CN102629030A - Liquid crystal display element and manufacturing method thereof, and liquid crystal orientation agent - Google Patents

Liquid crystal display element and manufacturing method thereof, and liquid crystal orientation agent Download PDF

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Publication number
CN102629030A
CN102629030A CN2012100282102A CN201210028210A CN102629030A CN 102629030 A CN102629030 A CN 102629030A CN 2012100282102 A CN2012100282102 A CN 2012100282102A CN 201210028210 A CN201210028210 A CN 201210028210A CN 102629030 A CN102629030 A CN 102629030A
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liquid crystal
aforementioned
substrate
crystal display
display cells
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宫本佳和
德久博昭
杉山文隆
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JSR Corp
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JSR Corp
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    • 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
    • G02F1/133753—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—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
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • 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
    • G02F1/133753—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle
    • G02F1/133757—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle with different alignment orientations

Abstract

The invention refers to a liquid crystal display element and manufacturing method thereof, and liquid crystal orientation agent. The invention provides a liquid crystal orientation agent used for obtaining a liquid crystal display element which can display a high voltage holding ratio and an excellent low residual shadow property at high temperatures. The liquid crystal display element (10) forms, on a surface of a substrate selected from the pair of substrates (11a,11b),a first orientation film (13) for making liquid crystal molecules obliquely orientate relative to a direction perpendicular to the substrate surface; and on the surface of the other substrate, a second orientation film (15) for making the liquid crystal molecules orientate perpendicularly. In particular, the first orientation film (13) is formed by using a liquid crystal orientation agent including radiation sensitive compounds of light orientation perssad; the light orientation perssad comprises at least one compound selected from the group formed by free azobenzene, stilbene, alpha- imino group-beta ketonic ester, spiropyrane, spirooxazine, cinnamic acid, chalcone, stilbazole, toluenesulfonic adjacent benzene 2 formyl imine, coumarin, dibenzenyl and anthraquinone.

Description

Liquid crystal display cells and manufacturing approach thereof and aligning agent for liquid crystal
Technical field
The present invention relates to liquid crystal display cells and manufacturing approach thereof and aligning agent for liquid crystal; In particular to have through optical alignment method give liquid crystal aligning can liquid crystal display cells and manufacturing approach thereof and the aligning agent for liquid crystal that is used to obtain this liquid crystal display cells of liquid crystal orientation film.
Background technology
At present, as liquid crystal display cells, for example known having makes vertical orientated VA (vertical orientated) the type liquid crystal display cells of the relative substrate of liquid crystal molecule etc.VA type liquid crystal display cells is under the state that does not apply voltage, and the relative substrate surface of liquid crystal molecule vertically is orientated; Applying under the state of voltage, making the relative substrate surface horizontal direction of liquid crystal molecule ground orientation.This VA type liquid crystal display cells for example through rib or electrode narrow slit are set, is controlled the vergence direction of the liquid crystal molecule of vertical orientated state at present.
In addition, as the liquid crystal aligning technology, concentrate and pay close attention to the irradiates light of filming in recent years, thereby on this is filmed, give the optical alignment method of liquid crystal aligning ability, to replace existing rubbing manipulation forming on the substrate surface.According to this method, have that can make films and itself manifest the performance of the liquid crystal tilted alignment of sening as an envoy to (crooked orientation), the good advantage of response speed that the liquid crystal molecule relative voltage is changed.In addition, the advantage that also has the tilt angle that to control the relative substrate surface of liquid crystal molecule this moment accurately.
Propose to have various schemes (for example, with reference to patent documentation 1 or patent documentation 2) to liquid crystal display cells with the liquid crystal orientation film that forms through this optical alignment method.In patent documentation 1,2; Disclose on two substrate surfaces separately; Use comprises the aligning agent for liquid crystal of radiation-sensitive polysiloxane and forms and film, and uses to have the substrate to the optical alignment film of these irradiates lights of filming, and makes liquid crystal display cells.
[prior art document]
[patent documentation]
No. 4416054 communique of [patent documentation 1] japanese
[patent documentation 2] TOHKEMY 2010-185001 communique
Summary of the invention
In recent years, have the requirement that further raising liquid crystal indicator is realized high image quality, in order to realize this target, liquid crystal display cells is necessary further to improve the response (response speed) of liquid crystal molecule to change in voltage.
The present invention proposes in view of the above problems, and its fundamental purpose is to provide liquid crystal molecule to the response property of change in voltage excellent liquid crystal display cells and manufacturing approach thereof, is used to make the aligning agent for liquid crystal of this liquid crystal display cells.
The present invention adopts following means to achieve these goals.
Liquid crystal display cells of the present invention is the liquid crystal display cells with a pair of substrate; It is characterized in that: on the substrate surface in aforementioned a pair of substrate; Formation makes the 1st alignment films of the direction tilted alignment of vertical relatively this substrate surface of liquid crystal molecule; And on another substrate surface; Formation makes the 2nd vertical orientated alignment films of liquid crystal molecule; Aforementioned the 1st alignment films use comprises the aligning agent for liquid crystal of the radiation-sensitive compound with light orientation group and forms, the structure of at least a compound of selecting in the group that this light orientation group has free azobenzene, talan, alpha-imino-'beta '-ketoester, spiro-pyrans, spiral shell oxazine, cinnamic acid, chalcone, stilbene azoles, benzal phthalimide, cumarin, dibenzenyl and anthraquinone to constitute.
In addition; The manufacturing approach of liquid crystal display cells of the present invention is the manufacturing approach with liquid crystal display cells of a pair of substrate; It is characterized in that: comprise the manufacturing process that makes liquid crystal display cells; On the substrate surface of this liquid crystal display cells in aforementioned a pair of substrate; Formation makes the 1st alignment films of the direction tilted alignment of vertical relatively this substrate surface of liquid crystal molecule; And on another substrate surface; Formation makes the 2nd vertical orientated alignment films of liquid crystal molecule, and aforementioned the 1st alignment films uses the light orientation that comprises the radiation-sensitive compound with light orientation group to form the structure of at least a compound of selecting in the group that this light orientation group has free azobenzene, talan, alpha-imino-'beta '-ketoester, spiro-pyrans, spiral shell oxazine, cinnamic acid, chalcone, stilbene azoles, benzal phthalimide, cumarin, dibenzenyl and anthraquinone to constitute with aligning agent for liquid crystal.
According to the present invention; In liquid crystal display cells; A conduct in the liquid crystal orientation film that a pair of substrate has makes the alignment films of the direction tilted alignment on the relative vertical substrate of liquid crystal molecule surface, and another is as vertical alignment layer, simultaneously; Previous alignment films is to form through the aligning agent for liquid crystal that comprises the radiation-sensitive compound with specific light orientation group, can obtain the excellent liquid crystal display cells of response characteristic of the liquid crystal molecule of liquid crystal molecule relative voltage variation.
In the present invention, aforementioned lights orientation group also can have the structure from cinnamic acid.In addition, can be the compound that comprises polysiloxane as aforementioned radiation-sensitive compound with aforementioned lights orientation group, in this case, can be used as further to the excellent compound of long-time light-struck permanance (photostability).
As the manufacturing approach of liquid crystal display cells of the present invention, can enumerate out following two kinds of schemes particularly here.At first, as first kind of scheme, can enumerate out following proposal, promptly aforementioned manufacturing process comprises: on the surface of a substrate in aforementioned a pair of substrate, use the aforementioned lights orientation use aligning agent for liquid crystal, form the 1st the 1st film formation operation of filming; Through to the aforementioned the 1st irradiates light of filming, make the 1st to film and become the rayed of aforementioned the 1st alignment films operation; On another substrate surface in aforementioned a pair of substrate, use can form the aligning agent for liquid crystal of vertical alignment layer, forms the 2nd film of filming as the 2nd of aforementioned the 2nd alignment films and forms operation; And make aforementioned the 1st alignment films and the aforementioned the 2nd aforementioned a pair of substrate of subtend ground configuration of filming, and between this substrate the filling liquid crystal molecule, the box that constitutes liquid crystal cell constitutes operation.
In addition, as second kind of scheme, can enumerate out following proposal, promptly aforementioned manufacturing process comprises: on the surface of a substrate in aforementioned a pair of substrate, use the aforementioned lights orientation to use aligning agent for liquid crystal, form the 1st film of filming and form operation; On another substrate surface in aforementioned a pair of substrate, use the aligning agent for liquid crystal that does not contain the compound with light orientation group in fact, the 2nd film that forms aforementioned the 2nd alignment films forms operation; Make aforementioned filming and the aforementioned a pair of substrate of aforementioned the 2nd alignment films subtend ground configuration, and between this substrate the filling liquid crystal molecule, the box that constitutes liquid crystal cell constitutes operation; And, between aforementioned a pair of substrate, apply under the state of voltage the rayed operation of irradiates light to the foregoing liquid crystal box that aforementioned box formation operation constitutes.In these two kinds of schemes, from the viewpoint of liquid crystal molecule to the response of change in voltage, more preferably above-mentioned first kind of scheme.
Description of drawings
Fig. 1 is the longitudinal section of liquid crystal display cells.
Fig. 2 is the figure of the pattern form of expression nesa coating.
Embodiment
[liquid crystal display cells]
Below, suitably liquid crystal display cells of the present invention is described with reference to accompanying drawing.Fig. 1 is the synoptic diagram of an example of expression liquid crystal display cells of the present invention.
As shown in Figure 1, liquid crystal display cells 10 has a pair of substrate 11a, 11b, and they are configuration each other with leaving.Substrate 11a, 11b can pass through for example by glass such as float glass, soda-lime glass; Polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, gather the transparency carrier that plastics such as (ester ring type alkene) form and constitute.
In a pair of substrate,, the 1st electrode 12 is set on the substrate 11a and on the surface of another substrate 11b opposite side.So long as generally use, just do not have special qualification as the 1st electrode 12, can use for example nesa coating as the electrode of liquid crystal display cells.As nesa coating, can use by tin oxide (SnO 2) form NESA film (registered trademark of U.S. PPG company), by indium oxide-tin oxide (In 2O 3-SnO 2) the ITO film that forms etc.
In the 1st electrode 12, with the surface of substrate 11b opposite side on, form the 1st alignment films 13.The 1st alignment films 13 is by the direction on relative vertical substrate surface, can make the organic film of liquid crystal molecules tilt orientation and constitutes.In other words, as shown in Figure 1, in the 1st alignment films 13, the angle that liquid crystal molecule stretches out from substrate surface (tilt angle) is θ (0＜θ＜90 °).The thickness of the 1st alignment films 13 is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
In substrate 11b, with the surface of the opposite side of substrate 11a on, the 2nd electrode 14 is set.Can use and the same electrode of the 1st electrode 12 illustrative nesa coatings as the 2nd electrode 14.For example, when liquid crystal display cells of the present invention is applied to use the mode of TFT, can with one in the 1st electrode 12 and the 2nd electrode 14 as counter electrode, with another as pixel electrode.
In the 2nd electrode 14, form the 2nd alignment films 15 on surface with substrate 11a opposite side.The 2nd alignment films 15 constitutes through making the vertical orientated organic film of the relative substrate surface of liquid crystal molecule.The thickness of the 2nd alignment films 15 is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
15 of the 1st alignment films 13 and the 2nd alignment films, form the liquid crystal layer 17 of filling liquid crystal molecule 16.As liquid crystal molecule 16, preferably use for example nematic crystal, dish-like liquid crystal etc.Particularly, preferably have the nematic crystal of negative dielectric anisotropy, particularly, can use for example dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, schiff alkali class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal etc.The thickness of liquid crystal layer 17 is preferably 1.2～8.0 μ m, and more preferably 1.3～5.5 μ m further are preferably 1.4～4.0 μ m.
At the outside surface of a pair of substrate 11a, 11b polaroid 18,19 is installed respectively.As polaroid 18,19, when can use, clamp absorption iodine with the acetyl cellulose diaphragm and be called the film formed polaroid of polarisation of " H film " or the polaroid that forms by H film itself polyvinyl alcohol (PVA) extension orientation.
Then, the 1st alignment films 13 among the present invention and the 2nd alignment films 15 are described.The 1st alignment films 13 among the present invention and the 2nd alignment films 15 use any one polymkeric substance at least of comprising polyamic acid and polyimide as the aligning agent for liquid crystal (the 1st alignment agent, the 2nd alignment agent) of component of polymer and form respectively.
[the 1st alignment agent]
The 1st alignment agent that is used to form the 1st alignment films 13 comprises the radiation-sensitive compound with light orientation group and constitutes.
< radiation-sensitive compound >
The light orientation group that radiation-sensitive compound among the present invention is had is to give anisotropic functional group through rayed to film; In the present invention; Particularly through produce light opposite sexization reaction and photodimerization reaction at least any one, give anisotropic group to film.
The light orientation group that is fit to use during as formation the 1st alignment films 13, concrete is the group that has the structure of at least a compound of selecting in the group of free azobenzene, talan, alpha-imino-'beta '-ketoester, spiro-pyrans, spiral shell oxazine, cinnamic acid, chalcone, stilbene azoles, benzal phthalimide, cumarin, dibenzenyl and anthraquinone formation.As glazing orientation group, among them, especially preferably has group from the cinnamic acid structure.As structure from cinnamic acid, can use particularly shown in the following formula (c1),
Figure BSA00000668597200061
In the formula, R is that carbon number is 1～6 alkyl or alkoxy, fluorine atom or cyanic acid.A is 0～4 integer, and a is 2～4 o'clock, and a plurality of R have above-mentioned definition independently of one another." * " representes connecting key.
As the carbon number among the R of above-mentioned formula (c1) is 1～6 alkyl, can enumerate out for example methyl, ethyl, butyl etc.In addition, be 1～6 alkoxy as carbon number, can enumerate out for example methoxyl, ethoxy, propoxyl group etc.
As a, preferred 0 or 1, more preferably 0.
As light orientation group with the structure shown in the above-mentioned formula (c1), the group shown in preferred particularly following formula (c1-1) or the formula (c1-2),
Figure BSA00000668597200071
In the formula, R 1And R 3The carbon number that is hydrogen atom independently of one another, has an ester ring type group is 3～40 1 valency organic group, or the carbon number with fluorine atom be 1～40 alkyl.R 2And R 4Be independently of one another methylene ,-Si (CH 3) 2-,-CH=CH-,-C ≡ C-or divalent group with ring type structure.X 1, X 2And X 3Be independently of one another singly-bound, oxygen atom ,-CO-,-COO-,-NR a,-CO-NR a,-NR a-CO-O-,-NR a-CO-NR a,-O-CO-O-(wherein, R aBe that hydrogen atom or carbon number are 1～4 alkyl independently of one another).X 4Be singly-bound or oxygen atom.B and c are 0～3 integer independently of one another, and b, c are 2 or 3 o'clock, a plurality of R 2, R 4, X 2, X 4Has above-mentioned definition independently of one another.R, a are identical with the definition of above-mentioned formula (c1) respectively with " * ".
R as above-mentioned formula (c1-1) 1R with above-mentioned formula (c1-2) 3In the carbon number with ester ring type group be 3～40 1 valency organic group, can enumerate out for example cyclohexyl methyl, cyclohexyl propyl group, cyclohexyl amyl group, cyclohexyl heptyl, ring octyl group, adamantyl, cholestane base, cholesteryl, lanostane base etc.
As R 1And R 3In carbon number be 1～40 alkyl, can be the straight chain shape, also can be branched.As this alkyl; Preferred carbon number is 1～20, can enumerate out for example methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base, n-eicosane base etc. particularly.If this alkyl is from can showing the viewpoint of good liquid crystal aligning property, among them, preferred carbon number is the alkyl of 1～12 straight chain shape, and preferred especially carbon number is the alkyl of 4～12 straight chain shape.
R 1And R 3In at least 1 hydrogen atom that carbon atom had of alkyl can be replaced by fluorine atom.As the object lesson of this fluoro-alkyl, for example can enumerate out 3,3,3-three fluoro propyl group, 4,4,4-three fluoro butyl, 4,4; 5,5,5-five fluoro amyl groups, 4,4,5,5,6; 6,6-seven fluoro hexyls, 3,3,4,4,5,5; 5-seven fluoro amyl groups, 2,2,2-trifluoroethyl, 2,2,3,3,3-five fluoropropyls, 2-(perfluoro butyl) ethyl, 2-(perfluoro capryl) ethyl, 2-(perfluor decyl) ethyl etc.As R 1And R 3In fluoro-alkyl, particularly from making the good viewpoint of liquid crystal aligning property, preferred carbon number is 3～6 straight chain shape.
The R of above-mentioned formula (c1-1) 2R with above-mentioned formula (c1-2) 4In the divalent group with ring type structure, can enumerate out divalent aromatic group, ester ring type group, hetero ring type group, condensed ring formula group, and can be the divalent group that combines a plurality of these groups to form.
Among them, be respectively, for example can enumerate out 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6-tetrafluoro generation-1,4-phenylene etc. as the divalent aromatic group;
As divalent ester ring type group, for example can enumerate out 1,4-cyclohexylidene, 2-fluoro-1,4-cyclohexylidene, 3-fluoro-1,4-cyclohexylidene, 2,3,5,6-tetrafluoro generation-1,4-cyclohexylidene etc.;
As divalent hetero ring type group, for example can enumerate out 1, the inferior pyridine radicals, 2 of 4-, the inferior pyridine radicals, 1 of 5-, 4-furylidene etc.;
As divalent condensed ring formula group, can enumerate out for example naphthylene etc.
As X 1, X 2And X 3, respectively preferred singly-bound, oxygen atom or-COO-.
The integer of b preferred 0～2, more preferably 1 or 2.
As the group shown in the above-mentioned formula (c1-1), the group shown in particularly can the following formula of illustration (c1-1-1)～(c1-1-28),
Figure BSA00000668597200091
In the formula, R 1" * " is identical with the definition of formula (c 1-1) respectively, and d is 1～10 integer.
As the group shown in the above-mentioned formula (c1-2), the group shown in can the following formula of illustration (c1-2-1)～(c1-2-4),
Figure BSA00000668597200121
In the formula, R 3" * " is identical with the definition of formula (c1-2) respectively.
As radiation-sensitive compound with light orientation group, the preferred polymkeric substance that connects above-mentioned smooth orientation group directly or through linking group.As this polymkeric substance; Can enumerate out and for example on any polymkeric substance at least of polyamic acid and polyimide, be connected the polymkeric substance that above-mentioned smooth orientation group forms, with polyamic acid and polyimide different polymer on be connected the polymkeric substance of above-mentioned smooth orientation group formation.Under latter event,, for example can enumerate out and gather (methyl) acrylic ester, gather (methyl) acrylic amide, polyvinylether, polyolefin, polysiloxane etc. as the basic framework of polymkeric substance with light orientation group.In addition, in this manual, described " (methyl) propenyl " is meant propenyl and methylpropenyl.
Can improve in the liquid crystal display cells liquid crystal molecule effectively to aspect the response speed of change in voltage, as the radiation-sensitive compound preferably with polyamic acid, polyimide or polysiloxane as basic framework.In addition, among them, preferred especially polysiloxane.Through in the 1st alignment agent, containing the polysiloxane with above-mentioned smooth orientation group, thereby make in the liquid crystal display cells, liquid crystal molecule is better to the response speed of change in voltage, and also better to long light-struck permanance (photostability).
< specific polysiloxane >
Have above-mentioned smooth orientation group polysiloxane (below; Be also referred to as specific polysiloxane); For example can obtain through making polysiloxane (silicone precursor) and having with the group of epoxy reaction and the compound of above-mentioned smooth orientation group (below, be also referred to as reactive compounds X1) reaction with epoxy radicals.
(silicone precursor)
Silicone precursor for example can be through making the silane compound (1) with epoxy radicals and hydrolization group preferably in the presence of organic solvent, water and catalyzer, and hydrolysis, condensation obtain.
As silane compound (1); Can enumerate out for example 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxysilane, 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 triethoxysilane, 4-glycidoxypropyl butyl methyl dimethoxy silane, 4-glycidoxypropyl butyl methyl diethoxy silane, 4-glycidoxypropyl butyl dimethyl methyl TMOS, 4-glycidoxypropyl butyl dimethylethoxysilane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3; The 4-epoxycyclohexyl) ethyl triethoxysilane, 3-(3; The 4-epoxycyclohexyl) propyl trimethoxy silicane, 3-(3, the 4-epoxycyclohexyl) propyl-triethoxysilicane etc.; Can use and be selected among them more than one.
Being used for the silane compound of synthetic silicone precursor, can be silane compound (1), except silane compound (1), can also comprise the silane compound that do not have epoxy radicals (below, be called " silane compound (2) ").
As the silane compound that can here use (2), can enumerate out silane compound with 1 silicon atom, and for example KC-89 that representes with trade name and X-21-3153 partial condensates such as (all being SHIN-ETSU HANTOTAI's chemical industry (Co., Ltd.) manufacturing) etc.As the preferred object lesson of silane compound (2), can enumerate out tetramethoxy-silicane, tetraethoxysilane, MTMS, MTES, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, vinyltrimethoxy silane, VTES, allyltrimethoxysilanis, allyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, mercapto methyl trimethoxy silane, mercapto methyl triethoxysilane, dimethyldimethoxysil,ne or dimethyldiethoxysilane.
The epoxide equivalent of silicone precursor is preferably 100～10,000g/mol, and more preferably 150～1,000g/mol is preferably 150～300g/mol especially.Therefore, when synthesizing silicone precursor, the epoxide equivalent that the usage ratio of silane compound (1) and silane compound (2) is preferably the polysiloxane for preparing is in above-mentioned scope.During synthetic above-mentioned silicone precursor, preferably only use silane compound (1).
As the organic solvent that can be used for synthetic silicone precursor, can enumerate out for example hydrocarbon, ketone, ester, ether, alcohol etc., preferably non-water-soluble among them.In addition, as above-mentioned organic solvent, can use separately or with two or more mixing.In addition, with respect to the whole silane compound of 100 weight portions, the consumption of organic solvent is preferably 10～10,000 weight portion, more preferably 50～1,000 weight portion.
The consumption of the water when synthesizing silicone precursor is preferably 0.5～100 times of mole with respect to whole silane compounds, more preferably 1～30 times of mole.
As the catalyzer that is used for synthetic silicone precursor, can enumerate out for example acid, alkali metal compound, organic base, titanium compound, zirconium compounds etc.Among them,, can enumerate out for example NaOH, potassium hydroxide etc. as alkali metal compound; As organic base, can enumerate out for example organic primary amine, organic secondary amine such as triethylamine, diethylamide, piperazine, trimethylamines such as triethylamine, pyridine, 4-dimethylaminopyridine; Organic quaternary amine such as tetramethyl ammonium hydroxide etc.As above-mentioned catalyzer, among them, preferred as alkali compound or organic base, more preferably organic solvent.In addition, as organic base, preferred especially trimethylamine or organic quaternary amine.
When using organic base as catalyzer, its consumption can suitably be set according to reaction conditionss such as the kind of organic base, temperature, and for example, relatively all silane compounds are preferably 0.01～3 times of mole, more preferably 0.05～1 times of mole.
The synthetic reaction of silicone precursor (hydrolysis, condensation reaction) for example; The silane compound (2) of silane compound (1) and use as required is dissolved in the organic solvent; This solution is mixed with organic base and water as catalyzer, carry out through heating such as for example oil baths.During this hydrolysis-condensation reaction, the expectation heating-up temperature is preferably below 130 ℃, and more preferably 40～100 ℃, preferably heated 0.5～12 hour, more preferably heated 1～8 hour.During heating, can mix liquid, under refluxing, carry out.In addition, after reaction finishes, the organic solvent layer of preferably obtaining from reactant liquor with water washing.It is after the neutrality that washing proceeds to water layer after the washing, as required with organic solvent layer with drying agent dryings such as dead plaster, molecular sieve after, except that desolvating.Thus, can obtain needed silicone precursor.
Silicone precursor is preferably 1,000～1 through the weight-average molecular weight Mw of the polystyrene conversion of gel permeation chromatography, and 000,000, more preferably 1,500～300,000.
In addition, when using commercially available commodity, for example can use DMS-E01, DMS-E12, DMS-E21, EMS-32 (more than, チ Star ソ Co., Ltd. makes) etc. as silicone precursor.
(reactive compounds X1)
Reactive compounds X1 has the group of the epoxy reaction that is had with silicone precursor and the compound of above-mentioned smooth orientation group.As with the preferred carboxyl of the group of epoxy reaction.Object lesson as this reactive compounds X; Can enumerate out the compound that the connecting key in the group shown in the above-mentioned formula (c1-1-1)～(c1-1-28) is connected with hydroxyl, the compound that the connecting key in the group shown in the above-mentioned formula (c1-2-1)～(c1-2-4) is connected with carboxyl.
The silicon atom that relative silicone precursor is had, the ratio of the reactive compounds X1 that uses when synthesizing polysiloxane is preferably 5～80 moles of %, and more preferably 10～65 moles of % further are preferably 15～50 moles of %.
During silicone precursor and reactive compounds X1 reaction, can have there not being light orientation group with compound of the group of epoxy reaction (below, be called other reactive compounds X2) and reactive compounds X1 and contain together.As other reactive compounds X2, for example can enumerate out compound (X2-1), [2] that [1] help to show the tilt angle of the liquid crystal orientation film that obtains have be selected from produce free radical through rayed structure with at least a compound (X2-2), [3] in the structure that light enhanced sensitivity function is arranged other compound (X2-3) beyond above-mentioned.
[1] other reactive compounds (X2-1)
As other reactive compounds (X2-1), can use the compound shown in the for example following formula (x2-1),
A 1-L 0-L 1-Z (x2-1)
In the formula, A 1Be carbon number be 1～30 alkyl, can by carbon number be 1～20 alkyl or the substituted carbon number of alkoxy be 3～10 naphthenic base, or the carbon number with steroid skeleton be 17～51 alkyl.Wherein, A 1In alkyl and at least a portion of the hydrogen atom in the alkoxy can be substituted.L 0Be singly-bound, *-O-, *-COO-or *-OCO-, the connection base and the A of band " * " 1Connect.L 1Be that singly-bound, carbon number are 1～20 alkylidene, phenylene, biphenylene, cyclohexylidene, inferior dicyclohexyl or following formula (L 1-1) or (L 1-2) group shown in,
Figure BSA00000668597200161
In the formula, " * " expression is connected to the connecting key on the Z.
Z is the 1 valency organic group that can form linking group with epoxy reaction.Wherein, L 1When being singly-bound, L 0It is singly-bound.
A as above-mentioned formula (4) 1In carbon number be 1～30 alkyl, can be the straight chain shape, also can be branched; Can enumerate out for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, 3-methyl butyl, 2-methyl butyl, 1-methyl butyl, 2,2-dimethyl propyl, n-hexyl, 4-methyl amyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 3,3-dimethylbutyl, 2; 3-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1; 2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5-methyl hexyl, 4-methyl hexyl, 3-methyl hexyl, 2-methyl hexyl, 1-methyl hexyl, 4; 4-dimethyl amyl group, 3,4-dimethyl amyl group, 2,4-dimethyl amyl group, 1; 4-dimethyl amyl group, 3,3-dimethyl amyl group, 2,3-dimethyl amyl group, 1; 3-dimethyl amyl group, 2,2-dimethyl amyl group, 1,2-dimethyl amyl group, 1; 1-dimethyl amyl group, 2,3,3-trimethyl butyl, 1; 3; 3-trimethyl butyl, 1,2,3-trimethyl butyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-heptadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base etc.
A 1In, be 3～10 naphthenic base as carbon number, can enumerate out for example cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl etc.These naphthenic base can be 1～20 alkyl or alkoxy replacement by carbon number.It as carbon number the object lesson of 1～20 alkyl; Be fit to using above-mentioned carbon number is the object lesson of enumerating in the explanation of 1～30 alkyl; As carbon number is 1～20 alkoxy, can enumerate out above-mentioned carbon number and be on the alkyl of the object lesson of enumerating in the explanation of 1～30 alkyl to connect the group that oxygen atom forms.
A 1In alkyl and at least a portion hydrogen atom of alkoxy can be substituted, can enumerate out cyanic acid, fluorine atom, trifluoromethyl etc. as the substituting group of this situation.
As the carbon number with steroid skeleton is 17～51 alkyl, can enumerate out the group shown in the for example following formula (s-1)～(s-3),
Figure BSA00000668597200181
In the formula, " * " expression is connected to L 0On connecting key.
As A 1, be preferably from carbon number be 1～20 alkyl, carbon number be the group shown in 1～20 fluoro-alkyl, the above-mentioned formula (s-1) with (s-3) shown in group the group selected.
Z is preferably carboxyl.
As L 1In carbon number be 1～20 alkylidene, can enumerate out from above-mentioned carbon number is to remove the group that 1 hydrogen atom forms in each group of enumerating the explanation of 1～30 alkyl.
As the compound shown in the above-mentioned formula (x2-1), the compound of preferred following formula (x2-1-1)～(x2-1-8) shown in each,
Figure BSA00000668597200191
In the formula, u is 1～5 integer, and v is 1～18 integer, and w is 1～20 integer.K is 1～5 integer, and p is 0 or 1, and q is 1～18 integer.R is 0～18 integer, and j is 1～18 integer.S and t are 0～2 integer independently of one another.Wherein, s and t are not 0 simultaneously.
As the integer of the v preferred 1～18 of above-mentioned formula (x2-1-1), more preferably 1～12 integer.
For w, as the integer of the w preferred 5～20 of above-mentioned formula (x2-1-2), more preferably 10～18 integer.In addition, as the integer of the w preferred 1～17 of above-mentioned formula (x2-1-3), more preferably 3～12 integer.As the integer of the w preferred 1～15 of above-mentioned formula (x2-1-4), more preferably 1～8 integer.As the integer of the w preferred 1～15 of above-mentioned formula (x2-1-8), more preferably 1～8 integer.
As the integer of the r preferred 0～15 of above-mentioned formula (x2-1-5) and formula (x2-1-6), more preferably 0～8 integer.
As the integer of the q preferred 1～12 of above-mentioned formula (x2-1-6), more preferably 1～5 integer.
As the integer of the j preferred 1～15 of above-mentioned formula (x2-1-8), more preferably 1～8 integer.
In these compounds, preferred above-mentioned formula (x2-1-2)～(x2-1-5), (x2-1-7) and the compound shown in each at least (x2-1-8), the compound shown in the preferred particularly following formula (x2-2-1)～(x2-2-8),
Figure BSA00000668597200201
Compound shown in the above-mentioned formula (x2-1) is that polysiloxane and reactive compounds X1 one with epoxy radicals are reacted, and in the liquid crystal orientation film that obtains, forms and gives the compound at manifesting property of tilt angle position.In this manual, sometimes the compound shown in the above-mentioned formula (x2-1) is called below " other manifesting property of tilt angle compound ".
With respect to the silicon atom that polysiloxane had, the usage ratio of other manifesting property of tilt angle compound is preferably 0～50 mole of %, and more preferably 0～35 mole of % further is preferably 0～20 mole of %.In addition, with respect to the total amount of reactive compounds X1, other manifesting property of tilt angle compound preferably with 75 moles below the %, more preferably uses with 50 moles of scopes below the %.Through the usage ratio that makes other manifesting property of tilt angle compound is 75 moles below the %, can make the high-speed response property of liquid crystal better.
[2] other reactive compounds (X2-2)
In other reactive compounds (X2-2); As structure that produces free radical through rayed and structure with light enhanced sensitivity function; Can enumerate out for example benzophenone structural, 1,3-dinitro benzene structure, 9,10-dioxo dihydro-anthraquinone structure, 1; 4-dioxo cyclohexyl-2,5-diene structure etc.Here, after described smooth enhanced sensitivity function is meant the excited state through rayed formation singlet, produces between item fast and intersect; Move to triple excited states, in these triple excited states and other molecules strike; Element is changed into excited state, return to the function of ground state naturally.This light enhanced sensitivity function can with produce the function of free radical through rayed and deposit.
As compound with this structure; Particularly can enumerate out for example 3-benzoyl benzoic acid, 4-benzoyl benzoic acid, 3-(4-diethylamino-2-hydroxy benzoyl) benzoic acid, 4-(2-hydroxy benzoyl) benzoic acid, 3-(2-hydroxy benzoyl) benzoic acid, 2-(2-hydroxy benzoyl) benzoic acid, 4-(4-methyl benzoyl) benzoic acid, 4-(3; The 4-dimethylbenzoyl) benzoic acid, 3-(4-benzoyl-phenoxy group) propionic acid, 9, and 10-dioxo dihydroanthracene-2-carboxylic acid (anthraquinone-2-carboxylic acid), 3-(9,10-dioxo-9; 10-dihydroanthracene-2-yl) propionic acid, [3-(4; 5-dimethoxy-3,6-dioxo hexamethylene-1,4-dialkylene) propoxyl group] acetate, 3; 5-dinitrobenzoic acid, 4-methyl-3; 5-dinitrobenzoic acid, 3-(3,5-2,4-dinitrophenoxy base) propionic acid, 2-methyl-3,5-dinitrobenzoic acid etc.
With respect to the silicon atom that polysiloxane had, total usage ratio of other reactive compounds (X2-2) is preferably 0～10 mole of %, more preferably 0～5 mole of %.
[3] other reactive compounds (X2-3)
As other reactive compounds (X2-3), can enumerate out for example carboxylic acids such as formic acid, acetate, propionic acid, benzoic acid.With respect to the silicon atom that polysiloxane had, the usage ratio of other reactive compounds (X2-3) is preferably 0～25 mole of %, more preferably 0～10 mole of %.
The consumption of reactive compounds X1 when containing other reactive compounds X2, the total amount with respect to reactive compounds X1 and other reactive compounds X2 is preferably 10 moles of %.In addition, the total amount Q1 of reactive compounds X1 and other reactive compounds X2 with respect to the silicon atom that the polysiloxane precursor is had, is preferably 5～90 moles of %, more preferably 10～70 moles of %.In addition, when using other reactive compounds (X2-2),, with respect to above-mentioned total amount Q1, be preferably 30 moles of %, more preferably 15 moles of % in order to ensure better ghost character.
The reaction of silicone precursor and reactive compounds X1 can preferably be carried out in suitable organic solvent in the presence of suitable catalyzer.
As catalyzer used herein; For example can use the illustrative organic base of catalyzer as the synthetic use of silicone precursor, and as promote epoxy radicals that silicone precursor had with the so-called like this curing accelerator of reaction of the group of the epoxy reaction that can be had with reactive compounds X1 known compound.
With respect to 100 weight portion silicone precursor, catalyst consumption is preferably below 100 weight portions, and more preferably 0.01～100 weight portion further is preferably 0.1～20 weight portion.
The organic solvent that uses during as the reaction of silicone precursor and reactive compounds X1 can be enumerated out for example hydrocarbon compound, ether compound, ester compounds, ketonic compound, amide compound, alcoholic compound etc.Among them, ether compound, ester compounds, ketonic compound are preferred from the viewpoint of the refining easy property of the dissolubility of raw material, product, product.Solvent, more preferably uses with the amount of 5～50 weight % preferably with more than the 0.1 weight % with solid component concentration (general assembly (TW) of the composition beyond the solvent in the reaction solution occupies the ratio of solution total weight).
Temperature of reaction is preferably 0～200 ℃, more preferably 50～150 ℃.Reaction time is preferably 0.1～50 hour, more preferably 0.5～20 hour.
Specific polysiloxane is preferably 1,000～500,000 through the weight-average molecular weight of the polystyrene conversion that gel permeation chromatography (GPC) is measured.Through being more than 1,000, can give suitable anisotropy to film, through being below 500,000, formation is filmed uniformly easily.More preferably 2,000～200,000.In addition, Mw is preferably 1.0～5.0 with respect to the ratio (Mw/Mn) of the number-average molecular weight of the polystyrene conversion of GPC (below, be called " Mn "), and more preferably 1.0～3.5, further be preferably 1.0～2.5.
When the polyamic acid that in the 1st alignment agent, contains and the total amount of polyimide are 100 weight portions; In the component of polymer that contains in the 1st alignment agent; Specific polysiloxane contain proportional 0.1～100 weight portion that is preferably, more preferably 1～50 weight portion further is preferably 5～15 weight portions.Through in above-mentioned scope, can keep the coating and the printing of resulting aligning agent for liquid crystal, and can demonstrate suitable tilt angle.
< specific polyamic acid >
On the other hand; The 1st alignment agent among the present invention comprise polyamic acid with above-mentioned smooth orientation group (below; Being called specific polyamic acid) during as the radiation-sensitive compound, this specific polyamic acid for example can obtain through making tetracarboxylic dianhydride and the diamine reactant with above-mentioned smooth orientation group.
(tetracarboxylic dianhydride)
The tetracarboxylic dianhydride who uses during as synthetic specific polyamic acid can enumerate out for example aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.As their example particularly, be respectively as the aliphatics tetracarboxylic dianhydride, can enumerate out for example butanetetra-carboxylic acid dianhydride etc.;
As the ester ring type tetracarboxylic dianhydride, for example can enumerate out 1,2,3,4-ring fourth tetracarboxylic acid dianhydride, 2,3; 5-tricarboxylic basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2; 5-dioxo-3-furyl)-and 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] hot-2; 4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5; 6-three carboxyls-2-ethyloic norbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxylic two ring [3.3.0] octane-2:4; 6:8-dianhydride, 4,9-dioxa three ring [5.3.1.02.6] undecanes-3,5,8,10-tetraketone etc.;
As aromatic tetracarboxylic acid's dianhydride, for example can enumerate out all benzene tertacarbonic acid's dianhydride etc.; And the tetracarboxylic dianhydride who puts down in writing in the use TOHKEMY 2010-97188 communique.
As the tetracarboxylic dianhydride, among them, preferably comprise the ester ring type tetracarboxylic dianhydride, especially preferably from 2; 3,5-tricarboxylic basic ring amyl group acetate dianhydride, 3,5; 6-three carboxyls-2-ethyloic norbornane-2:3,5:6-dianhydride and 2,4; 6,8-tetracarboxylic two ring [3.3.0] octane-2:4, that selects in the group that the 6:8-dianhydride constitutes is at least a.
(diamines)
As the dianhydride that synthetic specific polyamic acid uses, comprise diamines with above-mentioned smooth orientation group (below, be called specific diamines).Light orientation group as in this case preferably has the group from the structure of cinnamic acid.
Specific diamines can have more than one above-mentioned smooth orientation group in a part, preferably have one or two.As this specific diamines, can enumerate out for example above-mentioned smooth orientation group through for example *-COO-(CH 2) r-O-, *-(CH 2) r-linking groups such as (wherein, r represent 1～10 integer, and " * " expression is connected to the connecting key of two amine structures) is connected to the structural compound of diamines.
As the object lesson of specific diamines, can enumerate out the compound shown in the following formula (d1-1)～(d1-15),
Figure BSA00000668597200251
Figure BSA00000668597200261
Figure BSA00000668597200271
As the diamines that is used for synthetic specific polyamic acid, can use together with diamines beyond the specific diamines (below, be called other diamines).As this other diamines, particularly, be respectively as aliphatic diamine, can enumerate out for example m-xylene diamine, 1,3-propane diamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexane diamine etc.;
As the ester ring type diamines, for example can enumerate out 1,4-DACH, 4,4 '-methylene two (cyclo-hexylamine), 1,3-two (amino methyl) cyclohexane etc.; As aromatic diamine, can enumerate out for example o-phenylenediamine, m-phenylene diamine, p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1; 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamido-2; 2 '-two (trifluoromethyl) biphenyl, 2,7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9; 9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to phenylene two isopropylidenes) two (aniline), 4; 4 '-(metaphenylene two isopropylidenes) two (aniline), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2,6-diamino-pyridine, 3; 4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diamido carbazole, N-methyl-3; 6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl)-biphenylamine, N; N '-two (4-aminophenyl)-N, N '-dimethylbenzidine, 1,4-two (4-aminophenyl) piperazine, 3,5-diaminobenzoic acid, dodecyloxy-2; 4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, 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, hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2; 5-diaminobenzene, cholestane oxygen base-3,5-diaminobenzene, cholestene oxygen base-3,5-diaminobenzene, cholestane oxygen base-2; 4-diaminobenzene, cholestene oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3; 5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane, 3; 6-two (4-amino-benzene oxygen) cholestane, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethyl benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 1; 1-two (4-((aminophenyl) methyl) phenyl)-4-butyl cyclohexane, 1,1-two (4-((aminophenyl) methyl) phenyl)-4-heptyl cyclohexane, 1,1-two (4-((amino-benzene oxygen) methyl) phenyl)-4-heptyl cyclohexane, 1; 1-two (4-((aminophenyl) methyl) phenyl)-4-(4-heptyl cyclohexyl) cyclohexane, 2,4-diamino-N, N-diallyl aniline, 4-aminobenzyl amine, 3-aminobenzyl amine, 1-(2; The 4-diamino-phenyl) piperazine-4-acid, 4-(morpholine-4-yl) benzene-1,3-diamines, 1,3-two (N-(4-aminophenyl) piperidyl) propane, alpha-amido-omega-amino-phenyl alkylidene etc.;
As the diamido organosiloxane, for example can enumerate out 1,3-two (3-aminopropyl)-tetramethyl disiloxane etc.; And the diamines of putting down in writing in the TOHKEMY 2010-97188 communique.
In addition, based on making the well-behaved purpose of tilt angle, the diamines that uses during as specific polyamic acid synthetic, can contain simultaneously the compound shown in compound shown in specific diamines and the following formula (A-1) and the following formula (A-2) at least any one,
Figure BSA00000668597200291
In the formula, X I, X IIAnd X IIIBe singly-bound, *-O-, *-COO-or *-OCO-(wherein, the connecting key of band " * " is connected on the phenyl ring) independently of one another, R IBe that carbon number is 1～3 alkylidene, a is 0 or 1, and b is 0～2 integer, and c is 1～20 integer, and n is 0 or 1,
Figure BSA00000668597200292
In the formula, R IIIBe that hydrogen atom or carbon number are 1～12 alkyl independently of one another, R IVAnd R VBe hydrogen atom or methyl independently of one another
As in the above-mentioned formula (A-1)-X I-(R I-X II) n-shown in the divalent group to be preferably carbon number be 1～3 alkylidene, *-O-, *-COO-or *-OCH 2CH 2-O-(wherein, the connecting key of band " * " is connected with diamino-phenyl).As group C cH 2c+1-object lesson, for example can enumerate out methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base, n-eicosane base etc.2 primary amine groups in the diamino-phenyl are preferably 2 with respect to other group, 4-position or 3,5-position.
As the object lesson of the compound shown in the above-mentioned formula (A-1), can enumerate out compound that for example following formula (d2-1)～(d2-7) representes respectively etc.,
As the compound shown in the above-mentioned formula (A-2), preferred N, N-diallyl-2,4-diamido aniline.
The diamines that is used for synthetic specific polyamic acid is with respect to whole diamines, specific diamines contain proportional 50～100 moles of % that are preferably, more preferably 80～100 moles of %.
(synthesizing of specific polyamic acid)
The tetracarboxylic dianhydride who uses in the synthetic reaction as polyamic acid and the usage ratio of diamines, with respect to the amino of 1 equivalent diamines, the ratio of preferred 0.2～2 equivalent of tetracarboxylic dianhydride's anhydride group, the more preferably ratio of 0.3～1.2 equivalent.
The synthetic reaction of polyamic acid is preferably carried out in organic solvent, preferably at-20 ℃～150 ℃, more preferably under 0 ℃～100 ℃, preferably carries out 0.1～120 hour, more preferably carries out 0.5～48 hour.
As organic solvent, can enumerate out for example N-N-methyl-2-2-pyrrolidone N-, DMAC N,N, N, aprotic polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA here; Phenol property solvents such as metacresol, xylenol, phenol, halogenated phenol.The total amount (b) that the consumption of organic solvent (a) is preferably tetracarboxylic dianhydride and diamines is the amount of 0.1～50 weight % with respect to whole amounts (a+b) of reaction solution.
As far as specific polyamic acid, the weight-average molecular weight of the polystyrene conversion of measuring through gel permeation chromatography (GPC) is preferably 1,000～500, and 000, more preferably 5,000～300,000.Through in above-mentioned scope, can give suitable anisotropy to film, and can form more uniformly and film.
< specific polyimide >
The 1st alignment agent among the present invention comprise polyimide with above-mentioned smooth orientation group (below; Being called specific polyimide) during as the radiation-sensitive compound, this specific polyimide can be through obtaining above-mentioned specific polyamic acid dehydration closed-loop imidizate.
Specific polyimide can be the complete imidizate thing as the amic acid structure fully dehydrating closed loop that polyamic acid had of its precursor; Also can be a part of dehydration closed-loop of amic acid structure, amic acid structure and imide ring structure and the part imidizate thing of depositing.The imidizate rate of specific polyimide is preferably more than 30%, and more preferably 40～90%.In addition, this imidizate rate is to represent that with percent the quantity of imide ring structure occupies the ratio of total amount of quantity of quantity and imide ring structure of the amic acid structure of polyimide.
The dehydration closed-loop of polyamic acid preferably with the method through the heating polyamic acid, perhaps is dissolved in polyamic acid in the organic solvent, in this solution, adds dewatering agent and dehydration closed-loop catalyzer, and the method for heating is carried out as required.Wherein, a kind of method in preferred back.
In above-mentioned polyamic acid solution, add in the method for dewatering agent and dehydration closed-loop catalyzer,, can use for example acid anhydrides such as acetic anhydride, propionic andydride, TFAA as dewatering agent.The consumption of dewatering agent, the amic acid structure with respect to the 1mol polyamic acid is preferably 0.01～20mol.As the dehydration closed-loop catalyzer, can enumerate out for example tertiary amines such as pyridine, trimethylpyridine, lutidines, triethylamine.As the dehydration closed-loop catalyst consumption, the dewatering agent with respect to 1mol uses is preferably 0.01～10mol.As the organic solvent that uses in the dehydration closed-loop reaction, can enumerate out the illustrative organic solvent of solvent that acid is used as synthesizing polyamides.The temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.Reaction time is preferably 1.0～120 hours, more preferably 2.0～30 hours.
When the total amount of polyamic acid that contains as component of polymer and polyimide is 100 weight portions, specific polyamic acid and specific polyimide contain proportional 5～100 weight portions that are preferably, more preferably 10～100 weight portions.
< polyamic acid and polyimide >
When above-mentioned radiation-sensitive compound is specific polysiloxane, the 1st alignment agent contain the polyamic acid that do not have light orientation group or polyimide at least any one as neccessary composition; Perhaps when above-mentioned radiation-sensitive compound is specific polyamic acid or specific polyimide, the 1st alignment agent contain the polyamic acid that do not have light orientation group or polyimide at least any one as composition arbitrarily.This polyamic acid for example can use as the carboxylic acid dianhydride of using in specific polyamic acid synthetic and illustrative compound and reaction product as the illustrative compound of other diamines.In addition, this polyimide can use the material that the product polyamic acid dehydration closed-loop imidizate with above-mentioned reaction obtains.
(other composition of the 1st alignment agent)
The 1st alignment agent preferably is dissolved into the component of polymer that contains in this alignment agent in the suitable organic solvent, is prepared as liquid composite.As this organic solvent, can be the above-mentioned component of polymer of dissolving, and the solvent of their reactions of getting along well, for example can enumerate out the solvent that uses as synthetic above-mentioned specific polysiloxane and illustrative organic solvent.
In addition, the 1st alignment agent contains other composition beyond the component of polymer arbitrarily.As this other composition, can enumerate out the for example polymkeric substance beyond polysiloxane, polyamic acid and the imide amination polymer, hardening agent, curing catalysts, curing accelerator, epoxy compound, functional silanes compound, surfactant, photosensitizing agent etc.
< the 2nd alignment agent >
Be used to form the 2nd alignment agent of the 2nd alignment films 15, can form the vertical alignment layer that makes liquid crystal molecule vertical orientated.As the 2nd alignment agent can be the alignment agent that (1) is substantially free of the compound with light orientation group, and any of alignment agent of above-mentioned radiation-sensitive compound contained in (2).Under the situation of (1); For example, use the carboxylic acid dianhydride used when comprising as component of polymer and the polyamic acid that illustrative compound and reaction as the illustrative compound of above-mentioned other diamines obtain or the composition of its imide amination polymer as above-mentioned specific polyamic acid synthetic.On the other hand, under the situation of (2), can use and the identical composition of the illustrative composition of above-mentioned the 1st alignment agent.In addition, when forming the 2nd alignment films,, suitably select to use in (1), (2) aligning agent for liquid crystal arbitrarily according to the operation of making above-mentioned liquid crystal display cells.
[manufacturing approach of liquid crystal display cells]
The manufacturing approach of liquid crystal display cells of the present invention comprises following operation: the surface of a substrate in a pair of substrate; Make the direction tilted alignment of vertical relatively this substrate surface of liquid crystal molecule; Form the 1st alignment films 13; Make the 2nd vertical orientated alignment films 15 of liquid crystal molecule in another substrate surface formation, make liquid crystal display cells 10.As this manufacturing approach, preferred particularly following two kinds of schemes.
[the 1st manufacturing approach]
The 1st manufacturing approach that is used to make liquid crystal display cells 10 of the present invention is to use the substrate that forms the 1st alignment films 13 to constitute liquid crystal cell, thereby makes liquid crystal display cells 10 of the present invention, particularly comprises following operation.
[the 1st film forms operation]
This operation is to use as light orientation above-mentioned the 1st alignment agent with aligning agent for liquid crystal, and the surface of a substrate in a pair of substrate forms the 1st operation of filming.More in detail at first, through for example suitable coating processes such as rolling method, spin-coating method, print process, ink-jet method,, be coated with the 1st alignment agent in the electrode surface side of the substrate 11a with the 1st electrode 12.Substrate 11a used herein can be the substrate through the vergence direction of gap electrode that forms the slit-shaped pattern or rib (projection) control liquid crystal molecule, also can be the substrate that gap electrode or rib are not set.In addition; At the conducting film that use to form the slit-shaped pattern during as the 1st electrode 12; In order to obtain this electrode, for example can, formation form method of patterning after not having the conducting film of pattern through photoetch; Perhaps when forming conducting film, use the method etc. of mask to carry out with desirable pattern.
Then, through this coated face is preheated (prebake), fire (afterwards curing) formation then and film.The prebake condition for example is under 40～120 ℃, to carry out 0.1～5 minute, after cure condition optimization at 120～300 ℃, more preferably under 150～250 ℃, preferably carried out 5～200 minutes, more preferably carried out 10～100 minutes.After the thickness of filming after curing be preferably 0.001～1 μ m, 0.005～0.5 μ m more preferably.
The solid component concentration of the aligning agent for liquid crystal that on substrate, uses during the coating of liquid crystalline alignment agent (general assembly (TW) of the composition beyond the solvent of aligning agent for liquid crystal occupies the ratio of the total weight of aligning agent for liquid crystal); Consider suitably selection such as viscosity, volatility, be preferably the scope of 1～10 weight %.During solid component concentration less than 1 weight %, the thickness of filming is too small, is difficult to obtain good liquid crystal orientation film.On the other hand, when solid component concentration surpassed 10 weight %, the thickness of filming was excessive, is difficult to obtain good liquid crystal orientation film, and perhaps the viscosity of aligning agent for liquid crystal increases, and coating character maybe be not enough.
The method that the scope of preferred especially solid component concentration adopts during according to coated with liquid crystal alignment agent on substrate and different.For example, when using spin-coating method to carry out, solid component concentration is preferably the scope of 1.5～4.5 weight % especially.When using adherography to carry out, preferred especially solid component concentration is the scope of 3～9 weight %, and thus, solution viscosity is the scope of 12～50mPas.When using ink jet printing method to carry out, solid component concentration is the scope of 1～5 weight %, and thus, solution viscosity is preferably the scope of 3～15mPas especially.
In addition, before the coated with liquid crystal alignment agent,, can in substrate surface, should form on the face of filming, apply functional silanes compound, functionality titanium compound etc. in advance and carry out pre-treatment in order to make substrate surface (the 1st electrode 12) and the cohesiveness of filming better.
[rayed operation]
This operation is through irradiates light that the 1st of the last formation of substrate 11a is filmed, and filming the 1st forms the operation as the 1st alignment films 13 of optical alignment film.Any one of radioactive ray of radioactive ray and the non-polarisation of polarisation can be used to the 1st irradiates light of filming, when using the radioactive ray of polarisation, linear polarization, part polarisation etc. can be used, preferred linear polarization.In addition, as radioactive ray, can use the ultraviolet ray and the luminous ray of the light of the wavelength that comprises 150nm～800nm.Wherein, preferably comprise the ultraviolet ray of light of the wavelength of 300nm～400nm.
In order to give tilt angle, be the direction that relative substrate surface tilts to the 1st irradiation direction of light of filming.The tilt angle that the irradiating angle of this moment shows in can filming according to the 1st is suitably set.Through this rayed, preferably making the tilt angle in the 1st alignment films 13 is 85～89.5 °, more preferably 87～89 °.
Light source as the irradiation radioactive ray can use for example Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, mercury xenon lamp, deuterium lamp, Halogen lamp LED, metal halide lamp, argon resonance lamp, xenon lamp, PRK etc.The ultraviolet ray in above-mentioned preferred wavelength zone can obtain through mechanism that aforementioned light source and for example light filter, diffraction grating etc. are used together etc.
The exposure of radioactive ray is preferably 1J/m 2More than, less than 10,000J/m 2, more preferably 10～3,000J/m 2
[the 2nd film forms operation]
This operation is in a pair of substrate 11a, 11b, does not form the surface of the 1st another substrate 11b of filming, uses the 2nd alignment agent as the aligning agent for liquid crystal that can form vertical alignment layer, forms the 2nd operation of filming.The 2nd films carries out through forming the identical method that formation is filmed in the operation with above-mentioned the 1st film basically.In addition, substrate 11b used herein also can also can not be provided with these electrodes through the vergence direction of gap electrode or rib control liquid crystal molecule.
Can use (1) not contain the alignment agent of the compound with light orientation group in fact as the 2nd alignment agent in this manufacturing approach, any one in the alignment agent of above-mentioned radiation-sensitive compound contained in (2)., can use as the identical material of the illustrative alignment agent of above-mentioned the 1st alignment agent during as the 2nd alignment agent at the alignment agent that uses (2), at this moment, the identical kind of using in the time of can be with formation that the 1st films of material also can be different kind.Wherein, at the alignment agent that uses (2) during, this substrate 11b is not gone up the 2nd irradiates light of filming that forms as the 2nd alignment agent.
In addition; As above the 2nd of formation the film and directly to use as vertical alignment layer (the 2nd alignment films 15); Through for example through having reeled, with the friction treatment on certain orientation (friction treatment) of filming that forms by the roller of fibroplastic cloth such as nylon, rayon, cotton.
[box formation operation]
Then, with the two substrate 11a, the 11b that form liquid crystal orientation film respectively, make the 1st alignment films 13 and, constitute liquid crystal cell as the 2nd vertical alignment layer (the 2nd alignment films 15) the subtend ground configuration of filming.When constituting liquid crystal cell, can enumerate out for example following two kinds of methods.
The 1st kind of method is at first to pass through gap (box gap), with each liquid crystal orientation film subtend, with two substrate 11a, the configuration of 11b subtend, uses sealant that the periphery of two substrate 11a, 11b is fitted.Then, in the box gap of dividing through substrate surface and sealant, behind the injection filling liquid crystal, seal filling orifice.Thus, constitute liquid crystal cell.
Second method is the method that is called ODF (under the liquid crystal drop) mode.Just; Assigned position on forming two substrate 11a of liquid crystal orientation film, a substrate among the 11b; Apply the for example sealant of ultraviolet light curable, then after dripping liquid crystal on the liquid crystal aligning face, another substrate and make the liquid crystal orientation film subtend of fitting.Then, whole irradiating ultraviolet light at substrate makes sealant cures.Thus, constitute liquid crystal cell.
In addition, in any one method, the purpose of the flow orientation when removing liquid crystal and fill, after the liquid crystal that preferably liquid crystal cell of above-mentioned manufacturing is heated to use is isotropic temperature, slow cool to room temperature.
To the liquid crystal cell of above-mentioned formation, at each outer surface of two substrate 11a, 11b, applying polaroid 18,19 obtains liquid crystal display cells 10 of the present invention.At this moment, the polarization direction of polaroid 18,19 is mutually orthogonal, and on the substrate that forms the 1st alignment films 13, ultraviolet optical axis forms 45 ° angle, applying polaroid toward the projecting direction of real estate.
As aforementioned sealant, can use and for example contain as the alumina balls of partition and the epoxy resin of hardening agent etc.
[the 2nd manufacturing approach]
The 2nd manufacturing approach that is used to make liquid crystal display cells 10 of the present invention is to use aligning agent for liquid crystal; Film in each substrate surface formation; After using this substrate of filming of formation to constitute liquid crystal cell,, thereby make liquid crystal display cells 10 of the present invention to the liquid crystal cell irradiates light.Particularly comprise following operation.
[the 1st film forms operation]
This operation is to use as 1st alignment agent of light orientation with aligning agent for liquid crystal, and the surface of a substrate 11a in a pair of substrate 11a, 11b forms the operation of filming.Wherein, in manufacturing approach of the present invention, substrate 11a, 11b as formation is filmed use the substrate that comprises the electrode (the 1st electrode the 12, the 2nd electrode 14) with slit-shaped pattern.In addition, for the formation method of filming, can use the 1st film in above-mentioned the 1st manufacturing approach to form the method that operation is put down in writing.
[the 2nd film forms operation]
This operation is to use the surface of another substrate 11b of the 2nd alignment agent in a pair of substrate 11a, 11b to form the operation of the 2nd alignment films 15.At this moment, as the 2nd alignment agent, use the aligning agent for liquid crystal that does not contain the compound with light orientation group in fact, the 2nd film in just above-mentioned the 1st manufacturing approach forms (1) in illustrative the 2nd alignment agent (1), (2) in the operation.
In addition, the 2nd alignment films 15 that as above forms can directly be used, and also can carry out friction treatment to filming of formation.
[box formation operation]
In this operation, two substrate 11a, 11b forming film are made each film subtend configuration, constitute liquid crystal cell.As the method that constitutes liquid crystal cell, the box that can enumerate out in above-mentioned the 1st manufacturing approach constitutes two kinds of methods explaining in the operation.
[rayed operation]
In this operation,,, give the light orientation to filming of the 1st alignment agent formation through irradiates light under the state that applies voltage between a pair of substrate to the liquid crystal cell of above-mentioned formation.Thus, this is filmed becomes the film of the liquid crystal molecule direction tilted alignment that substrate surface is vertical relatively (the 1st alignment films 13).
As the voltage that applies can be direct current or the alternating voltage of for example 5～50V.At this moment, as the conducting film of substrate surface, when formation is divided into the pattern-like conducting film in a plurality of zones, when applying this voltage,, can change in above-mentioned the filming the vergence direction of liquid crystal molecule in each zone through applying different voltages with different in each zone.Thus, perspective nature is further enlarged.
Can use in the radioactive ray of radioactive ray and non-polarisation of polarisation any one to the light of liquid crystal cell irradiation, preferred non-polarisation.In addition, when shining the radioactive ray of non-polarisation, preferably carry out from the vertical direction of relative substrate surface.
As radioactive ray, can use the ultraviolet ray and the luminous ray of the light of the wavelength that for example comprises 150nm～800nm, preferably comprise the ultraviolet ray of light of the wavelength of 300nm～400nm.As the light source of irradiation radioactive ray, can illustration with above-mentioned the 1st manufacturing approach in the identical light source of illustrative light source.
Exposure as radioactive ray is preferably 1,000J/m 2More than, less than 100,000J/m 2, more preferably 1,000～50,000J/m 2
Through this rayed, preferably making the tilt angle in the 1st alignment films 13 is 85～89.5 °, more preferably 87～89 °.
To the liquid crystal cell after the rayed, through with the identical method of above-mentioned the 1st manufacturing approach, at each outer surface of two substrate 11a, 11b, applying polaroid 18,19 obtains liquid crystal display cells 10 of the present invention.
Liquid crystal display cells of the present invention; As VA type liquid crystal display cells; Can be applicable to various devices effectively, for example can in display device such as clock and watch, pocket game machine, word processor, notebook computer, automatic navigator, video camera-video recorder, PDA, digital camera, mobile phone, various monitor, LCD TV, use.
[embodiment]
Below, through embodiment, the present invention is more specifically explained, but the present invention does not receive the qualification of these embodiment.
In addition, hereinafter, the imidizate rate of the solution viscosity of weight-average molecular weight Mw, number-average molecular weight Mn, epoxide equivalent, polymer solution and polyimide is measured as follows.
What weight-average molecular weight Mw and number-average molecular weight Mn carried out through following condition is that the gel permeation chromatography (GPC) of standard is measured with the monodisperse polystyrene.
Post: eastern ソ one (Co., Ltd.) makes, TSKgelGRCXLII
Solvent: tetrahydrofuran
Temperature: 40 ℃
Pressure: 68kgf/cm 2
Epoxide equivalent is measured according to JIS C2105 " hydrochloric acid-MEK method ".
The solution viscosity of polymer solution (mPas) is to use E type rotational viscosimeter, under 25 ℃, is determined at the viscosity of the concentration 20 weight % of each polyamic acid in the nmp solvent.
The imidizate rate of polyimide is in the nmp solution input pure water with polyimide, behind the at room temperature abundant drying under reduced pressure of deposition with gained, is dissolved in the heavy-hydrogenated dimethyl sulfoxide (DMSO),, at room temperature measures as primary standard substance with TMS 1H-NMR.From gained 1H-NMR spectrum is tried to achieve the imidizate rate through the formula shown in the following mathematical expression (1).
Imidizate rate (%)=(1-A 1/ A 2* α) * 100 (1)
(in the mathematical expression (1), A 1Be peak area near the proton of the NH base that shows the chemical shift 10ppm, A 2Be the peak area from other proton, α is the ratio of the number of other proton proton basic with respect to the NH in the precursor (polyamic acid) of 1 polymkeric substance).
1H-NMR analyzes and uses nuclear magnetic resonance device (trade name: JNM-ECX400, NEC's manufactured).
Synthesizing of starting compound and polymkeric substance, repeat as required, to guarantee the necessary amount of following synthetic use according to following synthetic scale.
[polysiloxane synthetic] with epoxy radicals
(synthetic routine E-1)
In the reaction vessel that has stirrer, thermometer, tap funnel and reflux condensing tube, add 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 500g methyl isobutyl ketone and the 10.0g triethylamine of 100.0g, at room temperature mix.Then, from tap funnel, dripped the 100g deionized water with 30 minutes after, refluxing following the mixing, the limit is 80 ℃ of reactions 6 hours down.After reaction finishes, take out organic layer, be neutrality through the water after the aqueous ammonium nitrate solution washing of 0.2 weight % after, under reduced pressure distillate solvent and water, obtain having the polysiloxane (EPS-1) of epoxy radicals, be the transparency liquid of thickness.
(EPS-1) carries out to this polysiloxane 1H-NMR analyzes, and near chemical shift (δ)=3.2ppm, obtains the peak based on epoxy radicals of theoretical strength.Thus, confirm that epoxy radicals does not produce subsidiary reaction in reaction.
The weight-average molecular weight Mw of the polysiloxane that obtains (EPS-1) is 2,200, and epoxide equivalent is 186g/mol.
[synthesizing of cinnamic acid derivative (A)]
(synthetic routine A-1)
According to following synthetic route 1, synthesizing cinnamic acid derivant (A-1).
Figure BSA00000668597200411
Synthetic route 1
In the eggplant type flask of 1L, add the N-N-methyl-2-2-pyrrolidone N-of 4-methyl hydroxybenzoate, 182.4g sal tartari and the 320mL of 91.3g, at room temperature stir 1 hour after; The 1-iodate-4 that adds 157.1g; 4,4-three fluoro butane stirred 5 hours down at 100 ℃.After reaction finished, water precipitated once more.Then, in this deposition, add 48g NaOH and 400mL water, refluxed 3 hours, reaction is hydrolyzed.After reaction finished, through the hydrochloric acid neutralization, the deposition of generation obtained the white crystals of 110g compound (A-1-1) through ethyl alcohol recrystallization.
With the reaction vessel of packing into of the 12.41g in this compound (A-1-1), add the N of 100mL thionyl chloride and 77 μ L therein, dinethylformamide stirred 1 hour down at 80 ℃.Then, under reduced pressure distillate thionyl chloride, add methylene chloride,, use dried over mgso, after concentrating, add tetrahydrofuran, form solution with the sodium bicarbonate aqueous solution washing.
Then, with the there-necked flask of above-mentioned different 500mL in, add 4-hydroxycinnamic acid, 13.82g sal tartari, 0.48g TBuA, 50mL tetrahydrofuran and the 100mL water of 7.39g.Ice-cooled this WS slowly drips above-mentioned tetrahydrofuran solution, stirs then and reacts in 2 hours.After reaction finishes, add the hydrochloric acid neutralization, behind ethyl acetate extraction, use dried over mgso, after concentrating,, obtain the white crystals of 10.0g cinnamic acid derivative (A-1) through ethyl alcohol recrystallization.
(synthetic routine A-2)
According to following synthetic route 2, synthesizing cinnamic acid derivant (A-2).
Figure BSA00000668597200421
[synthetic route 2]
In the there-necked flask of the 500mL that has reflux condensing tube, thermometer and nitrogen ingress pipe; The N that adds compound (A-2-1), 0.23g palladium, 1.2g three (neighbour-tolyl) phosphine, 56mL triethylamine, 8.2mL acrylic acid and the 200mL of 31g; The N-dimethyl acetamide stirs under 120 ℃ and reacted in 3 hours.After reaction finished, filter reaction mixture added 1L ethyl acetate in the filtrating that obtains, and the organic layer that obtains with watery hydrochloric acid washing 2 times, with water washing 3 times, is used dried over mgso successively.Afterwards, under reduced pressure remove and desolvate, the solid that obtains obtains the crystallization of 15g cinnamic acid derivative (A-2) from the mixed solvent recrystallization of ethyl acetate and tetrahydrofuran.
(synthetic routine A-3)
According to following synthetic route 3, synthesizing cinnamic acid derivant (A-3).
Figure BSA00000668597200431
[synthetic route 3]
In the eggplant type flask of the 300mL that has reflux condensing tube and nitrogen ingress pipe, add the N of 21g compound (A-3-1), 80mL thionyl chloride and 0.1mL, dinethylformamide stirs under 80 ℃ and reacted in 1 hour.Reaction distillates thionyl chloride from reaction mixture after finishing, and adds the 150mL methylene chloride then, and the organic layer that obtains is with water washing 3 times.This organic layer with dried over mgso after, removal of solvent under reduced pressure adds the 400mL tetrahydrofuran in the solid that obtains.
On the other hand, in the there-necked flask of the 1L that has tap funnel and thermometer, add 16g p-Coumaric Acid, 24g sal tartari, 0.87g Tetrabutylammonium bromide, 200mL water and 100mL tetrahydrofuran, ice-cold to below 5 ℃.Dripped above-mentioned tetrahydrofuran solution with 3 hours therein, stir then and reacted in 1 hour.After reaction finishes, in reaction mixture, add watery hydrochloric acid, make pH be 4 below after, adding 3L toluene and 1L tetrahydrofuran, the organic layer that obtains is with water washing 3 times.This organic layer with dried over mgso after, removal of solvent under reduced pressure, the solid of gained is through by the mixed solvent recrystallization of ethanol and tetrahydrofuran, thereby obtains the compound (A-3) of 21g as cinnamic acid derivative.
[synthesizing of radiation-sensitive polysiloxane]
(synthetic routine S-1)
In the there-necked flask of 300mL; Add the cinnamic acid derivative (A-1) that the above-mentioned synthetic routine A-1 of compound (EPS-1), 140g methyl isobutyl ketone, 31.9g that 30.1g obtains as the above-mentioned synthetic routine E-1 with polysiloxane of epoxy radicals the obtains (silicon atom that is had with respect to compound (EPS-1); Be equivalent to 50 moles of %), the 4.60g stearic acid (silicon atom that is had with respect to compound (EPS-1); Be equivalent to 10 moles of %), 3,5 dinitrobenzoic acids (, being equivalent to 0.2 mole of %) and the 3.00g Tetrabutylammonium bromide of 0.0686g with respect to the silicon atom that compound (EPS-1) is had; Stirred 5 hours down at 80 ℃, react.Reaction precipitates with methyl alcohol after finishing once more, and sediment is dissolved in the ethyl acetate; Obtain solution, this solution distillates solvent after washing 5 times; As the radiation-sensitive polysiloxane, obtaining 55.6g weight-average molecular weight (Mw) is the white powder of the compound (S-1) of 12,600 (Mw/Mn=1.42).
(synthetic routine S-2)
In the there-necked flask of 200mL; Add the cinnamic acid derivative (A-2) that the above-mentioned synthetic routine A-2 of compound (EPS-1), 60g methyl isobutyl ketone, 1.62g that 10.0g obtains as the above-mentioned synthetic routine E-1 with polysiloxane of epoxy radicals the obtains (silicon atom that is had with respect to compound (EPS-1); Be equivalent to 10 moles of %), the cinnamic acid derivative (A-3) that obtains of the above-mentioned synthetic routine A-3 of the 3.45g (silicon atom that is had with respect to compound (EPS-1); Be equivalent to 15 moles of %) and the 1.00g Tetrabutylammonium bromide; Stirred 2 hours down at 80 ℃, react.Reaction precipitates with methyl alcohol after finishing once more, and sediment is dissolved in the ethyl acetate; Obtain solution, this solution distillates solvent after washing 5 times; As the radiation-sensitive polysiloxane, obtaining 12.8g weight-average molecular weight (Mw) is the white powder of the compound (S-2) of 11,200 (Mw/Mn=1.13).
(embodiment S-3)
In the there-necked flask of 50mL; Add the cinnamic acid derivative (A-2) that the above-mentioned synthetic routine A-2 of compound (EPS-1), 16g methyl isobutyl ketone, 1.61g that 2.01g obtains as the above-mentioned synthetic routine E-1 with polysiloxane of epoxy radicals the obtains (silicon atom that is had with respect to compound (EPS-1); Be equivalent to 50 moles of %), the 4-tert-butyl group oxygen base carbonyl benzoic acid of the 0.356g (silicon atom that is had with respect to compound (EPS-1); Be equivalent to 15 moles of %) and the 0.20g Tetrabutylammonium bromide; Stirred 2 hours down at 80 ℃, react.Reaction precipitates with methyl alcohol after finishing once more, and sediment is dissolved in the ethyl acetate; Obtain solution, this solution distillates solvent after washing 5 times; As the radiation-sensitive polysiloxane, obtaining 3.46g weight-average molecular weight (Mw) is the white powder of the compound (S-3) of 14,700 (Mw/Mn=1.51).
[synthesizing of polyamic acid and polyimide]
(synthetic routine P-1)
With 1,2,3 of 19.61g (0.1mol), 4-ring fourth tetracarboxylic acid dianhydride and 21.23g (0.1mol) 4,4 '-diamido-2,2 '-dimethyl diphenyl are dissolved in the N-N-methyl-2-2-pyrrolidone N-of 367.6g, at room temperature react 6 hours.Then, reaction mixture is injected a large amount of excessive methyl alcohol, make the reaction product deposition.Sediment is used methanol wash, and decompression, 40 ℃ dry 15 hours down obtain 35g polyamic acid (PA-1).
(synthetic routine P-2)
With 21.81g (0.0973mol) 2; 3; 5 ξ-cholestane shown in 5-tricarboxylic basic ring amyl group acetate dianhydride and the following formula of 19.29g (0.0390mol) (p1)-3-base 2; 3 of 4-diamino-phenyl ether, 8.90g (0.0585mol), 5-diaminobenzoic acid are dissolved in the N-N-methyl-2-2-pyrrolidone N-of 200g, react 5 hours down at 60 ℃.The viscosity of measuring this polymeric solution is 1450mPas.Then, in this solution, add the N-N-methyl-2-2-pyrrolidone N-of 250g, stir one after the meeting, add 11.55g pyridine and 14.90g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours.Afterwards, reaction mixture is injected a large amount of excessive methyl alcohol, make the reaction product deposition.Sediment is used methanol wash, and under reduced pressure 40 ℃ of dryings are 15 hours, obtains the polyimide (PI-1) of 37.5g imidizate rate 69%.
Figure BSA00000668597200461
(synthetic routine P-3)
With 23.38g (0.104mol) 2; 3; 5 ξ-cholestane shown in 5-tricarboxylic basic ring amyl group acetate dianhydride and the following formula of 15.50g (0.0313mol) (p 1)-3-base 2; 3 of 4-diamino-phenyl ether, 11.12g (0.0731mol), 5-diaminobenzoic acid are dissolved in the N-N-methyl-2-2-pyrrolidone N-of 200g, react 5 hours down at 60 ℃.Then, in this solution, add the N-N-methyl-2-2-pyrrolidone N-of 250g, stir one after the meeting, add 12.37g pyridine and 15.97g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours.Afterwards, reaction mixture is injected a large amount of excessive methyl alcohol, make the reaction product deposition.Sediment is used methanol wash, and decompression, 40 ℃ dry 15 hours down obtain the polyimide (PI-2) of 36.4g imidizate rate 71%.
(synthetic routine P-4)
With 26.73g (0.119mol) 2; 3; 6-{ shown in 5-tricarboxylic basic ring amyl group acetate dianhydride and the following formula of 73.27g (0.119mol) (p2) [((2E)-3-{4-[(4-(3,3,3-three fluoro propoxyl group) benzoyl) oxygen base] phenyl } third-2-acyl group) the oxygen base] } benzyl-3; 5 diaminobenzoic acid esters are dissolved in the N-N-methyl-2-2-pyrrolidone N-of 185.7g, react 24 hours down at 60 ℃.The viscosity of measuring this polymeric solution is 4800mPas.Then, reaction mixture is injected big excessive methyl alcohol, make the reaction product deposition.Sediment is used methanol wash, and under reduced pressure 40 ℃ of dryings are 15 hours, obtain 70g polyamic acid (PA-2).
Figure BSA00000668597200462
(synthetic routine P-5)
With 27.07g (0.121mol) 2; 3; 6-{ shown in 5-tricarboxylic basic ring amyl group acetate dianhydride and the above-mentioned formula of 66.79g (0.109mol) (p2) [((2E)-3-{4-[(4-(3,3,3-three fluoro propoxyl group) benzoyl) oxygen base] phenyl } third-2-acyl group) the oxygen base] } benzyl-3; 5 ξ-cholestane shown in 5 diaminobenzoic acid esters, the above-mentioned formula of 2.99g (0.00604mol) (p 1)-3-base 2; Shown in the following formula of 4-diamino-phenyl ether and 3.16g (0.00604mol) (p3) 3,5-diaminobenzoic acid=5 ξ-cholestane-3-base ester is dissolved in the N-methyl 3-pyrrolidone of 185.7g, reacted 24 hours down at 60 ℃.The viscosity of measuring this polymeric solution is 2100mPas.Then, reaction mixture is injected big excessive methyl alcohol, make the reaction product deposition.Sediment is used methanol wash, and under reduced pressure 40 ℃ of dryings are 15 hours, obtain 68g polyamic acid (PA-3).
Figure BSA00000668597200471
(synthetic routine P-6)
With 18.75g (0.0836mol) as tetracarboxylic dianhydride's 2; 3; 5-tricarboxylic basic ring amyl group acetate dianhydride, 7.359g (0.0681mol) are as 3 shown in the P-pHENYLENE dI AMINE of diamine compound and the above-mentioned formula of 8.895g (0.0170mol) (p3); 5-diaminobenzoic acid=5 ξ-cholestane-3-base ester is dissolved in the N-N-methyl-2-2-pyrrolidone N-of 140g, reacted 5 hours down at 60 ℃.The viscosity of measuring this polymeric solution is 2000mPas.Then, in this solution, add the N-N-methyl-2-2-pyrrolidone N-of 325g, stir one after the meeting, add 6.61g pyridine and 8.54g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours.Afterwards, reaction solution is injected big excessive methyl alcohol, make the reaction product deposition.Sediment is used methanol wash, and under reduced pressure 40 ℃ of dryings are 15 hours, obtains the polyimide (PI-3) of 26.6g imidizate rate 51%.
[preparation of aligning agent for liquid crystal]
(preparation example 1)
The polyimide (PI-1) that the polyamic acid (PA-1) that the above-mentioned synthetic routine P-1 of relative 30 weight portions obtains, the synthetic routine P-2 of 70 weight portions obtain; Adding radiation-sensitive polysiloxane (S-1), N-N-methyl-2-2-pyrrolidone N-(NMP) and the butyl cellosolve (BC) that the synthetic routine S-1 of 10 weight portions obtains and making solvent composition is NMP: BC=45: 55 (weight ratios), the solution of formation solid component concentration 3.5 weight %.This solution uses the filtrator of aperture 0.2 μ m to filter, preparation aligning agent for liquid crystal (AF-1).
(preparation example 2～7)
Except the kind of the kind of radiation-sensitive polysiloxane and addition, polyamic acid and polyimide and addition, solvent composition respectively as 1 of below table the record and preparation example 1 likewise prepare aligning agent for liquid crystal (AF-2)～(AF-7) respectively.
[table 1]
Figure BSA00000668597200481
(preparation example 8)
The polyamic acid (PI-3) that the above-mentioned synthetic routine P-6 of relative 100 weight portions obtains; Add 20 weight portion N; N, N ', N '-four glycidyl group-4; 4 '-diaminodiphenyl-methane, N-N-methyl-2-2-pyrrolidone N-(NMP) and butyl cellosolve (B C) and to make solvent composition be NMP: BC=50: 50 (weight ratios) form the solution of solid component concentration 3.5 weight %.This solution uses the filtrator of aperture 0.2 μ m to filter, preparation aligning agent for liquid crystal (AF-8).
[manufacturing of liquid crystal display cells]
(embodiment 1)
On the transparency electrode face that has by the glass substrate of the film formed transparency electrode of ITO, use spinner, be coated with the aligning agent for liquid crystal (AF-1) of above-mentioned preparation example 1 preparation; On 80 ℃ hot plate; After the prebake 1 minute, in the baking oven of inner nitrogen replacement, under 200 ℃; Heated 1 hour, and formed filming of thickness 80nm.Then, on this surface of filming, use Hg-Xe lamp and Glan-Taylor prism, from tilt 40 ° direction of the direction on relative vertical substrate surface, irradiation contains the ultraviolet 200J/m of polarisation of the bright line of 313nm 2, make substrate A.
In addition, likewise on the transparency electrode face that has by the glass substrate of the film formed transparency electrode of ITO, use spinner; Be coated with the aligning agent for liquid crystal (AF-1) of above-mentioned preparation example 1 preparation, on 80 ℃ hot plate, prebake is after 1 minute; In the baking oven of inner nitrogen replacement, under 200 ℃, heated 1 hour; Form filming of thickness 80nm, make substrate B.In addition, substrate B side is not shone polarisation UV.
The periphery of the face of filming having of aforesaid substrate B, apply the epoxy adhesive of the alumina balls that added diameter 5.5 μ m through serigraphy after, with the coated surface subtend crimping of substrate A, under 150 ℃, spend 1 hour with the bonding agent heat curing.Then, from liquid crystal injecting port, in the gap between substrate, fill negative type liquid crystal (メ Le Network manufactured, MLC-6608) after, through acrylic compounds Photocurable adhesive encapsulated liquid crystals inlet.Then, the flow orientation when injecting in order to remove liquid crystal, with it 150 ℃ of heating after 10 minutes, slow cool to room temperature.Then, on the two sides, the outside of substrate A, B, the applying polaroid is so that its polarization direction is mutually orthogonal, and in substrate A and ultraviolet optical axis form 45 ° angle toward the projecting direction of real estate, make liquid crystal display cells.
(embodiment 2～7)
The material that use below table 2 is put down in writing is as beyond the aligning agent for liquid crystal, through making liquid crystal cell with embodiment 1 same method.
(embodiment 8)
1, evaluation is with the manufacturing of box [1]
At first, on the transparency electrode face of peeling off substrate, be coated with the aligning agent for liquid crystal (AF-1) of above-mentioned preparation example 1 preparation through spinner with the nesa coating (ITO film) that forms the slit-shaped pattern.This baseline shown in Figure 2 as the pattern use of transparency electrode is respectively the pattern of the slit-shaped of 5 μ m with the interval.Then, on 80 ℃ hot plate, prebake in the baking oven of inner nitrogen replacement, under 200 ℃, heated 1 hour after 1 minute, formed filming of thickness 80nm, made substrate A.Likewise, on the transparency electrode face of the glass substrate with the ITO film that forms the slit-shaped pattern shown in Figure 2, use spinner; Be coated with the aligning agent for liquid crystal (AF-8) of above-mentioned preparation example 8 preparations, on 80 ℃ hot plate, prebake is after 1 minute; In the baking oven of inner nitrogen replacement, under 200 ℃, heated 1 hour; Form the liquid crystal orientation film of thickness 80nm, make substrate B.
Periphery at the face of aforesaid substrate B with liquid crystal orientation film; Apply the epoxy adhesive of the alumina balls that added diameter 5.5 μ m through serigraphy after; The liquid crystal orientation film of substrate A is faced to crimping, under 150 ℃, spent 1 hour the bonding agent heat curing.Then, from liquid crystal injecting port, in the gap between substrate, fill negative type liquid crystal (メ Le Network manufactured, MLC-6608) after, use the acrylic compounds Photocurable adhesive, encapsulated liquid crystals inlet, manufacturing liquid crystal cell.Then, the flow orientation when injecting in order to remove liquid crystal, with it 150 ℃ of heating after 10 minutes, slow cool to room temperature.Then,, use Halogen lamp LED, carry out 50,000J/m at the liquid crystal cell of the state of the AC voltage that applies 10V 2Rayed after, on the two sides, the outside of box substrate, the applying polaroid also makes its polarization direction mutually orthogonal; And in substrate A; Form 45 ° angle with ultraviolet optical axis toward the projecting direction of real estate, make liquid crystal display cells, with it as estimating with box [1].
2, evaluation is with the manufacturing of box [2]
Except using the glass substrate of substrate do not form pattern as the band transparency electrode, through with above-mentioned evaluation with the same method of box 1, on substrate, form and film, manufacturing substrate A, B.Then, use these substrates A, B, through constituting liquid crystal cell with box 1 same method with above-mentioned evaluation; Flow orientation when injecting in order to remove liquid crystal descends heating after 10 minutes at 150 ℃ it, slowly behind the cool to room temperature; To not applying the liquid crystal cell of voltage status; Use Halogen lamp LED, rayed 50,000J/m 2Afterwards, on the two sides, the outside of box substrate, the applying polaroid is so that its polarization direction is mutually orthogonal, and in substrate A and ultraviolet optical axis form 45 ° angle toward the projecting direction of real estate, make liquid crystal display cells, with it as estimating with box [2].
(embodiment 9～14)
Except the material that uses below table 2 records as the aligning agent for liquid crystal and embodiment 8 likewise make two kinds of liquid crystal display cells (evaluation) with box [1], [2].
(comparative example 1～3)
Except the material that uses below table 2 records as aligning agent for liquid crystal, and substrate A and substrate B both is not shone beyond the polarisation UV and embodiment 1 likewise makes liquid crystal display cells.
(comparative example 4,5)
Except the material that uses below table 2 records as the aligning agent for liquid crystal, the method through same with embodiment 1 forms on each surface of two substrates and films.Then, on each surface of filming, use Hg-Xe lamp and Glan-Taylor prism, from tilt 40 ° direction of the direction on relative vertical substrate surface, irradiation contains the ultraviolet 200J/m of polarisation of the bright line of 313nm 2, form liquid crystal orientation film, make substrate A, B.
Then; Periphery at the face of aforesaid substrate A with liquid crystal orientation film; Apply the epoxy adhesive of the alumina balls that added diameter 5.5 μ m through serigraphy after; With the liquid crystal orientation film of substrate B in the face of to configuration, crimping so that the ultraviolet optical axis of each substrate toward the projecting direction antiparallel of real estate, 150 ℃ down with 1 hour with the bonding agent heat curing.Then, from liquid crystal injecting port, in the gap between substrate, fill negative type liquid crystal (メ Le Network manufactured, MLC-6608) after, the limit is with the shading of box part, the limit is through acrylic compounds Photocurable adhesive encapsulated liquid crystals inlet.Then, the flow orientation when injecting in order to remove liquid crystal, with it at 150 ℃ down after the heating, slow cool to room temperature.Then, on the two sides, the outside of substrate, the applying polaroid is so that its polarization direction is mutually orthogonal, and forms 45 ° angle with the ultraviolet optical axis of liquid crystal orientation film toward the projecting direction of real estate, makes liquid crystal display cells.
[evaluation of liquid crystal display cells]
Liquid crystal display cells to making carries out the character evaluation through following method to projects.
(1) evaluation of voltage retention
To the liquid crystal display cells of above-mentioned manufacturing, apply the voltage of 5V with the application time of 60 microseconds, 167 milliseconds interval after, measure and be applied to the voltage retention (VHR) after 167 milliseconds from releasing.Measuring apparatus (manufactured) Dongyang Te ni black grades manufactured VHR-1.In addition, embodiment 8～14 in-service evaluations carry out with box [2].
(2) evaluation of response speed (the electrooptics response during beginning)
In the device that has comprised polarizing microscope and photodetector and pulse producer, measure the start time of liquid crystal response.Liquid crystal response speed definition described here applied for 1 second during 5V voltage for the state that in the liquid crystal display cells of making, never applies voltage to maximum, was changed to the 90% needed time of transmittance (unit: millisecond) from transmittance 10%, estimated.In addition, embodiment 8～14 in-service evaluations carry out with box [1].
(3) photostability evaluation
Through being that the VHR of irradiation after 3000 hours likewise measured in weather-proof appearance and above-mentioned (1) of light source with the carbon arc.Evaluation is to compare with the measured value of pre-irradiation, the VHR variable quantity be 1% with interior as zero, 1～3% as △, the conduct more than 3% *.In addition, embodiment 8～14 in-service evaluations carry out with box [2].
(4) contrast evaluation
In following method, to the not good evaluation light transmission degree of orientation in the liquid crystal cell of making, estimate black level, as a comparison the alternative evaluation of degree evaluation.At first,, make the visual field the most secretly dispose liquid crystal cell, take a picture and take this image through the polarized light microscope observing of quadrature Nikkor condition.The data separation that obtains be 0.2mm square * 25 pixels, image processing software is used in the brightness of each pixel, numerical value turns to 255 contrasts.The contrast difference of each pixel (25 pixel) is in 30 the time, is evaluated as contrast good (zero), and the contrast difference was evaluated as contrast bad (*) greater than 30 o'clock.In addition, embodiment 8～14 in-service evaluations carry out with box [1].
The evaluation result of above-mentioned (1)～(4) is represented in below table 2.
[table 2]
Figure BSA00000668597200531
As shown in table 2, the liquid crystal display cells of embodiment 1～14 demonstrates high voltage retention, and liquid crystal molecule is good to the response property of change in voltage simultaneously.In addition, the contrast of these liquid crystal display cells is also good.Particularly, use the liquid crystal display cells (embodiment 1～3,8～10) of the aligning agent for liquid crystal formation that comprises the radiation-sensitive polysiloxane, its permanance is also excellent.
In addition, for embodiment 1～14, if the embodiment 1～7 that photocatalytic coating film irradiation back is constituted liquid crystal cell with constitute liquid crystal cell after light-struck embodiment 8～14 compare, the response property of the former liquid crystal molecule is better.
On the other hand, the response speed of comparative example 1～5 is all fast, but liquid crystal molecule is bad to the response speed of change in voltage.

Claims (9)

1. liquid crystal display cells, this liquid crystal display cells has a pair of substrate, it is characterized in that:
On the substrate surface in aforementioned a pair of substrate, form the 1st alignment films of the direction tilted alignment that makes vertical relatively this substrate surface of liquid crystal molecule, and on another substrate surface, form and make the 2nd vertical orientated alignment films of liquid crystal molecule,
Aforementioned the 1st alignment films use comprises the aligning agent for liquid crystal of the radiation-sensitive compound with light orientation group and forms,
The structure of at least a compound of selecting in the group that this light orientation group has free azobenzene, talan, alpha-imino-'beta '-ketoester, spiro-pyrans, spiral shell oxazine, cinnamic acid, chalcone, stilbene azoles, benzal phthalimide, cumarin, dibenzenyl and anthraquinone to constitute.
2. the liquid crystal display cells of putting down in writing according to claim 1, wherein aforementioned lights orientation group has the structure from cinnamic acid.
3. the liquid crystal display cells of being put down in writing according to claim 1 or 2 wherein comprises the polysiloxane with aforementioned lights orientation group as aforementioned radiation-sensitive compound.
4. the manufacturing approach of a liquid crystal display cells, this manufacturing approach is the manufacturing approach with liquid crystal display cells of a pair of substrate, it is characterized in that:
Comprise the manufacturing process that makes liquid crystal display cells; On the substrate surface of this liquid crystal display cells in aforementioned a pair of substrate; Formation makes the 1st alignment films of the direction tilted alignment of vertical relatively this substrate surface of liquid crystal molecule; And on another substrate surface, form and make the 2nd vertical orientated alignment films of liquid crystal molecule
Aforementioned the 1st alignment films uses the light orientation that comprises the radiation-sensitive compound with light orientation group to form with aligning agent for liquid crystal,
The structure of at least a compound of selecting in the group that this light orientation group has free azobenzene, talan, alpha-imino-'beta '-ketoester, spiro-pyrans, spiral shell oxazine, cinnamic acid, chalcone, stilbene azoles, benzal phthalimide, cumarin, dibenzenyl and anthraquinone to constitute.
5. the manufacturing approach of the liquid crystal display cells of putting down in writing according to claim 4 is characterized in that aforementioned manufacturing process comprises:
On the surface of a substrate in aforementioned a pair of substrate, use the aforementioned lights orientation use aligning agent for liquid crystal, form the 1st the 1st film formation operation of filming;
Through to the aforementioned the 1st irradiates light of filming, make the 1st to film and become the rayed of aforementioned the 1st alignment films operation;
On another substrate surface in aforementioned a pair of substrate, use can form the aligning agent for liquid crystal of vertical alignment layer, forms the 2nd film of filming as the 2nd of aforementioned the 2nd alignment films and forms operation; And
Make aforementioned the 1st alignment films and the aforementioned the 2nd aforementioned a pair of substrate of subtend ground configuration of filming, and between this substrate the filling liquid crystal molecule, the box that constitutes liquid crystal cell constitutes operation.
6. the manufacturing approach of the liquid crystal display cells of putting down in writing according to claim 4, wherein aforementioned manufacturing process comprises:
On the surface of a substrate in aforementioned a pair of substrate, use the aforementioned lights orientation to use aligning agent for liquid crystal, form the 1st film of filming and form operation;
On another substrate surface in aforementioned a pair of substrate, use the aligning agent for liquid crystal that does not contain the compound with light orientation group in fact, the 2nd film that forms aforementioned the 2nd alignment films forms operation;
Make aforementioned filming and the aforementioned a pair of substrate of aforementioned the 2nd alignment films subtend ground configuration, and between this substrate the filling liquid crystal molecule, the box that constitutes liquid crystal cell constitutes operation; And
Aforementioned box is constituted the foregoing liquid crystal box that operation constitutes, between aforementioned a pair of substrate, apply under the state of voltage the rayed operation of irradiates light.
7. the manufacturing approach of the liquid crystal display cells of putting down in writing according to claim 4, wherein aforementioned lights orientation group has the structure from cinnamic acid.
8. the manufacturing approach of the liquid crystal display cells of putting down in writing according to claim 4～7 wherein comprises the polysiloxane with aforementioned lights orientation group as the aforementioned lights reactive compounds.
9. aligning agent for liquid crystal, this aligning agent for liquid crystal is used to make each liquid crystal display cells of being put down in writing of claim 1～3.
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Application publication date: 20120808