particularly preferably 40 DEG C～100 DEG C.The prebake conditions time is preferably 0.25 minute～and 10 minutes, more preferably 0.5 minute～5 minutes.Then, for solvent is removed completely, optionally existing amido acid structure in polymkeric substance is carried out the object of hot-imide, and implement calcining (baking afterwards) step.Calcining temperature (rear storing temperature) is now preferably 80 DEG C～300 DEG C, more preferably 120 DEG C～250 DEG C.Rear baking time is preferably 5 minutes～and 200 minutes, more preferably 10 minutes～100 minutes.As mentioned above, the thickness of the film forming is preferably 0.001 μ m～1 μ m, more preferably 0.005 μ m～0.5 μ m.
(1-2) in manufacturing in the situation of IPS type or FFS type liquid crystal display device, be provided with comprise the electrode forming surface of the patterned substrate for the nesa coating of interdigitated electrode structure or the electrode of metallic membrane, with the one side of subtend substrate that electrode is not set, be coated with respectively liquid crystal aligning agent of the present invention, then, each coated face is heated, form thus film.About the preferred thickness of the pre-treatment of the patterning method of heating condition, nesa coating or metallic membrane after the material of the substrate that now used and nesa coating, coating process, coating, substrate and the film that forms, identical with described (1-1).Metallic membrane for example can use the film that comprises the metals such as chromium.
In described (1-1) and arbitrary situation (1-2), all by after coating of liquid crystalline alignment agent on substrate, remove organic solvent and form the film that becomes alignment films.Now, in the case of liquid crystal aligning agent of the present invention comprise polyamic acid, poly amic acid ester or there is imide ring structure and the imide amination polymer of amido acid structure as component of polymer, also can further heat to carry out dehydration closed-loop reaction by after forming at film, make the further film through imidization.
[step (2a): orientation process]
In manufacturing in the situation of TN type, STN type, IPS type or FFS type liquid crystal display device, conventionally the film forming in described step (1) is given the processing (orientation process) of liquid crystal aligning ability.Thus, the alignment capability of liquid crystal molecule is imparted to film and forms liquid crystal orientation film.Orientation process for example can be enumerated: utilize the roller of the cloth that is wound with fibers such as comprising nylon (nylon), artificial silk (rayon), cotton (cotton), the friction treatment to film to certain orientation wiping; Or utilize processing of optical alignment method etc.Wherein, with regard to the aspect of the decline of the bad generation of the demonstration that can suppress to be caused by dust or static or yield and can give equably with regard to the aspect of liquid crystal aligning ability film, be preferably use optical alignment method.On the other hand, in manufacturing in the situation of VA type liquid crystal display device, the film forming directly can be used as to liquid crystal orientation film, but also can carry out described processing to this film in described step (1).
In addition, also can further carry out following processing to the liquid crystal orientation film after friction treatment: by a part of irradiation ultraviolet radiation of liquid crystal orientation film is made liquid crystal orientation film a part of region tilt angle change processing; Or form after resist film in the part on liquid crystal orientation film surface, carry out friction treatment to the direction different from friction treatment just now, then remove the processing of resist film; Thereby make liquid crystal orientation film there is different liquid crystal aligning abilities in each region.In this situation, can improve the visual field characteristic of gained liquid crystal display device.The liquid crystal orientation film that is suitable for VA type liquid crystal display device also can be suitable for the liquid crystal display device of PSA pattern.
In optical alignment method, give liquid crystal aligning ability by the radioactive rays that irradiate polarisation or non-polarisation to being formed at film on substrate to film.Radioactive rays for example can use ultraviolet ray and the visible rays of the light that comprises 150nm～800nm wavelength.In the situation that is polarisation in radioactive rays, can be linear polarization, can be also part polarisation.In addition, in the situation in used radioactive rays for linear polarization or part polarisation, can irradiate from the direction vertical with real estate, also can irradiate from vergence direction, or they are combined to irradiate.In the situation of radioactive rays of irradiating non-polarisation, the direction of irradiation is made as vergence direction.
The light source using for example can use: Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.The ultraviolet ray of preferred wavelength region may is by obtaining the means of light source and such as spectral filter, diffraction grating etc. use etc.
Rayed can utilize following methods to carry out: the method that the film after rear baking procedure is irradiated; The method that film after pre-bake step and before rear baking procedure is irradiated; In at least arbitrary step of pre-bake step and rear baking procedure, the method for hankering film to irradiate in adding of film etc.The irradiation dose of light is preferably 100J/m 2～50,000J/m 2, more preferably 300J/m 2～20,000J/m 2.In addition, can, in order to improve reactivity, carry out the rayed to film and film is heated to one side on one side.Temperature when heating is generally 30 DEG C～250 DEG C, is preferably 40 DEG C～200 DEG C, more preferably 50 DEG C～150 DEG C.By photo-irradiation treatment as above, and on substrate, form liquid crystal orientation film.
[step (3): liquid crystal cells construct]
By preparing two substrates that are formed with in the above described manner liquid crystal orientation film, between two substrates of subtend configuration, configure liquid crystal and manufacture liquid crystal cells.Herein, in film being carried out in the situation of friction treatment, the substrate of two is mutually to become the angle of regulation, for example orthogonal or antiparallel mode with the frictional direction in each film to carry out subtend configuration.
In order to manufacture liquid crystal cells, for example, can enumerate following 2 kinds of methods.The first method is front known method for it.First, in the mode of each liquid crystal orientation film subtend, across gap (cell gap), two substrate subtends are configured, use sealing agent by the periphery laminating of two substrates, in the cell gap of being divided by substrate surface and sealing agent, inject after filling liquid crystal, by filling orifice sealing, can manufacture thus liquid crystal cells.In addition, the second method is for being called the gimmick of liquid crystal drip-injection (One Drop Fill, ODF) mode.Can be by the regulation position on the wherein substrate in two substrates that are formed with liquid crystal orientation film, be coated with the sealing material of for example ultraviolet light photopolymerization, and then several positions of regulation on liquid crystal aligning face drip after liquid crystal, with the mode of liquid crystal orientation film subtend another piece substrate of fitting, and liquid crystal is spread out on whole of substrate, then, to whole irradiating ultraviolet light of substrate, make hardening seal, thereby manufacture liquid crystal cells.In the situation that utilizing any method, it is desirable to by the liquid crystal cells of manufacturing in the above described manner, and then be heated to used liquid crystal and become after the temperature of isotropic phase, be slowly cooled to room temperature, thus the flow orientation when removing liquid crystal and filling.
In addition, in the situation that contains the organopolysiloxane with liquid crystal aligning base in liquid crystal aligning agent of the present invention, use in the manufacture of VA type liquid crystal display device of The liquid crystal aligning drug, even if adopt the situation of ODF mode (liquid crystal drip-injection mode), also there is excellent vertical orientated restraint, ODF is uneven few, suitable especially for the application of the manner.
Sealing agent for example can use and contain stiffening agent and as epoxy resin of the alumina balls of spacer etc.In addition, liquid crystal can be enumerated: nematic liquid crystal and smectic liquid crystal (smectic liquid crystal), wherein be preferably nematic liquid crystal, for example, can use: schiff bases (Schiff base) is that liquid crystal, azoxy (azoxy) are that liquid crystal, biphenyl are that liquid crystal, Santosol 360 are that liquid crystal, ester are that liquid crystal, terphenyl are that liquid crystal, cyclohexyl biphenyl hexane are that liquid crystal, pyrimidine are that liquid crystal, dioxan are that liquid crystal, double-octane are that liquid crystal, cubane (cubane) are liquid crystal etc.In addition, also can in these liquid crystal, add below material use: the cholesteric liquid crystals (cholesteric liquid crystal) such as such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate (cholesteryl carbonate); The chirality agent (chiral agent) of selling with trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company); To oxygen base α-tolylene-to ferroelectric liquid crystals such as amino-2-methyl butyl laurate (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) (ferroelectric liquid crystal) etc. in the last of the ten Heavenly stems.
[the 2nd manufacture method]
Step (1 ') in described the 2nd manufacture method and step (2 ') can be carried out in the mode identical with described step (1) and step (3) respectively.In addition, the film forming by step (1 ') can directly offer it next step (2 '), also can at random carry out as described in the friction treatment of step (2) and so on.The liquid crystal molecule using in step (2 ') is preferably the nematic liquid crystal with negative dielectric anisotropy, and for example can use dicyano benzene series liquid crystal, pyridazine (pyridazine) is that liquid crystal, schiff bases are that liquid crystal, azoxy are that liquid crystal, biphenyl are that liquid crystal, Santosol 360 are liquid crystal etc.The thickness of the layer of liquid crystal molecule is preferably and is made as 1 μ m～5 μ m.
In addition, in the situation of liquid crystal display device of manufacturing PSA pattern, also can will there is the compound (thiazolinyl liquid crystal) of thiazolinyl structure and be used as the liquid crystal molecule using in step (2 ').By making to contain thiazolinyl liquid crystal in liquid crystal layer, with regard to can accelerating the aspect of response speed of liquid crystal molecule preferably.Thiazolinyl liquid crystal can use existing known liquid crystal, for example, can enumerate the represented compound of following formula (L-1)～formula (L-10) difference etc.
[changing 12]
(in formula (L-1)～formula (L-10), the integer that n is 1～6.)
In step (3 '), the light that liquid crystal cells is irradiated for example can use ultraviolet ray and the visible rays of the light that comprises 150nm～800nm wavelength.Wherein, be preferably the ultraviolet ray of the light that comprises 300nm～400nm wavelength.The light source of light irradiation for example can use: Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.In addition, the ultraviolet ray of described preferred wavelength region may can be by obtaining the means of light source and such as spectral filter, diffraction grating etc. use etc.The irradiation dose of light is preferably 1,000J/m 2above and be less than 100,000J/m 2, more preferably 1,000J/m 2～50,000J/m 2.
After described step (3) or step (3 '), can obtain liquid crystal display device by the outer surface laminating Polarizer at liquid crystal cells.The Polarizer that fits in the outside surface of liquid crystal cells can be enumerated: be called as the Polarizer that the light polarizing film of " H film " forms or comprise itself Polarizer of H film with rhodia protective membrane clamping, described " H film " is to make polyvinyl alcohol extend orientation while light polarizing film that its absorption iodine is formed.
Liquid crystal display device of the present invention can be effectively applied to multiple device, for example can be used in: clock and watch, portable game machine (portable game), word processor (word processor), notes type PC (note type personal computer), auto-navigation system (car navigation system), video camera (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart mobile phone (smartphone), various watch-dogs, the display unit of LCD TV etc.
[embodiment]
Below, utilize embodiment to be specifically described the present invention, but the present invention is not limited to these embodiment.
In the present embodiment, the viscosity of the weight average molecular weight Mw of polymkeric substance and epoxy equivalent (weight) and polymers soln is to utilize following methods to measure.
[weight average molecular weight Mw]
Weight average molecular weight Mw is the polystyrene conversion value of utilizing the gel permeation chromatography under following condition to measure.
Tubing string: eastern Cao (Tosoh) (thigh) manufactures, TSKgelGRCXLII
Solvent: tetrahydrofuran (THF)
Temperature: 40 DEG C
Pressure: 68kgf/cm 2
[soltion viscosity of polymers soln]
The soltion viscosity (mPas) of polymers soln is to use E type rotational viscosimeter, at 25 DEG C, measures.
[the imide rate of polyimide]
The solution of polyimide is fed in pure water, at room temperature the precipitation of gained fully after drying under reduced pressure, is dissolved in deuterate dimethyl sulfoxide (DMSO), using tetramethylsilane as primary standard, at room temperature measure 1h-nucleus magnetic resonance ( 1h-Nuclear magnetic resonance, 1h-NMR).According to gained 1h-NMR spectrum, obtains imide rate [%] by the represented formula of following numerical expression (x).
Imide rate [%]=(1-A 1/ A 2× α) × 100... (x)
(in numerical expression (x), A 1for near the peak area of the proton that is derived from NH base that occurs chemical shift 10ppm, A 2for being derived from the peak area of other protons, α is the number ratios of other protons with respect to 1 proton of the NH base in the precursor (polyamic acid) of polymkeric substance.)
The synthetic > of < polymkeric substance (S)
[synthesis example 1-1]
To possessing in the reaction vessel of stirrer, thermometer, addition funnel and reflux cooling pipe, drop into the 2-(3 as alkoxysilane compound containing trialkylsilyl group in molecular structure (A), 4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane (ECETS) 167.088g (100 molar part), as 1 of alkoxysilane compound containing trialkylsilyl group in molecular structure (B), two (Trimethoxy silane base) the hexane 5.325g (3 molar part) of 6-, as the methyl iso-butyl ketone (MIBK) 172g of solvent and as the triethylamine 17g of catalyzer, at room temperature mix.Then, spend 30 minutes and in addition funnel, drip after deionized water 140g, at 80 DEG C, stir, carry out reaction in 6 hours.After reaction finishes, take out organic layer, after utilizing 0.2 % by weight aqueous ammonium nitrate solution to clean to become till neutrality to the water after cleaning, add as the methyl iso-butyl ketone (MIBK) 1000g of solvent, under decompression, solvent and water distillation are removed, obtained thus polymkeric substance (S-1) 123g.The Mw of this polymkeric substance (S-1) is 6,100.Prepare the ethylene glycol butyl ether 50 % by weight solution of this polymkeric substance (S-1), at 40 DEG C, leave standstill 10 days.By the both not also not gelations of tackify of state after leaving standstill, be storage stability " well " and keep the average evaluation of mobility; Though will there is mobility the average evaluation of tackify be storage stability " can "; The average evaluation that gelation and mobility are disappeared is " bad ", not gelation of polymers soln described in result, and storage stability is good.
[synthesis example 1-2～synthesis example 1-9]
In described synthesis example 1-1, except using respectively the compound of the kind shown in following table 1 and amount to be used as, alkoxysilane compound containing trialkylsilyl group in molecular structure (A) and alkoxysilane compound containing trialkylsilyl group in molecular structure (B), obtaining polymkeric substance (S-2)～polymkeric substance (S-9) in the mode identical with synthesis example 1-1.In addition, the numeric representation of the alkoxysilane compound containing trialkylsilyl group in molecular structure in table (A) and alkoxysilane compound containing trialkylsilyl group in molecular structure (B) for the synthesis of the alkoxysilane compound containing trialkylsilyl group in molecular structure (A) of polymkeric substance the usage quantity (molar part) with respect to entire amount 100 molar part.
Abbreviation in table 1 is as described below.
ECETS:2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane
M-503:3-methacryloxypropyl trimethoxy silane
TEOS: tetraethoxysilane
MTMS: methyltrimethoxy silane
DMDMS: dimethyldimethoxysil,ne
TMES: trimethylethoxysilane
DTES: dodecyl triethoxyl silane
M-3066:1, two (Trimethoxy silane base) hexanes of 6-
M-9659: isocyanuric acid three-(3-Trimethoxy silane base propyl group) ester
M-3086:1,8-pair-(Trimethoxy silane base) octane
M-666P: two [3-(Trimethoxy silane base) propyl group] amine
X-1056: triethoxysilicane alkyl thiopropyl Trimethoxy silane
[synthesis example 1-10]
In the there-necked flask of 300mL, drop into tetraethoxysilane 3.51g, dodecyl triethoxyl silane 33.6g, 1,6-two (triethoxysilicane alkyl) hexane 6.9g, Union carbide A-162 36.05g and the ethylene glycol butyl ether 66.9g as solvent, at room temperature stir.At room temperature, be pre-mixed ethylene glycol butyl ether 33.4g, water 30.0g and the oxalic acid solution as the oxalic acid 0.3g of catalyzer to dripping in this solution, drip and finish rear stirring 30 minutes.Then, place heat 1 hour at 70 DEG C of solution temperatures after cooling.Then, add ethyl acetate 500g, utilize distilled water to carry out separatory purifying, and remove catalyzer.Then take out organic layer, add ethylene glycol butyl ether 5000g, under reduced pressure solvent and water distillation are removed, obtain thus the solution of the organopolysiloxane (S-17) containing liquid crystal aligning base that comprises 10 % by weight.The Mw of the organopolysiloxane (S-17) containing liquid crystal aligning base of gained is 39,000.
[synthesis example 1-11]
In the there-necked flask of 300mL, drop into tetraethoxysilane 55.6g, dodecyl triethoxyl silane 22.2g and the ethylene glycol butyl ether 66.9g as solvent, at room temperature stir.At room temperature, be pre-mixed ethylene glycol butyl ether 33.4g, water 30.0g and the oxalic acid solution as the oxalic acid 0.3g of catalyzer to dripping in this solution, drip and finish rear stirring 30 minutes.Then, place heat 1 hour at 70 DEG C of solution temperatures after cooling.Then, add ethyl acetate 500g, utilize distilled water to carry out separatory purifying, and remove catalyzer.Then take out organic layer, add ethylene glycol butyl ether 5000g, under reduced pressure solvent and water distillation are removed, obtain thus the solution of the organopolysiloxane (S-18) containing liquid crystal aligning base that comprises 10 % by weight.The Mw of the organopolysiloxane (S-18) containing liquid crystal aligning base of gained is 3,000.
[synthesis example 2-1]
In the there-necked flask of 200mL, drop into polymkeric substance synthetic in described synthesis example 1-2 (S-2) 11.48g, methyl iso-butyl ketone (MIBK) 85g, there is 4-(4-n-pentyl cyclohexyl) phenylformic acid (PCPA) 3.52g of the carboxylic acid of liquid crystal aligning base and the four-normal-butyl bromination ammonium 1.15g as catalyzer, at 90 DEG C, stir and react for 12 hours.After reaction finishes, reaction mixture is made an addition in methyl alcohol, generate throw out., after the solution obtaining washing 3 times solvent distillation is removed this throw out being dissolved in ethyl acetate, obtain thus polymkeric substance (S-10) 14.3g.The Mw of this polymkeric substance (S-10) is 32,000.In addition, to carry out the test of storage stability with described identical mode, result is good.
[synthesis example 2-2～synthesis example 2-7]
In described synthesis example 2-1, except using respectively the compound of the kind shown in following table 2 and amount as the compound using in synthetic, obtain polymkeric substance (S-11)～polymkeric substance (S-16) in the mode identical with synthesis example 2-1.In addition, in table 2, the mol ratio of the Siliciumatom that the numeric representation of carboxylic acid has with respect to polymkeric substance (S).
[table 2]
Abbreviation in table 2 is as described below.
PCPA:4-(4-n-pentyl cyclohexyl) phenylformic acid
BMBA:3, two (the methacryloyl oxygen base) phenylformic acid of 5-
4POCA:4-phenoxy group styracin
The synthetic > of < polymkeric substance (P)
[synthesis example P-1]
Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic base NSC 60134 dianhydride 18.85g and cholestane oxygen base-2 as diamines, 4-diaminobenzene 8.83g and Ursol D 7.31g are dissolved in the NMP of 140g, carry out reaction in 4 hours at 60 DEG C.After reaction, measure the viscosity of this polymer fluid, result is 4,450mPas.Reaction soln is injected in excessive methyl alcohol, makes reaction product precipitation.Then, utilize methyl alcohol to clean, under reduced pressure at 40 DEG C, be dried 24 hours, obtain thus polyamic acid (PA-1) 32.8g.
[synthesis example P-2]
Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic base NSC 60134 dianhydride 13.94g and as cholestane oxygen base-2 of diamines, 4-diaminobenzene 6.23g and 3,5-diaminobenzoic acid 4.79g and 1-(4-aminophenyl) 2,3-dihydro-1,3,3-trimethylammonium-1H-indenes-6-amine 5.03g is dissolved in the NMP of 120g, carries out reaction in 4 hours at 60 DEG C.After reaction, measure the viscosity of this polymer fluid, result is 2,650mPas.Reaction soln is injected in excessive methyl alcohol, makes reaction product precipitation.Then, utilize methyl alcohol to clean, be under reduced pressure dried 24 hours with 40 DEG C, obtain thus polyamic acid.The polyamic acid of gained is all dissolved in the NMP of 170g again, add N-methyl piperidine 3.09g and diacetyl oxide 9.08g, at 110 DEG C, carry out 4 hours dehydration closed-loops, precipitating with described identical mode, cleaning, drying under reduced pressure, obtain polyimide (PI-1) 22.7g that imide rate is 65%.
[synthesis example P-3]
Make the pyromellitic acid anhydride 11g, 1 as tetracarboxylic dianhydride, 2,3,4-tetramethylene tetracarboxylic dianhydride 190g, as 4-aminophenyl-PABA ester 160g, 4,4 '-[4 of diamine compound, 4 '-propane-1,3-bis-bases two (piperidines-Isosorbide-5-Nitrae-bis-bases)] pentanoic 110g is dissolved in METHYLPYRROLIDONE 1300g, gamma-butyrolactone 1300g, carries out reaction in 6 hours at 40 DEG C, solid component concentration is 15%, and soltion viscosity is 420mPas.Reaction soln is injected in excessive methyl alcohol, makes reaction product precipitation.Then, utilize methyl alcohol to clean, be under reduced pressure dried 24 hours with 40 DEG C, obtain thus polyamic acid (PA-2) 465g.
The preparation > of < liquid-crystal composition
By nematic liquid crystal, (Merck & Co., Inc. manufactures, MLC-6608) be made as LCl, taken 10g, add wherein the represented optical polymerism compound 0.03g of the represented liquid crystal compounds 0.5g of following formula (L1-1) and following formula (L2-1), mix, obtain thus liquid-crystal composition LC2.
[changing 13]
[changing 14]
[embodiment 1]
The preparation > of < liquid crystal aligning agent
Get polyimide (PI-1) 100 weight parts that obtain in described synthesis example P-2 as other polymkeric substance, add wherein polymkeric substance (S-10) 10 weight parts, and then add NMP and ethylene glycol butyl ether (BC), making solvent composition is NMP: BC=50: 50 (weight ratios), solid component concentration are the solution of 6.0 % by weight.Utilize aperture be the strainer of 0.2 μ m by this solution filter, prepare thus liquid crystal aligning agent (E-1).
The evaluation > of < printing
The printing of the liquid crystal aligning agent to described preparation is evaluated.First, by described liquid crystal aligning agent, use the liquid crystal orientation film printing press (Japan's description printing (thigh) is manufactured) of hectograph type, coat the transparent electrical pole-face with the glass substrate of the transparency electrode that comprises ITO film, on the hot-plate of 80 DEG C, heat (prebake conditions) 1 minute and remove after solvent heating on the hot-plate of 200 DEG C (baking afterwards) 10 minutes.Thus, form taking contact pin type film thickness gauge (manufactures of KLA Tencor company) measure and must average film thickness as film.Utilizing multiplying power is this film of microscopic examination of 100 times and 20 times, finds out having or not of printing inequality and pin hole.Evaluate as follows: be printing " well " by the average evaluation of not observing printing inequality and pin hole under 100 times of multiplying powers, by the average evaluation of not observing printing inequality and pin hole under 20 times of multiplying powers be printing " can ", be printing " bad " by least any average evaluation of observing printing inequality and pin hole under 20 times of multiplying powers.Its result is, in the film forming with the liquid crystal aligning agent of described preparation, even if also all do not observe printing inequality and pin hole under 100 times of multiplying powers, printing is " well ".
The > of resistance to cleaning of < film
It is NMP: BC=50 that the liquid crystal aligning agent (E-1) of preparation in described embodiment 1 is diluted to solvent composition: 50 (weight ratios), solid component concentration 3.0 % by weight.Use turner by this solution coat in comprising on the glass substrate of 2cm × 6cm, on the hot-plate of 80 DEG C, carry out after 1 minute prebake conditions, in the baking oven that is replaced into nitrogen, at 200 DEG C, carry out baking after 1 hour, form thus the film that thickness is 100nm (liquid crystal orientation film).This film is flooded 10 hours at 60 DEG C in Virahol.Then, make film at 200 DEG C, be dried 1 hour in the baking oven that is replaced into nitrogen.Then, carry out the evaluation of the resistance to cleaning (solvent resistance) of film by measuring thickness (residual-film thickness).Evaluate as follows: be that more than 99nm average evaluation is solvent resistance " well " by film, by be less than 99nm and for more than 97nm average evaluation be solvent resistance " can ", be solvent resistance " bad " by the average evaluation that is less than 97nm, result, this film is 100nm, and the resistance to cleaning of film is good.
(manufacture of liquid crystal cells and evaluation)
The manufacture > of < liquid crystal cells
Use liquid crystal orientation film printing press (Japan's description printing (thigh) is manufactured), by the liquid crystal aligning agent of the embodiment of described preparation 1, coat on each electrode surface of two glass substrates respectively with ITO electrode, the patterned slit-shaped for as shown in Figure 1 of described ITO electrode and be divided into multiple regions, on the hot-plate of 80 DEG C, heat (prebake conditions) 1 minute and remove after solvent, heating on the hot-plate of 150 DEG C (baking afterwards) 10 minutes, formation average film thickness is film.For this film, in ultrapure water, carry out, after ultrasound cleaning in 1 minute, in 100 DEG C of cleaning ovens, being dried 10 minutes, obtain thus the substrate with liquid crystal orientation film.Repeat this operation, obtain a pair of (two) and have the substrate of liquid crystal orientation film.The pattern of the electrode using in addition, is the pattern identical with electrode pattern in PSA pattern.
Then,, in each outer rim with liquid crystal orientation film of described a pair of substrate, coating is added with after the epoxy resin adhesive of alumina balls that diameter is 5.5 μ m, with the overlapping crimping of the relative mode of liquid crystal aligning face, makes adhesive hardens.Then, after filling liquid crystal composition LC1 between a pair of substrate (Merck & Co., Inc. manufactures, MLC-6608), utilize acrylic acid series photo-hardening caking agent that liquid crystal injecting port is sealed from liquid crystal injecting port, manufacture thus liquid crystal cells.
Repeat described operation, manufacture the liquid crystal cells that adds up to the patterned transparency electrode of 5 have.Wherein 1 directly offers the evaluation of aftermentioned voltage retention.For remaining 4 liquid crystal cells, between to conducting film, execute under alive state, with 100,000J/m 2irradiation dose carry out, after rayed, offering the evaluation of liquid crystal cells.
The evaluation > of < liquid crystal aligning
Be 100,000J/m for rayed amount in the liquid crystal cells of described manufacture 2liquid crystal cells, utilizing multiplying power is the microscope of 50 times, observes having or not of abnormal area in the light and shade variation of connecting while disconnecting (ONOFF) (applying releasings) 5V voltage.Being liquid crystal aligning " well " by the average evaluation of not observing abnormal area, is liquid crystal aligning " bad " by the average evaluation of observing abnormal area, result, and the liquid crystal aligning of this liquid crystal display device is " well ".
The evaluation > of < voltage retention
Be 100,000J/m for the non-irradiated liquid crystal cells of light and rayed amount in the liquid crystal cells of described manufacture 2liquid crystal cells, at 23 DEG C, apply after 5V voltage with the application time of 60 microseconds, the interval of 167 milliseconds, measure voltage retention (the Voltage Holding Ratio after 167 milliseconds from applying releasing, VHR), result, the voltage retention of the non-irradiated liquid crystal cells of light is 99.2%, and irradiation dose is 100,000J/m 2the voltage retention of liquid crystal cells be 98.6%.In addition, determinator uses the VHR-1 that Dongyang Te Kenika (Toyo Technica) (thigh) manufactures.
Evaluation (evaluation of the tilt angle stability) > of < image retention characteristic
Be 100,000J/m for rayed amount in the liquid crystal cells of described manufacture 2liquid crystal cells, according to the method for recording in " people such as T.J.Scheffer " Japanese applied physics magazine " (Japanese Journal of Applied Physics; J.Appl.Phys.) the 48th volume the 1783rd page (1977) " and " people such as F. Nakano " Japanese applied physics magazine " the 19th volume the 2013rd page (1980) ", utilize and use the rotating-crystal method of He-Ne laser to measure.Subtend liquid crystal cells applies the tilt angle (initial pretilt theta ini) before voltage and at room temperature drives 13 hours tilt angles (pretilt theta ac after driving) afterwards to measure with the alternating-current (alternating current, AC) of 9V.In addition, utilize following formula (y) to calculate tilt angle velocity of variation β [%].Tilt angle velocity of variation β is less than to 4% average evaluation for " good ", be more than 4% by tilt angle velocity of variation β and be less than 5% average evaluation for " well ", be that more than 5% average evaluation is " bad " by tilt angle velocity of variation β, result, the tilt angle velocity of variation of this liquid crystal cells is 3.1%, is judged as " good ".
Tilt angle velocity of variation β [%]=(θ ac-θ ini)/θ ini × 100... (y)
The stable on heating evaluation of < >
In the evaluation of voltage retention, will be made as initial VHR through the voltage retention of light-struck liquid crystal display device bF.Then, by VHR bFliquid crystal display device after mensuration leaves standstill 1,000 hour in the baking oven of 100 DEG C.Then, by this liquid crystal display device at room temperature leave standstill, place be cooled to after room temperature, with initial voltage conservation rate VHR bFthe identical condition of mensuration measure voltage retention (VHR aF).In addition, utilize following numerical expression (2) to obtain thermal stresses and give the velocity of variation (△ VHR (%)) of the voltage retention of front and back.
△VHR(％)＝((VHR BF-VHR AF)÷VHR BF)×100...(2)
Evaluate as follows: velocity of variation △ VHR being less than to 4% average evaluation is thermotolerance " good ", being more than 4% by velocity of variation △ VHR and being less than 5% average evaluation for " well ", is that more than 5% average evaluation is thermotolerance " bad " by velocity of variation △ VHR.Its result is, △ VHR is 2.6%, and the thermotolerance of liquid crystal display device is " good ".
[embodiment 2～embodiment 9 and comparative example 1, comparative example 2]
Except by the kind of the polymkeric substance for the preparation of liquid crystal aligning agent and quantitative change more as described in Table 3, prepare respectively liquid crystal aligning agent in the mode identical with embodiment 1.In addition, use respectively these liquid crystal aligning agent, manufacture liquid crystal display device in the mode identical with embodiment 1, and the liquid crystal display device of manufacturing is evaluated.Their evaluation result is shown in following table 3.In addition,, in embodiment 4, embodiment 5, embodiment 7 and comparative example 1, comparative example 2, replace LC1 as liquid-crystal composition with LC2.
In the embodiment 1～embodiment 9 that comprises polymkeric substance (S), be film solvent resistance, printing, liquid crystal aligning, voltage retention, image retention characteristic and stable on heating being evaluated as " good ", " well " and " can " in any, various characteristics averages out.On the other hand, in comparative example 1, comparative example 2, solvent resistance and poor heat resistance in the film forming.
[embodiment 10:FFS type liquid crystal display device]
(1) preparation of liquid crystal aligning agent
Get polyimide (PA-2) 100 weight parts that obtain in described synthesis example P-3 as polymkeric substance (P), add wherein polymkeric substance (S-16) 10 weight parts, and then add NMP and ethylene glycol butyl ether (BC), making solvent composition is NMP: BC=50: 50 (weight ratios), solid component concentration are the solution of 6.0 % by weight.Utilize aperture be the strainer of 0.2 μ m by this solution filter, prepare thus liquid crystal aligning agent (E-12).
The evaluation > of < printing
For the liquid crystal aligning agent (E-12) of described preparation, carry out the evaluation of printing in the mode identical with the evaluation > of described embodiment 1< printing.Its result is, in the film forming with the liquid crystal aligning agent of described preparation, even if all do not observe printing inequality and pin hole under 100 times of multiplying powers, printing is " well ".
[the resistance to cleaning of film]
It is NMP: BC=50 that the liquid crystal aligning agent of described preparation (E-12) is diluted to solvent composition: 50 (weight ratios), solid component concentration are 3.0 % by weight.Use turner, by this solution coat in the glass substrate that comprises 2cm × 6cm, on the hot-plate of 80 DEG C, carry out after 1 minute prebake conditions, in the baking oven that is replaced into nitrogen, carry out baking after 1 hour with 200 DEG C, form thus the film that thickness is 100nm (liquid crystal orientation film).To this film, carry out the evaluation of the resistance to cleaning of film in the mode identical with the > of resistance to cleaning of described embodiment 1< film.Its result is, this film is 100nm, and the resistance to cleaning of film is " well ".
(manufacture of liquid crystal cells and evaluation)
The manufacture > of <FFS type liquid crystal display device
The liquid crystal display device 10 of the FFS type liquid crystal display device shown in construction drawing 2.First, the not figuratum bottom electrode 12 of tool, as the silicon nitride film 13 of insulation layer, and as the top electrode 14 glass substrate 11a that lamination forms successively of the patterned electrode pair for comb teeth-shaped, with the subtend glass substrate 11b that electrode is not set as a pair of, use turner, be coated with respectively the liquid crystal aligning agent (E-12) of described preparation in the face with electrode of glass substrate 11a and the one side of subtend glass substrate 11b, utilize the hot-plate of 80 DEG C to carry out after 1 minute prebake conditions, in to storehouse, carry out in the baking oven of nitrogen replacement with 200 DEG C of heating (baking afterwards) 1 hour, formation average film thickness is film.The floor map of top electrode 14 is shown in Fig. 3 (a) and Fig. 3 (b).In addition, Fig. 3 (a) is the vertical view of top electrode 14, and Fig. 3 (b) is the enlarged view of the part C1 by dotted line of Fig. 3 (a).In the present embodiment, use the live width d1 with transparency electrode be 4 μ m, interelectrode be the substrate of the top electrode of 6 μ m apart from d2.Hollow arrow in Fig. 3 (b) represents the direction of the ultraviolet plane of polarization of polarisation.
Each surface of the film to described formation, is used Hg-Xe lamp and Glan-Taylor prism (Glan-Taylor prism), irradiates the polarisation ultraviolet ray 300J/m that comprises 313nm open-wire line from substrate normal direction 2, obtain a pair of substrate with liquid crystal orientation film 15a, liquid crystal orientation film 15b.The wherein periphery of the face with liquid crystal orientation film of in described substrate, be coated with and be added with the epoxy resin adhesive that diameter is the alumina balls of 5.5 μ m by screen painting, then the liquid crystal orientation film that makes a pair of substrate in the face of to, become the overlapping crimping of parallel mode with the direction that ultraviolet polarisation plane of polarization is projected on substrate, at 150 DEG C, spend 1 hour and make caking agent heat embrittlement.Then, fill after the liquid crystal " MLC-6221 " of Merck & Co., Inc.'s manufacture in substrate gap from liquid crystal injecting port, utilize epoxy resin adhesive that liquid crystal injecting port is sealed.Then, the flow orientation when eliminating Liquid crystal pour, is slowly cooled to room temperature after being heated to 150 DEG C again.
Then,, at the two sides, outside of substrate laminating Polarizer, manufacture thus FFS type liquid crystal display device.Now, in Polarizer wherein one be the parallel mode of the projection direction of real estate to be attached with the ultraviolet plane of polarization of polarisation of liquid crystal orientation film with its polarization direction, another piece is to attach in the orthogonal mode of its polarization direction and the polarization direction of Polarizer just now.
Repeat described method, manufacture the FFS type liquid crystal display device that adds up to 2, offer one by one the evaluation of following liquid crystal aligning and the evaluation of voltage retention.
The evaluation > of < liquid crystal aligning
For the liquid crystal display device of described manufacture, carry out the evaluation of liquid crystal aligning in the mode identical with the evaluation > of described embodiment 1< liquid crystal aligning.Its result is that the liquid crystal aligning of this liquid crystal display device is " well ".
The evaluation > of < voltage retention
To the liquid crystal display device of described manufacture, carry out the evaluation of voltage retention in the mode identical with the evaluation > of described embodiment 1< voltage retention.Its result is that voltage retention is 99.1%.

Claims (12)

1. a liquid crystal aligning agent, it is characterized in that: contain polymkeric substance (S), described polymkeric substance (S) is in 1 molecule, to have the polymerization in the alkoxysilane compound containing trialkylsilyl group in molecular structure (A) of 1 alkoxysilane group and 1 molecule with the alkoxysilane compound containing trialkylsilyl group in molecular structure (B) of more than 2 alkoxysilane group to obtain by comprising in monomer composition, and
With respect to described alkoxysilane compound containing trialkylsilyl group in molecular structure (A), the described alkoxysilane compound containing trialkylsilyl group in molecular structure (B) using in the polymerization of described polymkeric substance (S) is 3 % by mole～30 % by mole.
2. liquid crystal aligning agent according to claim 1, it is characterized in that: the total mole number with respect to described alkoxysilane compound containing trialkylsilyl group in molecular structure (A) with described alkoxysilane compound containing trialkylsilyl group in molecular structure (B), in described alkoxysilane compound containing trialkylsilyl group in molecular structure (A), the amount of contained tetraalkoxysilane is below 30 % by mole.
3. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: described polymkeric substance (S) has epoxy group(ing).
4. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: contain described polymkeric substance (S) and select at least one polymkeric substance (P) in the cohort that free polyamic acid, poly amic acid ester and polyimide form as component of polymer.
5. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: contain the organopolysiloxane with the two keys of polymerizability as described polymkeric substance (S).
6. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: contain organopolysiloxane as described polymkeric substance (S), described organopolysiloxane contains the liquid crystal aligning base with the function that makes liquid crystal molecular orientation.
7. liquid crystal aligning agent according to claim 1 and 2, it is characterized in that: contain organopolysiloxane as described polymkeric substance (S), described organopolysiloxane has and can react or photodimerizationization reaction and give anisotropic smooth orientation base to film by photoisomerization.
8. a manufacture method for liquid crystal display device, is characterized in that comprising:
By coating respectively according to the liquid crystal aligning agent described in any one in claim 1 to 6 on the described conducting film of a pair of substrate with conducting film, then its heating is formed the step of film; With described film across the liquid crystal layer that comprises liquid crystal compounds and relative mode, by the step that is formed with a pair of substrate subtend configuration of described film and construct liquid crystal cells; And execute under alive state described liquid crystal cells is carried out to light-struck step between the conducting film that described a pair of substrate is had.
9. the manufacture method of liquid crystal display device according to claim 8, is characterized in that: make to contain the compound with thiazolinyl structure as described liquid crystal compounds in described liquid crystal layer.
10. a manufacture method for liquid crystal display device, is characterized in that comprising: orientation process step, is used liquid crystal aligning agent according to claim 7, on substrate, form film, then, at certain orientation, real estate is carried out to rayed, give anisotropy to described film.
11. 1 kinds of liquid crystal orientation films, is characterized in that: by forming according to the liquid crystal aligning agent described in any one in claim 1 to 7.
12. 1 kinds of liquid crystal display device, is characterized in that: possess liquid crystal orientation film according to claim 11.
CN201410025139.1A 2013-02-07 2014-01-20 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells and its manufacture method Active CN103980911B (en)

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KR102018163B1 (en) 2019-09-04

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