CN1813041A

CN1813041A - Polymers for use as alignment layers in liquid crystal devices

Info

Publication number: CN1813041A
Application number: CN 200480017692
Authority: CN
Inventors: L·科米托夫; B·赫尔基
Original assignee: Ecsibeo PPF2 AB
Current assignee: Ecsibeo PPF2 AB
Priority date: 2003-06-23
Filing date: 2004-03-04
Publication date: 2006-08-02
Also published as: CN100407012C; CN1813217A; SE0301810D0

Abstract

The invention relates to a polymer which is used as a surface direction finder calibration layer in a liquid crystal device, the polymer comprises a polymer backbone chain and lateral chains which are connected to the backbone chain, wherein the polymer backbone chain is provided with a ring structure which is directly coupled, at least one lateral chain of a plurality of lateral chains comprises a carbon-carbon singly-bound(-), a unit (-CH=CH-) which contains the carbon-carbon singly-bound, a unit (-C is equivalent to C-) which contains carbon-carbon triple bond, a methylene-ether unit (-CH2O-), an ethylidene ether unit (-CH2CH2O-), an ester (-COO-) and an azo unit (-N=N-) by means of at least two unsubstituted or substituted phenyls which are coupled and selected from the following coupling base, wherein the lateral chains display permanent and/or induced dipole moments and the dipole moments provide the dielectric anisotropy in an ordered phase form and are connected on the polymer backbone chain through at least two interval atoms.

Description

In liquid crystal device, be used as the polymkeric substance of alignment layer

Technical field

Relate generally to field of liquid crystals of the present invention.The invention particularly relates to the polymkeric substance that in liquid crystal device (LCD), is used as surface orientation device (director) alignment layer.

The invention still further relates to the method for the described polymkeric substance of preparation, contain the composition of described polymkeric substance, contain the surface orientation device alignment layer of described polymkeric substance, described polymkeric substance is as the purposes of surface orientation device alignment layer and the method for manufacturing liquid crystal device.

Background technology

One of basic principle of operation of liquid-crystal display and device is the switching that causes liquid crystal molecular orientation by the extra electric field on the dielectric anisotropy that is coupled to liquid crystal material (dielectric coupling).This coupling obtains the photoelectricity of extra electric field quadratic equation and replys, and is promptly irrelevant with electric polarity.

Have structural anisotropy, have ordered molecular structure (ordered phase), for example the dielectric anisotropy of the material of crystallization or liquid crystal structure (Δ ε) is in this material, with respect to preferred molecular orientation, the specific inductivity of measuring on vertical and parallel direction is poor respectively.

When electric field is applied on the liquid crystal material that demonstrates positive dielectric anisotropy (Δ ε＞0), molecule will be calibrated its major axis along (or basically along) direction of an electric field.

When electric field is applied on the liquid crystal material that demonstrates negative dielectric anisotropy (Δ ε＜0), molecule will be calibrated its major axis perpendicular to (or being substantially perpendicular to) direction of an electric field.

Liquid crystal molecule is long rodlike molecule (a so-called calamitic molecule), and it has along the ability (orientation) of its major axis calibration on some preferred directions.Determine the mean direction of molecule and be called orientor by vector.

In liquid-crystal display, there is not the outfield, for example under the situation of electric field, usually pass through surface treatment confining solid substrate surface suitably, for example by on the confining substrate surface of described body of liquid crystal, applying so-called (surface orientation device) alignment layer (being also referred to as oriented layer), thereby realize the required initial calibration of liquid crystal layer.Determine initial liquid crystal alignment by solid surface/mesomorphic phase mutual effect.The orientation of the liquid crystal molecule adjacent with the confining surface is transferred on the liquid crystal molecule in body with elastic force, thereby applies substantially the same being calibrated on all body of liquid crystal molecules.

The orientor (hereinafter being also referred to as the surface orientation device) of the liquid crystal molecule of close confining substrate surface is confined to some directions, on the point of for example vertical with the confining substrate surface (be also referred to as and reverse in the same way or vertical direction) or parallel (being also referred to as in-plane) direction.According to the symbol of dielectric anisotropy, the direction of extra electric field and the switch mode (in the face or outside the face) of required type, select to be coupled as the type of calibration of the liquid-crystal display of fundamental operation between liquid crystal dielectric anisotropy and the extra electric field.

Outside utilization has the face of body of liquid crystal of negative dielectric anisotropy, switch in the liquid crystal cells, importantly evenly the orientor (under field-free state) of aligned liquid-crystal body molecule perpendicular to substrate surface (so-called reverse in the same way calibration).

Set up the example reverse Calibration Method in the same way and comprise and use tensio-active agent that for example Yelkin TTS or cetyl trimethylammonium bromide are coated with the confining substrate surface.Then, the surface of also preferred wiping coat substrates in a predetermined direction is so that the field inductive planar orientation of liquid crystal molecule is orientated on predetermined wiping direction.In laboratory study, this method can obtain good result, but never finds industrial acceptance, and this is because alignment layer slowly is dissolved in the bulk liquid crystal, therefore can not get permanent stability (J.Cognard, Mol.Cryst.Liq.Cryst., Suppl.Ser., 1982,1,1).

Switch liquid crystal cells and utilize in the face of body of liquid crystal of the dielectric anisotropy with plus or minus outside utilization has the face of body of liquid crystal of positive dielectric anisotropy and switch in the liquid crystal cells, importantly evenly the orientor (under field-free state) of aligned liquid-crystal body molecule is parallel to substrate surface (so-called plane calibration).For the stable twisted nematic liquid crystal cells, it is also important that, to become orientation angles (pre-tilt angle) the aligned liquid-crystal body molecule of certain inclination with substrate.

The currently known methods of setting up plane calibration for example is mineral membrane CVD (Chemical Vapor Deposition) method and organic membrane wiping method.

In the mineral membrane CVD (Chemical Vapor Deposition) method, by vapour deposition inorganics obliquely, for example silicon oxide forms mineral membrane on substrate surface to the confining substrate, so that depend on inorganics and gasification condition, on a certain direction, pass through mineral membrane aligned liquid-crystal molecule.Because the production cost height, so this method is not suitable for scale operation, and in fact this method can not be used.

According to organic membrane wiping method, on substrate surface, for example form the organic coating of polyvinyl alcohol, polyoxyethylene, polymeric amide or polyimide.Use for example cloth of cotton, nylon or polyester afterwards, with this organic coating of pre-determined direction wiping, so that the liquid crystal molecule that contacts with this layer is orientated on the wiping direction.

Commercial, polyvinyl alcohol (PVA) is seldom as alignment layer, and this is because these polymkeric substance are hydrophilic, and the absorbent polymer that can absorb moisture is the molecular orientation of impact polymer unfriendly, and therefore influences the performance of liquid crystal device.In addition, PVA can attract ion, and described ion can damage the performance of liquid crystal device equally.

In addition, polyoxyethylene can attract ion, thereby causes the liquid crystal device performance damaged.

Polymeric amide has low solubleness in most of common acceptable solvent.Therefore, commercial polymeric amide seldom uses in liquid crystal device is made.

In most of the cases, polyimide is owing to its quite favourable feature, and for example therefore chemical stability, thermostability etc. are used as organic top coat.Applying polyimide layer generally includes as described below 200-300 ℃ of step of toasting down.

For example, prepare polyimide according to following flow process I or flow process II:

Flow process I

Flow process II

In the first step, the tetracarboxylic anhydride of equimolar amount and diamines for example mix in the N-Methyl pyrrolidone (NMP) at amide solvent.Spontaneous reaction takes place, and forms polyamic acid (it is the prepolymer of polyimide).Prepolymer under this state is distributed to its user, for example LCD manufacturers.Yet, because this pre-polymer solution rather unstable at room temperature, therefore,, cool off this solution usually, to avoid the degraded of prepolymer, perhaps any other undesired chemical reaction when transportation with when storing.

In general, often adopt the mixture of NMP and ethylene glycol butyl ether 4: 1 (w/w) to dilute polyamic acid by liquid crystal device manufacturers to about 0.5%.

The NMP ethylene glycol butyl ether

Usually use the printing technology of for example spin coating or some type, on the substrate of glass that is coated with indium tin oxide target (ITO) electrode layer transparent, composition, apply polyamic acid.Then, in baking oven, dry polyamic acid layer under about 100 ℃ was heated to about 200 ℃ afterwards through 1-2 hour.In this heating cycle process, polyamic acid changes into polyimide.This step is also referred to as the curing or the baking of polyimide.Very thermally-stabilised of gained polyimide and be insoluble to all solvents.Can only for example make it degraded, thereby remove this polymkeric substance by the use alkaline medium.

The shortcoming of this organic membrane method of application is a baking procedure, and this had both caused the long production time, caused high production cost again.

In addition, (LCOS) and in the manufacturing of thin film transistor (TFT), should avoid high temperature at the liquid crystal on silicon (liquid-crystal-on-silicon) for example, for example about 200 ℃, this is because high temperature can cause the productive rate that reduces, and therefore causes the defective of film.

Also be difficult to control and use organic membrane that described organic membrane method of application applies and the bonding strength between the liq-uid crystal bulk layer.

If can save described baking procedure and avoid above-mentioned shortcoming, then be very favorable.

Summary of the invention

The objective of the invention is to avoid the above-described shortcoming of known surface orientation device calibration materials, and be provided at liquid crystal device, for example be used as the improvement material of surface orientation device alignment layer in liquid crystal display device and other liquid crystal device etc.

According to a first aspect of the invention, employing contains main polymer chain and realizes this and other purpose with the polymkeric substance of the side chain that is connected thereto, wherein this main polymer chain does not have each side chain of direct link coupled ring structure and at least some side chains to comprise with being selected from following at least two phenyl that do not replace and/or replace of coupling base link coupled: the unit of carbon-carbon single bond (-), carbon-carbon double bonds (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), ester units (COO-) and the azo unit (N=N-), these side chains demonstrate permanent and/or inductive moment of dipole, described moment of dipole provides dielectric anisotropy with orderly phase form, and by at least two interval atoms, preferably at least 5 interval atoms are connected on the main polymer chain.

Main polymer chain is polyvinyl acetal preferably.

Adopt the advantage of this base polymer to be, they dissolve in organic solvent, for example the mixture of chloroform, tetrahydrofuran (THF), dimethylbenzene and butylacetate, N,N-DIMETHYLACETAMIDE, dimethyl formamide and N-Methyl pyrrolidone.Because polymkeric substance of the present invention dissolves in organic solvent, therefore, the solution of polymkeric substance itself (rather than solution of its prepolymer) but paint in liquid crystal device, be used as on the substrate surface of surface orientation device alignment layer, and do not need curing schedule, as disclosed in the background technology, described curing schedule is used to involve the calibration materials of prior art, for example in the method for polyimide etc.Therefore, avoided heating 1-2 hour step of prepolymer down at about 180-250 ℃.For liquid crystal device, avoid curing schedule to reduce the production cycle time, thereby save time, energy and money.Compare with the production method of routine, use polymkeric substance of the present invention can realize production time about 20% decline at most.

In addition, fierce heating can cause defective and reduce productive rate in the solidification process of the calibration materials of prior art.Use polymkeric substance of the present invention also to avoid these shortcomings, and can significantly increase productive rate,

In addition, do not require high-grade baking oven equipment, therefore, can reduce cost of investment for the production line that uses polymkeric substance of the present invention.

Another advantage of polymkeric substance of the present invention is, not only can be on substrate of glass, and can be on plastic-substrates applying polymer.Wherein, then can not use described plastic-substrates if adopt heating (curing) step.On plastic-substrates, apply and make and to use various substrate forms, for example curved surface substrate surface and curling substrate surface.

An advantage again of polymkeric substance of the present invention is, the solution of described polymkeric substance in organic solvent is at room temperature stable, and promptly dissolved polymers is non-degradable when at room temperature storing.Therefore, do not need to cool off this solution, and, require described cooling usually for the pre-polymer solution that uses according to prior art.

The another advantage of polymkeric substance of the present invention is, this polymkeric substance is provided at the improvement control of bonding strength between the alignment layer of polymkeric substance of the present invention and the liq-uid crystal bulk layer, and therefore answering time is provided, i.e. (strong bonding strength provides short time of lag and weak bonding strength that the short rise time is provided) controlled in the improvement of rising and time of lag.

Should be noted that and to utilize existing processing unit, in the existing manufacturing process of liquid crystal device, use polymkeric substance of the present invention.

According to a second aspect of the invention, the method for preparing polymkeric substance of the present invention is provided, this method comprises makes side chain precursor and the main polymer chain reaction that does not have direct link coupled ring structure, and wherein said side chain precursor comprises with being selected from following two phenyl that do not replace and/or replace of coupling base link coupled at least: the unit of carbon-carbon single bond (-), carbon-carbon double bonds (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), (COO-) (N=N-), these side chains demonstrate permanent and/or inductive moment of dipole to ester units, and described moment of dipole provides dielectric anisotropy with orderly phase form with the azo unit.

According to a third aspect of the invention we, the method for preparing polymkeric substance of the present invention is provided, this method comprises that the monomer polymerization that will have side chain becomes not have the main polymer chain of direct link coupled ring structure, and wherein each side chain at least some side chains comprises with being selected from following two phenyl that do not replace and/or replace of coupling base link coupled at least: the unit of carbon-carbon single bond (-), carbon-carbon double bonds (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), (COO-) (N=N-), these side chains demonstrate permanent and/or inductive moment of dipole to ester units, and described moment of dipole provides dielectric anisotropy with orderly phase form with the azo unit.

According to a forth aspect of the invention, be provided at the composition that is used as surface orientation device alignment layer in the liquid crystal device, described composition comprises at least a polymkeric substance of the present invention.

According to a fifth aspect of the invention, be provided at the surface orientation device alignment layer that uses in the liquid crystal device, described layer comprises at least a polymkeric substance of the present invention.

According to a sixth aspect of the invention, provide polymkeric substance of the present invention purposes as surface orientation device alignment layer in liquid crystal device.

According to a seventh aspect of the invention, provide the method for making liquid crystal device, described method comprises the steps:

-the surface orientation device that contains polymkeric substance of the present invention alignment layer is provided on the surface of at least one substrate; With

-between two substrates, accompany liquid crystal layer, wherein at least one substrate has described polymkeric substance, wherein arranges described substrate, so that described surface orientation device alignment layer is towards liquid crystal layer.

According to following explanation of the present invention, other features and advantages of the present invention will become apparent.

Description of drawings

Fig. 1 shows containing surface orientation device alignment layer of the present invention and demonstrating rising and the time of lag (referring to embodiment 17) that the liquid crystal device of the initial vertical calibration of liq-uid crystal bulk layer is measured.

Fig. 2 shows containing surface orientation device alignment layer of the present invention and demonstrating rising and the time of lag (referring to embodiment 18) that the liquid crystal device of the initial vertical calibration of liq-uid crystal bulk layer is measured.

Fig. 3 shows containing surface orientation device alignment layer of the present invention and demonstrating rising and the time of lag (referring to embodiment 19) that the liquid crystal device of the initial vertical calibration of liq-uid crystal bulk layer is measured.

Fig. 4 shows containing surface orientation device alignment layer of the present invention and demonstrating rising and the time of lag (referring to embodiment 21) that the liquid crystal device of the initial plane calibration of liq-uid crystal bulk layer is measured.

Embodiment

At this by with reference to introducing and requiring the pendent Sweden application 0301810-8 and the 0303041-8 of its right of priority to disclose a kind of liquid crystal device, it is included in the liq-uid crystal bulk layer that there is the surface orientation device in its body surface place, with be the surface orientation device alignment layer that interacts and to arrange with body layer at described body surface place, so that help to obtain the preferred orientation of the surface orientation device of body layer, wherein liq-uid crystal bulk layer and surface orientation device alignment layer are directly controlled with dielectric coupling by electric field separately.Depend on display type and required effect, surface orientation device alignment layer can show the dielectric anisotropy of plus or minus, and perhaps this layer can comprise the structure division of the dielectric anisotropy (Δ ε) that demonstrates contrary sign.

In these applications, contain main polymer chain (Z) and the following polymkeric substance of one or more side chains of being connected thereto in some example forms as suitable surface orientation device calibration materials provide.

In the application's chemical formula, use following writing a Chinese character in simplified form:

R1 and R2 are aliphatic hydrocarbon chain independently of one another, and for example alkyl preferably contains 1-20 carbon atom, the alkyl of 2-12 carbon atom for example,

R3 (expression is atom at interval) is to contain at least 2, preferred 2-20, for example 4-20, more preferably 5-20 carbon atom or heteroatomic aliphatic hydrocrbon, as alkyl, siloxanes, glycol chain, perhaps its any combination (should be noted that, carbon atom or heteroatoms number can be along the main polymer chain random variation)

R4 is an aliphatic hydrocarbon chain, alkyl for example, and it preferably contains 1-20 carbon atom, 1-5 carbon atom for example,

R5 and R6 are aliphatic hydrocrbon, siloxanes, glycol chain or its any combination independently of one another, and it preferably contains 4-22,6-20 for example, and more preferably 8-18, for example 9-15 carbon atom or heteroatoms,

X and Y are H, F, Cl, CN or CF independently of one another ₃,

X ₁And Y ₁Be F or Cl independently of one another, preferred F and

Z is a part that does not have the main polymer chain of direct link coupled ring structure, preferred following polyvinyl acetal:

Formula I-X is the example of polymkeric substance of the present invention, and it comprises the side chain that demonstrates permanent and/or inductive moment of dipole, and described moment of dipole provides positive dielectric anisotropy with orderly phase form.These polymkeric substance are suitable for switching outside face for example provides initial field-free vertical calibration in the liquid crystal device.

Formula I formula II

Formula III formula IV

Formula V

Formula VI

Formula VII

Formula VIII

Formula IX formula X

Formula XI-XIII is the example of polymkeric substance of the present invention, and it comprises the side chain (S that demonstrates permanent and/or inductive moment of dipole ₁), described moment of dipole provides positive dielectric anisotropy with orderly phase form and does not demonstrate any permanent and/or inductive moment of dipole, and therefore side chain (the S of any dielectric anisotropy is not provided ₃).These polymkeric substance are suitable for switching outside face for example provides initial field-free vertical calibration in the liquid crystal device.

Formula XI formula XII

Formula XIII

Formula XIV-XIX has provided the specific examples of this base polymer of the present invention.

Formula XIV formula XV

Formula XVI formula XVII

Formula XVIII formula XIX

Wherein R4 is CH ₃(m+n)/o in the 25/50-43/14 scope, preferably be higher than 40/20, for example 42/16 and m/n in the 9/1-1/9 scope, preferred 3/1-1/3, for example 2/1.

Formula XX represents the example of polymkeric substance of the present invention, and it comprises the side chain (S that two classes are different ₁And S ₂) and side chain (S ₃), described side chain (S ₁And S ₂) demonstrating permanent and/or inductive moment of dipole, described moment of dipole provides positive dielectric anisotropy with orderly phase form, described side chain (S ₃) do not demonstrate any permanent and/or inductive moment of dipole, and therefore any dielectric anisotropy is not provided.These polymkeric substance are suitable for switching outside face for example provides initial field-free vertical calibration in the liquid crystal device.

Formula XX

Formula XXI-XXII has provided the specific examples of this base polymer of the present invention.

Formula XXI formula XXII

Wherein R4 is CH ₃, R ₅Be CH ₃(m+n)/o in the 25/50-43/14 scope, preferably be higher than 40/20, for example 42/16 and m/n in the 9/1-1/9 scope, preferred 3/1-1/3, for example 2/1.

Formula XXIII-XXXIII is the example of polymkeric substance of the present invention, and it comprises side chain (S ₁), described side chain (S ₁) demonstrating permanent and/or inductive moment of dipole, described moment of dipole provides negative dielectric anisotropy with orderly phase form.These polymkeric substance are suitable for switching in the liquid crystal device outside face for example or in the face provides initial field-free plane calibration.

Formula XXIII formula XXIV

Formula XXV formula XXVI

Formula XXVII formula XXVIII

Formula XXIX formula XXX

Formula XXXI

Formula XXXII formula XXXIII

Formula XXXIV has provided the specific examples of polymkeric substance of the present invention, and it comprises side chain (S ₁) and side chain (S ₃), described side chain (S ₁) demonstrating permanent and/or inductive moment of dipole, described moment of dipole provides negative dielectric anisotropy with orderly phase form, described side chain (S ₃) do not demonstrate any permanent and/or inductive moment of dipole, and therefore any dielectric anisotropy is not provided.This polymkeric substance is suitable for switching in the liquid crystal device outside face for example or in the face provides initial field-free plane calibration.

Formula XXXIV

Wherein (m+n)/o preferably is higher than 40/20 in the 25/50-43/14 scope, for example 43/18 and m/n in the 9/1-1/9 scope, preferred 3/1-1/3, for example 1/1.

Formula XXXV-LI is the example of polymkeric substance of the present invention, and it comprises side chain (S ₁), described side chain (S ₁) demonstrating permanent and/or inductive moment of dipole, described moment of dipole provides positive dielectric anisotropy with orderly phase form.These polymkeric substance are suitable for switching in the liquid crystal device in face for example provides initial field-free plane calibration.

Formula XXXV formula XXXVI

Formula XXXVII formula XXXVIII

Formula IXL formula XL

Formula XLI formula XLII

Formula XLIII formula XLIV

Formula XLV formula XLVI

Formula XLVII formula XLVIII

Formula IL formula L

Formula LI

Formula LII-LVI is the example of polymkeric substance of the present invention, and it comprises side chain (S ₁) and side chain (S ₃), described side chain (S ₁) demonstrating permanent and/or inductive moment of dipole, described moment of dipole provides positive dielectric anisotropy with orderly phase form, described side chain (S ₃) do not demonstrate any permanent and/or inductive moment of dipole, and therefore any dielectric anisotropy is not provided.This polymkeric substance is suitable for switching in the liquid crystal device in face for example provides initial field-free plane calibration.

Formula LII formula LIII

Formula LIV

Formula LV formula LVI

Formula LVII-LX is the example of polymkeric substance of the present invention, and it comprises side chain (S ₁), described side chain (S ₁) demonstrating permanent and/or inductive moment of dipole, described moment of dipole provides negative dielectric anisotropy with orderly phase form.These polymkeric substance are suitable for switching outside face for example provides initial field-free vertical calibration in the liquid crystal device.

Formula LVII

Formula LVIII

Formula LIX

Formula LX

Formula LXI represents the example of polymkeric substance of the present invention, and it comprises side chain (S ₁) and side chain (S ₃), described side chain (S ₁) demonstrating permanent and/or inductive moment of dipole, described moment of dipole provides negative dielectric anisotropy with orderly phase form, described side chain (S ₃) do not demonstrate any permanent and/or inductive moment of dipole, and therefore any dielectric anisotropy is not provided.This polymkeric substance is suitable for switching outside face for example provides initial field-free vertical calibration in the liquid crystal device.

Formula LXI

Formula LXII represents the example of polymkeric substance of the present invention, and it comprises the side chain (S with dimeric structure ₁), each dimeric structure has first structure division that demonstrates permanent and/or inductive moment of dipole, described moment of dipole provides positive dielectric anisotropy with orderly phase form, with second structure division that demonstrates permanent and/or inductive moment of dipole, described moment of dipole provides negative dielectric anisotropy with orderly phase form.These polymkeric substance are suitable for switching in the liquid crystal device in face for example provides initial field-free plane calibration.

Formula LXII

Formula LXIII-LXVII is the example of polymkeric substance of the present invention, and it comprises the side chain (S with dimeric structure ₁), each dimeric structure has first structure division that demonstrates permanent and/or inductive moment of dipole, described moment of dipole provides positive dielectric anisotropy with orderly phase form, with second structure division that demonstrates permanent and/or inductive moment of dipole, described moment of dipole provides negative dielectric anisotropy with orderly phase form.These polymkeric substance are suitable for switching outside face for example provides initial field-free vertical calibration in the liquid crystal device.

Formula LXIII

Formula LXIV

Formula LXV

Formula LXVI

Formula LXVII

Formula LXVIII-LXX is the example of polymkeric substance of the present invention, and it comprises the side chain (S with tripolymer structure ₁), each tripolymer structure has first structure division that demonstrates permanent and/or inductive moment of dipole, described moment of dipole provides positive dielectric anisotropy with orderly phase form, with second structure division that demonstrates permanent and/or inductive moment of dipole, described moment of dipole provides negative dielectric anisotropy with orderly phase form, with the 3rd structure division that demonstrates permanent and/or inductive moment of dipole, described moment of dipole provides with orderly phase form or the dielectric anisotropy of plus or minus.These polymkeric substance are suitable for switching in the liquid crystal device outside face for example or in the face provides initial field-free plane calibration.

Formula LXVIII

Formula LXIX

Formula LXX

The polymkeric substance of formula I-LXX meets the present invention and discovery has above-described several advantages, wherein main polymer chain (Z) do not contain direct-coupled ring structure and wherein each side chain at least some side chains comprise with being selected from following at least two phenyl that do not replace and/or replace of coupling base link coupled: the unit of carbon-carbon single bond (-), carbon-carbon double bonds (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), (COO-) (N=N-), these side chains demonstrate permanent and/or inductive moment of dipole to ester units, and described moment of dipole provides dielectric anisotropy with orderly phase form, and are connected on the main polymer chain with at least two interval atoms with the azo unit.

Polymkeric substance of the present invention comprises main polymer chain and the side chain that is connected thereto, wherein each side chain of not containing in direct link coupled ring structure and at least some side chains of main polymer chain comprises with being selected from following two phenyl that do not replace and/or replace of coupling base link coupled at least: the unit of carbon-carbon single bond (-), carbon-carbon double bonds (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), ester units (COO-) and the azo unit (N=N-), these side chains demonstrate permanent and/or inductive moment of dipole, described moment of dipole provides dielectric anisotropy with orderly phase form, and with at least two interval atoms, preferably at least 5 interval atoms are connected on the main polymer chain.

Should be noted that the above coupling base that provides can comprise replacement and/or unsubstituted atom.For example, polymkeric substance of the present invention can comprise with the unit of fluorinated carbon-carbon double bond, for example-CF=CF-or-two phenyl of CH=CF-link coupled.

Two phenyl promptly do not have other atom or chemical bond between two phenyl preferably with only described coupling base coupling.

" side chain " as used herein is meant the atomic radical of going up branching from straight-chain molecule (main polymer chain herein).

" directly link coupled ring structure " as used herein is meant the condensed ring structure and with only singly-bound or multikey link coupled ring structure (promptly using only one or more chemical bond link coupled ring structures).

The example of fused rings structure is:

With the example of singly-bound link coupled ring structure only be:

Therefore, the repeating unit of the main polymer chain of polymkeric substance of the present invention can for example comprise with at least one replacement or unsubstituted carbon atom, for example-and (CH ₂) _n-,-(CHR) _n-and-(CR ₂) _n-and/or at least one replacement or unsubstituted heteroatoms link coupled ring structure.

The example that does not have the preferred main polymer chain of direct link coupled ring structure is a polyvinyl acetal.Should be noted that polyvinyl acetal as used herein comprises the polymkeric substance of being made by polyvinyl alcohol, the some of them side group, for example maximum 14% can be unreacted hydroxyl.The employed polyvinyl alcohol of preparation polyvinyl acetal can prepare by hydrolyzed poly vinyl acetate.Degree of hydrolysis preferably 〉=86% this means that the side group in maximum 14% polymkeric substance of the present invention still can be an acetate groups.

" unsubstituted phenyl " as used herein is meant phenyl, for example-and C ₆H ₄-and-C ₆H ₅

" substituted-phenyl " as used herein is meant wherein one or more hydrogen atoms quilts not homoatomic or group alternate phenyl.

" at interval atom " as used herein is meant side chain is connected to atom on the main polymer chain.These are atoms preferably at least 2 at interval, and more preferably at least 5 and most preferably 5-20 carbon atom or heteroatomic molecular chain.Molecular chain should preferably not comprise any ring texture (ring structure), and therefore, molecular chain is branching or nonbranched straight-chain molecule preferably.Interval atom in polymkeric substance of the present invention preferably includes aliphatic hydrocarbon chain, for example alkyl, siloxane chain, glycol chain or its any combination.

Should be noted that the interval atomic quantity that each side chain is connected on the main polymer chain can change by polymkeric substance according to the present invention.

As mentioned above, polymkeric substance of the present invention dissolves in organic solvent, for example the mixture of chloroform, tetrahydrofuran (THF), dimethylbenzene and butylacetate, N,N-DIMETHYLACETAMIDE, dimethyl formamide or N-Methyl pyrrolidone.Preferably, polymkeric substance of the present invention has solubleness in for example above-described any solvent, thereby is provided under the envrionment conditions at organic solvent, and concentration range is the stabilizing solution of 0.01-10% (w/w).The feasible polymkeric substance liquid storage that can prepare suitable high polymers concentration of the polymkeric substance of high-dissolvability in organic solvent, the polymkeric substance of for example about 5% (w/w).In addition, because polymkeric substance of the present invention dissolves in organic solvent easily, supplier even can they be flowed to the human consumer with solid-state form.Therefore, can reduce from polymkeric substance supplier flowing to the human consumer, the quantity of solvent flammable and dangerous as LCD manufacturer.

Preferably, the main polymer chain in polymkeric substance of the present invention comprises the unit according to the first kind random distribution of following formula:

S wherein ₁₀Represent first side chain, described first side chain comprises with being selected from following two phenyl that do not replace and/or replace of coupling base link coupled at least: the unit of carbon-carbon single bond (-), carbon-carbon double bonds (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), ester units (COO-) and the azo unit (N=N-), these side chains demonstrate permanent and/or inductive moment of dipole, described moment of dipole provides dielectric anisotropy with orderly phase form, with comprise at least two at interval atoms, wherein first side chain is connected on the main polymer chain with described interval atom; With the unit according to the second class random distribution of following formula:

When the main polymer chain in the polymkeric substance of the present invention comprised this class unit of random distribution, polymkeric substance was a polyvinyl acetal.

In addition, the main polymer chain in polymkeric substance of the present invention also can preferably include the unit according to the 3rd class random distribution of following formula:

S wherein ₂Represent second side chain, described second side chain is different from S ₁, demonstrating permanent and/or inductive moment of dipole, described moment of dipole provides dielectric anisotropy with orderly phase form and comprises at least two atoms at interval, and wherein second side chain is connected on the main polymer chain with described interval atom.By S ₂The dielectric anisotropy that provides can be different from by S ₁The dielectric anisotropy that provides.

Preferably, the described second side chain S ₂Comprise with being selected from following at least two phenyl that do not replace and/or replace of coupling base link coupled: the unit of carbon-carbon single bond (-), carbon-carbon double bonds (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), ester units (COO-) and the azo unit (N=N-).

The main polymer chain of polymkeric substance of the present invention also can comprise the unit according to further (the 3rd or the 4th) class random distribution of following formula:

S wherein ₃The expression side chain, described side chain is different from S ₁And S ₂, it does not demonstrate any permanent and/or inductive moment of dipole and therefore any dielectric anisotropy is not provided.Can use required specific side chain S ₁, randomly in conjunction with required specific side chain S ₂, this class unit is incorporated in the main polymer chain, to obtain polymkeric substance, described polymkeric substance demonstrates a certain required dielectric anisotropy with orderly phase form.Therefore, can use the side chain S that does not demonstrate any permanent and/or inductive moment of dipole and therefore any dielectric anisotropy is not provided ₃Reduce the dielectric anisotropy of the polymkeric substance of orderly phase form.

An embodiment of polymkeric substance of the present invention is the polymkeric substance that contains main polymer chain and the side chain that is connected thereto, wherein main polymer chain does not contain direct link coupled ring structure, comprises with being selected from two following similar or different three phenyl that do not replace and/or replace of coupling base link coupled with each side chain at least some side chains: the unit of carbon-carbon single bond (-), carbon-carbon double bonds (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), (COO-) (N=N-), these side chains demonstrate permanent and/or inductive moment of dipole to ester units, and described moment of dipole provides dielectric anisotropy with orderly phase form, and are connected on the main polymer chain by at least two interval atoms with the azo unit.For example, formula XIX, XXX, LII and LVII have provided the example of this class embodiment.

The invention still further relates to the composition that is used as surface orientation device alignment layer in liquid crystal device, described composition comprises at least a polymkeric substance of the present invention and second polymkeric substance, for example polyvinyl acetal.By changing the ratio between described at least a polymkeric substance of the present invention and described second polymkeric substance, can obtain required feature and processing parameter.

Composition of the present invention also can comprise at least two kinds of polymkeric substance of the present invention.

The invention still further relates to the surface orientation device alignment layer that uses in liquid crystal device, wherein this layer comprises at least a polymkeric substance of the present invention.Surface orientation device alignment layer can for example comprise a kind of polymkeric substance of the present invention or a kind of polymkeric substance of the present invention in conjunction with second polymkeric substance, for example polyvinyl acetal or another kind of polymkeric substance of the present invention.

Therefore, the invention still further relates to polymkeric substance of the present invention purposes as surface orientation device alignment layer in liquid crystal device.

Other purposes of polymkeric substance of the present invention can be to use in the material light chromium film that uses in for example eyes-glasses and automobile window in photo-alignment layer, polarizer, optical recording.

Now describe the present invention, wherein use following writing a Chinese character in simplified form: PCC=chloropyridine chromic salt, DCC=1 with following non-limiting example, the 3-dicyclohexylcarbodiimide, DMF=N, dinethylformamide, THF=tetrahydrofuran (THF), TsOH=tosic acid and PVA=polyvinyl alcohol.

A) example of the synthesis procedure of preparation polymkeric substance of the present invention

In the preparation of polymkeric substance of the present invention, side chain precursor is connected on the polymkeric substance that does not contain direct link coupled ring structure.The example of this polymkeric substance is a polyvinyl alcohol.

Employed side chain precursor or commercially available or can be by commercially available parent material is according to the operation preparation of for example listing in following embodiment 2 and 4.

Preferably, side chain precursor is connected on the polyvinyl alcohol by forming the acetal unit.The acetal groups of the low molar mass in aldehyde or the side chain precursor and two adjacent hydroxyl reactions on polyvinyl alcohol form the polyvinyl acetal of required high molecular weight.Reaction is for example carried out in DMF, the THF Huo diox preferably at acid amides or ether solvents.In addition, reaction is preferably at acid catalyst, and for example TsOH carries out under existing.

The preferred polyvinyl alcohol of hydrolysis at least 86% (promptly 14% or lower acetate groups stay) that use.The weight-average molecular weight of polyvinyl alcohol (Mw) is preferably in the 10000-40000 scope, more preferably in the 13000-23000 scope.

The side chain precursor of Shi Yonging has two classes in the following embodiments:

A) following molecule, described molecule demonstrates permanent and/or inductive moment of dipole, described moment of dipole provides dielectric anisotropy (demonstrating the molecule of liquid crystal behavior usually) with orderly phase form, and comprises with being selected from following at least two phenyl that do not replace and/or replace of coupling base link coupled: the unit of carbon-carbon single bond (-), carbon-carbon double bonds (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), ester units (COO-) and the azo unit (N=N-).This class side chain precursor also comprises at least two, preferably at least 5, and the above interval atom of Xiang Shuing.Therefore, side chain is connected to main polymer chain on described two interval atoms at least.The example of this class side chain precursor be according to below side chain precursor I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and the XV of the chemical formula that provides.

B) following molecule, for example simple alkyl aldehydes, described molecule does not demonstrate any permanent and/or inductive moment of dipole and therefore any dielectric anisotropy is not provided.The example of this class side chain precursor is an octanal.

Should also be noted that, the monomer that alternately has side chain by polymerization, preferred mesogenic group monomer, in the main polymer chain that does not contain direct link coupled ring structure, thereby prepare polymkeric substance of the present invention, wherein each side chain at least some side chains comprises with being selected from following two phenyl that do not replace and/or replace of coupling base link coupled at least: the unit of carbon-carbon single bond (-), carbon-carbon double bonds (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), (COO-) (N=N-), and demonstrate permanent and/or inductive moment of dipole, described moment of dipole provides dielectric anisotropy with orderly phase form to ester units with the azo unit.According to the polymkeric substance of this method preparation polyvinyl acetal preferably.Can be before being applied on the substrate surface or afterwards, carry out polymerization.

In all following embodiment, before using solvent, by making solvent streams through containing the shorter chromatogram column available from the ICN Alumina N super 1 of ICN Biomedicals GmbH Germany, dry solvent.

Owing to the statistics reason, maximum in the following embodiments functionality is 86%.Therefore, minimum 14% initial hydroxyl still keeps after reaction is finished.

In all following embodiment, the skilled known standard reaction of those skilled in the art is used for the preparation of polymkeric substance.

Embodiment 1: with 4`-(11,11-diethoxy undecyl oxygen base)-xenyl-4-carbon nitrile (side chain precursor I) and functionalized PVA of octanal

In the 100ml flask, with 0.70g side chain precursor I (referring to D Lacey etc., Macromolecular Chemistry and Physics 200,1222-1231 (1999)), 0.081g octanal, 0.198gPVA (number-average molecular weight Mw, about 15000) and 0.10g TsOH be dissolved among the dry DMF of 20ml, and stirred 24 hours down at about 55 ℃.

Then reaction mixture is poured in the 150ml methyl alcohol, and polymer precipitation.Collecting precipitation, and being dissolved in the 5ml chloroform, and in 100ml methyl alcohol redeposition, redeposition is 2 times repeatedly.

Output is 0.29g polymkeric substance (that is, the consumption based on the polyvinyl alcohol that is added is calculated as 40%).Loss is to cause owing to the polymkeric substance of low molar mass in comprehensive process operation (promptly precipitating operation) is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure A of flow process III.The side chain mol ratio I/ octanal in polymkeric substance that uses NMR to measure is found to be 2/1 (o/n the among=structure A).In addition, (o+n)/p is found to be about 42/16) (polymer A also provides with formula XVI.)

The side chain that is formed by side chain precursor I passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process III

Embodiment 2: with 4`-(11,11-diethoxy undecyl oxygen base)-xenyl-4-carboxylic acid, ethyl ester (side chain precursor II) and functionalized PVA of octanal

Prepare side chain precursor II according to flow process IV.

In the 250ml flask, 5.0g4`-hydroxyl-4-biphenyl carboxylic acids is dissolved in the 100ml dehydrated alcohol, and in ice bath, cools off.Dropwise add the 2.5ml thionyl chloride.Reaction mixture refluxed is 4 hours then, and makes it to reach room temperature.Be collected in formed precipitation on the strainer, with the washing with alcohol of 2 parts of 25ml and from toluene recrystallization.Output is 4.8g4`-hydroxyl-4-biphenyl carboxylic acids ethyl ester.

In the 250ml round-bottomed flask, 12.5g11-bromo-n-11 alcohol is dissolved in the 50ml methylene dichloride.Be added on the slurry of the 16.2g chloropyridine chromic salt (PCC) in the 100ml methylene dichloride.At room temperature stirred the mixture 2 hours, and poured into then in the 300ml diethyl ether.Filter out the solid of brown, and use diethyl ether, make liquid phase stream through short silicagel column as eluent.Vapourisation under reduced pressure organic solvent, and residue is dissolved in the dehydrated alcohol (EtOH), and regulate Calcium Chloride Powder Anhydrous and tosic acid (not shown in flow process IV) in a small amount together.Make this reaction mixture standing over night at room temperature.Solvent removed in vacuo, and in diethyl ether dissolved residue and wash with saturated sodium bicarbonate solution.Dry organic layer on sal epsom filters and evaporation, up to no longer steaming solvent.Residue is dissolved in 1: 4 mixture (V/V) of 15ml ethyl acetate/petroleum ether, and uses described solvent mixture as eluent, uses the column chromatography purifying.Separate 9.5g11-bromine undecyl aldehyde diethyl acetal.Find this compound ¹H-NMR spectrum is consistent with structure among the flow process IV.

In the 100ml round-bottomed flask, introduce 2.7g11-bromine undecyl aldehyde diethyl acetal, 2.42g4`-hydroxyl-4-xenyl carboxylic acid, ethyl ester, 50ml acetone.2g Anhydrous potassium carbonate and 0.2g potassiumiodide (not shown in flow process IV).Backflow mixture 72 hours.

About 40% solution partly is removed and is evaporated to dried in the reaction mixture, is dissolved in the 15ml ethyl acetate/petroleum ether 1: 4, and uses this solvent mixture as eluent, uses column chromatography purifying on silica gel.Separate 0.9g 4`-(11,11-diethoxy undecyl oxygen base)-xenyl-4-carboxylic acid, ethyl ester (being precursor II). ¹The H-NMR spectrum is consistent with the structure I I of flow process IV.

Flow process IV

In the 100ml flask, 0.80g side chain precursor II, 0.186g octanal, 0.097gPVA (Mw about 15000) and 0.1g TsOH are dissolved among the dry DMF of 25ml, and stirred 24 hours down at about 60 ℃.

Then reaction mixture is poured in the 250ml methyl alcohol, and polymer precipitation.Collecting precipitation, and being dissolved in the 5ml chloroform, and in 100ml methyl alcohol redeposition, redeposition is 2 times repeatedly.

Output is the 0.44g polymkeric substance.Loss is to cause owing to the polymkeric substance of low molar mass in the comprehensive process operation is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure B of flow process V.The side chain mol ratio II/ octanal in polymkeric substance that uses NMR to measure is found to be 7/3 (o/n the among=structure B).(polymer B also provides with formula XV.)

The side chain that is formed by side chain precursor II passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process V

Embodiment 3: with 4`-(11,11-diethoxy undecyl oxygen base)-xenyl-4-carboxylic acid 4-ethoxy carbonyl phenyl ester (side chain precursor III) and functionalized PVA of octanal

In the 50ml flask, 0.2g side chain precursor III, 0.029g octanal, 0.05gPVA (Mw about 15000) and TsOH are dissolved among the dry DMF of 10ml, and stirred 24 hours down at about 55 ℃.

Output is the 0.11g polymkeric substance.Loss is to cause owing to the polymkeric substance of low molar mass in the comprehensive process operation is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure C of flow process VI.The side chain mol ratio III/ octanal in polymkeric substance that uses NMR to measure is found to be 1.1/1 (o/n the in=structure C).

The side chain that is formed by side chain precursor III passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process VI

Embodiment 4: with 4`-(11,11-diethoxy undecyl oxygen base)-xenyl-4-carboxylic acid 4-methoxyl group phenyl ester (side chain precursor IV) and functionalized PVA of octanal

Prepare side chain precursor IV according to flow process IV and flow process VII.

In the solution part of the reaction mixture of remaining 60% described in the embodiment 2, add 40ml ethanol, 2g potassium hydroxide and 5ml water, and this mixture 48 hours of refluxing.With this mixture of hcl acidifying, topple in the entry and extracting 5 times with diethyl ether.Dry 20ml organic phase on sal epsom.Solvent removed in vacuo and from toluene recrystallized product, output is 1.8g4`-(11,11-diethoxy undecyl oxygen base)-xenyl-4-carboxylic acid.

In the 50ml flask, mix 0.54g4`-(11,11-diethoxy undecyl oxygen base)-xenyl-4-carboxylic acid, 20ml exsiccant methylene dichloride (not shown in flow process VII), 0.05g4-(N, N-dimethylamino) pyridine (not shown in flow process VII) and 0.24g4-methoxyphenol.This mixture of cooling on ice-water bath, and add 0.31g1,3-dicyclohexylcarbodiimide (not shown in flow process VII).Make reaction mixture reach room temperature, and continue to stir 24 hours.Filter reaction mixture, and solvent removed in vacuo then.The column chromatography that use is carried out in the gradient mode utilizes toluene/ethyl acetate as eluent, purified product.Output is 0.46g4`-(11,11-diethoxy undecyl oxygen base)-xenyl-4-carboxylic acid 4-methoxyl group phenyl ester (being precursor I V). ¹H-NMR spectrum is consistent with the structure I V of flow process VII.

Flow process VII

In the 100ml flask, 0.58g side chain precursor IV, 0.093g octanal, 0.049gPVA (Mw about 15000) and 0.1g TsOH are dissolved in the 25ml dry THF, and stirred 24 hours down at about 60 ℃.

Output is the 0.26g polymkeric substance.Loss is to cause owing to the polymkeric substance of low molar mass in the comprehensive process operation is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure D of flow process VIII.The side chain mol ratio IV/ octanal in polymkeric substance that uses NMR to measure is found to be 2.2/1 (o/n the among=structure D).(polymkeric substance D also provides with formula XVII.)

The side chain that is formed by side chain precursor IV passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process VIII

Embodiment 5: with 4`-(11,11-diethoxy undecyl oxygen base)-xenyl-4-carboxylic acid 4-(1-butoxy carbonyl oxyethyl group) phenyl ester (side chain precursor V) and functionalized PVA of octanal

In the 100ml flask, 0.61g side chain precursor V, 0.26g octanal, 0.26g PVA (Mw about 15000) and 0.02gTsOH are dissolved among the dry DMF of 25ml, and stirred 24 hours down at about 60 ℃.

Then reaction mixture is poured in the 250ml methyl alcohol, and polymer precipitation.Collecting precipitation, and being dissolved among the 7mlTHF, and in 75ml methyl alcohol redeposition, redeposition is 2 times repeatedly.

Output is the 0.40g polymkeric substance.Loss is to cause owing to the polymkeric substance of low molar mass in the comprehensive process operation is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure E of flow process IX.The side chain mol ratio V/ octanal in polymkeric substance that uses NMR to measure is found to be 1/2 (o/n the among=structure E).

The side chain that is become by the side chain precursor V-arrangement passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process IX

Embodiment 6: with 4`-(11,11-triethoxy undecyl oxygen base)-xenyl-4-carboxylic acid cyclohexyl (side chain precursor VI) and functionalized PVA of octanal

In the 50ml flask, 0.36g side chain precursor VI, 0.06g octanal, 0.10g PVA (Mw about 15000) and 0.1gTsOH are dissolved among the dry DMF of 10ml, and stirred 24 hours down at about 55 ℃.

Output is the 0.24g polymkeric substance.Loss is to cause owing to the polymkeric substance of low molar mass in the comprehensive process operation is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure F of flow process X.The side chain mol ratio VI/ octanal in polymkeric substance that uses NMR to measure is found to be 1.6/1 (o/n the among=structure F).

The side chain that is formed by side chain precursor VI passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process X

Embodiment 7: with 4`-(11,11-diethoxy undecyl oxygen base)-4`-11 carbon-10-thiazolinyl oxygen base biphenyl (side chain precursor VII) and functionalized PVA of octanal

In the 50ml flask, 0.40g side chain precursor VII, 0.055g octanal, 0.10gPVA (Mw about 15000) and 0.1gTsOH are dissolved among the dry DMF of 10ml, and stirred 24 hours down at about 55 ℃.

Output is the 0.19g polymkeric substance.Loss is to cause owing to the polymkeric substance of low molar mass in the comprehensive process operation is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure G of flow process XI.The side chain mol ratio VII/ octanal in polymkeric substance that uses NMR to measure is found to be 1.8/1 (o/n the among=structure G).

The side chain that is formed by side chain precursor VII passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process XI

Embodiment 8: with 4`-(11,11-diethoxy undecyl oxygen base)-xenyl-4-carboxylic acid 4-ethoxy carbonyl phenyl ester (side chain precursor III), 4`-(11,11-diethoxy undecyl oxygen base)-4`-11 carbon-10-thiazolinyl oxygen base biphenyl (side chain precursor VII) and functionalized PVA of octanal

In the 100ml flask, 0.11g side chain precursor III, 0.07g side chain precursor VII, 0.018g octanal, 0.037g PVA (Mw about 15000) and 0.03gTsOH are dissolved among the dry DMF of 10ml, and stirred 48 hours down at about 55 ℃.

Output is the 0.09g polymkeric substance.Loss is to cause owing to the polymkeric substance of low molar mass in the comprehensive process operation is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure H of flow process XII.

The side chain that is formed by side chain precursor III passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain and by the side chain that side chain precursor VII forms and passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process XII

Embodiment 9: with [4-(11,11-diethoxy undecyl oxygen base)-phenyl-(4-ethoxyl phenenyl)-diazene] (side chain precursor VIII) and functionalized PVA of octanal

In the 100ml flask, 0.82g side chain precursor VIII, 0.13g octanal, 0.24gPVA (Mw about 15000) and 0.1gTsOH are dissolved among the dry DMF of 25ml, and stirred 24 hours down at about 60 ℃.

Output is the 0.48g polymkeric substance.Loss is to cause owing to the polymkeric substance of low molar mass in the comprehensive process operation is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure I of flow process XIII.The side chain mol ratio VIII/ octanal in polymkeric substance that uses NMR to measure is found to be 1.8/1 (o/n the in=structure I).

The side chain that is formed by side chain precursor VIII passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process XIII

Embodiment 10: with 2-[4-(11,11-diethoxy undecyl oxygen base)-3-(4-ethoxyl phenenyl azo-group) phenoxy group] butyl propionate (side chain precursor IX) and the functionalized PVA of octanal

In the 100ml flask, 1.0g side chain precursor IX, 0.205g octanal, 0.25g PVA (Mw about 15000) and 0.1gTsOH are dissolved in the 25ml dry THF, and stirred 24 hours down at about 60 ℃.

Output is the 0.56g polymkeric substance.Loss is to cause owing to the polymkeric substance of low molar mass in the comprehensive process operation is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure J of flow process XIV.The side chain mol ratio IX/ octanal in polymkeric substance that uses NMR to measure is found to be 1/1 (o/n the among=structure J).In addition, find that (o+n)/p is about 43/18.(polymkeric substance J also provides with formula XXXIV).

The side chain that is formed by side chain precursor IX passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process XIV

Embodiment 11: with 2-(11,11-diethoxy undecyl oxygen base)-4-tolyl acid 4`-butoxy biphenyl-4-base ester (side chain precursor X) and functionalized PVA of octanal

In the 100ml flask, 0.53g side chain precursor X, 0.065g octanal, 0.12g PVA (Mw about 15000) and 0.1gTsOH are dissolved among the dry DMF of 25ml, and stirred 24 hours down at about 60 ℃.

Output is the 0.22g polymkeric substance.Loss is to cause owing to the polymkeric substance of low molar mass in the comprehensive process operation is removed.

Resulting polymers ¹H-NMR spectrum is consistent with the structure K of flow process XV.The side chain mol ratio X/ octanal in polymkeric substance that uses NMR to measure is found to be 1.7/1 (o/n the among=structure K).

The side chain that is become by the side chain precursor X-shaped passes through-(CH ₂) ₁₀The interval atom of-form is connected on the main polymer chain.

Flow process XV

Embodiment 12: with 4-(11,11-diethoxy undecyl oxygen base)-2,3,5,6,2`, 3`, 5`, 6`-octafluoro-4`-hexyloxy biphenyl (side chain precursor XI) and functionalized PVA of octanal

According to previous embodiment, in flask, mix and stir an amount of side chain precursor XI, octanal, PVA, TsOH and exsiccant DMF by (for example about 60 ℃ following 24 hours), thus preparation polymkeric substance L.

Then reaction mixture is poured into an amount of organic solvent, in methyl alcohol, with the polymkeric substance of structure L among the precipitation flow process XVI.

Flow process XVI

Embodiment 13: with 2-(11,11-diethoxy undecyl oxygen base)-4-methyl-phenylformic acid 4`-butoxy-2,3,5,6, and 2`, 3`, 5`, 6`-octafluoro-biphenyl-4-base ester (side chain precursor XII) and functionalized PVA of octanal

According to previous embodiment, by in flask (for example about 60 ℃ following 24 hours) mix and stir an amount of side chain precursor XII, octanal, PVA, TsOH and exsiccant DMF, thereby preparation polymkeric substance M.

Then reaction mixture is poured into an amount of organic solvent, in methyl alcohol, with the polymkeric substance of structure M among the precipitation flow process XVII.

Flow process XVII

Embodiment 14: with 4`-(11,11-diethoxy undecyl oxygen base)-functionalized PVA of biphenyl-4-carboxylic acid ethyl ester (side chain precursor II)

According to previous embodiment, by in flask (for example about 60 ℃ following 24 hours) mix and stir an amount of side chain precursor II, PVA, TsOH and exsiccant DMF, thereby preparation polymkeric substance N.

Then reaction mixture is poured into an amount of organic solvent, in methyl alcohol, with the polymkeric substance of structure N among the precipitation flow process XVIII.

Flow process XVIII

Embodiment 15: with 4`-(11,11-diethoxy undecyl oxygen base)-functionalized PVA of biphenyl-4-carboxylic acid 4-methoxyl group phenyl ester (side chain precursor IV)

According to previous embodiment, by in flask (for example about 60 ℃ following 24 hours) mix and stir an amount of side chain precursor IV, PVA, TsOH and exsiccant DMF, thereby preparation polymkeric substance O.

Then reaction mixture is poured into an amount of organic solvent, in methyl alcohol, with the polymkeric substance of structure O among the precipitation flow process XIX.

Flow process XIX

Embodiment 16: with 1, and 21-pair-(4`-ethoxycarbonyl-4-xenyl oxygen base)-functionalized PVA of 10-diethoxymethyl-21 carbon-10-alkene (side chain precursor XIII)

According to previous embodiment, by in flask (for example about 60 ℃ following 24 hours) mix and stir an amount of side chain precursor XIII, PVA, TsOH and exsiccant DMF, thereby the preparation polymer P.

Then reaction mixture is poured into an amount of organic solvent, in methyl alcohol, with the polymkeric substance of structure P among the precipitation flow process XX.

Flow process XX

Embodiment 16: with 1, and 21-pair-(4`-ethoxycarbonyl-4-xenyl oxygen base)-10-diethoxymethyl-21 carbon-10-alkene (side chain precursor XIII) and functionalized PVA of octanal

According to previous embodiment, by in flask (for example about 60 ℃ following 24 hours) mix and stir an amount of side chain precursor XIII, octanal, PVA, TsOH and exsiccant DMF, thereby preparation polymkeric substance Q.

Then reaction mixture is poured into an amount of organic solvent, in methyl alcohol, with the polymkeric substance of structure Q among the precipitation flow process XXI.

Flow process XXI

B) embodiment of the method for manufacturing liquid crystal device of the present invention

Can prepare liquid crystal device by the method that comprises the steps: at least one substrate surface, provide the surface orientation device that contains polymkeric substance of the present invention alignment layer, between two substrates, accompany liquid crystal layer then, wherein at least one substrate provides described polymkeric substance, wherein arrange described substrate, so that described surface orientation device alignment layer is towards liquid crystal layer.

Preferably, remove described solvent from this surface then, thereby surface orientation device alignment layer is provided by on described surface, applying the solution that contains described polymkeric substance.Therefore, do not need to solidify prepolymer, so that on substrate surface, form polymer layer.

Used thickness is the liquid crystal display glass substrate of 1.10mm.It is 80 Ω/cm that substrate one side provides surface resistivity ²Indium tin oxide target (ITO) layer (electrode materials).Use the known conventional photolithographic methods of those skilled in the art, addressing electrode structures is provided.Substrate of glass is cut into the sheet material that is of a size of 9.5 * 12.5mm, and milled border.Also use the substrate of glass that is of a size of 25.4 * 25.4mm.

Then, in ultra sonic bath, washing substrate several in distilled water, drying is washed 2 times in Virahol then.Afterwards substrate is moved into the indoor of cleaning.

With being dissolved in the ITO side that the interior concentration of tetrahydrofuran (THF) (THF) is the surface orientation device calibration materials spin coating substrate of about 0.1% (w/w) (testing the concentration of maximum 0.5%w/w).Speed is about 3000-4000rpm and was coated with in 30 seconds.

After coating, the heating substrate is about 5-10 minute under 125 ℃ temperature, removes and desolvates (THF), and form alignment layer.Can or carry out drying on the hot plate and/or under the vacuum in baking oven.Make the substrate cooling then.

Should be noted that two-step approach test also obtains acceptable result, described two-step approach is included in 60 ℃ of heating about 5-10 minute down, then heats about 10-30 minute down at 130 ℃.Yet, be noted that the temperature that surpasses room temperature is optional for drying step in principle.

Use the roller diameter of 120mm, the drum speed of 300rpm, the accumulation contact length of the linear velocity of 15mm/sec and about 0.5mm, the surface orientation device alignment layer that on the ITO layer, applies with the nylon cloth rubbing down.All substrates of rubbing down in the same direction.

Afterwards, two edges, in the string of a musical instrument (string), use UV-glue (NorlandNOA68) and separant (spacer), two substrates are placed in the unit together, one of them substrate Rotate 180 ° makes rubbing down direction antiparallel in this unit.Can be the separant that on this cell surface, sprays from alcohol dispersion liquid for the alternate method.This unit was placed under pressure in the UV exposure box 15 minutes.

Little cable is ultrasonically welded on this unitary each ITO surface.

Then, with capillary force, the nematic liquid crystal that will be in isotropic phase is incorporated in the unit (this can have or do not have under the situation of the vacuum of adding and carry out).

Should be noted that above-described device is simple relatively type.Device can have much bigger size and can for example pass through to use passive matrix addressing class or the addressing by different way of active array addressing class.In these cases, comprise the step that involves complicated microelectronics production stage.

Embodiment 17: the face with surface orientation device alignment layer of the stable vertical calibration of electricity switches liquid crystal device outward

As mentioned above, adopt the ITO side of the polymer A coat substrates of embodiment 1 preparation.Yet, should be noted that can in this embodiment, use any according to the structure of formula I-XXII.

Folk prescription is to wiping polymer layer (about 100nm) very gently, and the meso of induced polymer cooperates the little pre-tilt of side group and assembles this unit afterwards.

Use nematic mixture M BBA/MLC6608 (Merck, Germany) then, 40/60wt% fills interlayer element (cell gap is about 3 microns), wherein Δ ε=-4.2 of Δ ε=-0.8 of MBBA and MLC6608.

In this unit, polymer layer serves as surface orientation device alignment layer.

With polarizing microscope, observe this unitary calibration after cool to room temperature, evenly vertical with discovery.

In the device that contains polarizing microscope, photodetector, oscilloscope and surge generator, measure to reply and rise and time of lag.

Fig. 1 has described and has applied under low frequency (about 1Hz) unipolar pulse, and the unitary photoelectricity with vertical calibration is replied.Under the voltage (U) of 9.2V, are respectively measured rising and time of lag about 1.9 and 3.8ms.Therefore, measured time of lag is than lacking about 5 times the time of lag that the face with initial vertical calibration switches common measurement in the liquid crystal cells outward.

Embodiment 18: the face with surface orientation device alignment layer of the stable vertical calibration of electricity switches liquid crystal device outward

Repeat embodiment 17, different is that with nematic mixture M BBA/MLC6884 (Merck, Germany), 40/60wt% fills interlayer element, wherein Δ ε=-0.8 of Δ ε=-5.0 of MLC6884 and MBBA.

As shown in Figure 2, under the voltage (U) of 6.1V, are respectively measured rising and time of lag about 2.5 and 1.8ms.

Embodiment 19: the face with surface orientation device alignment layer of the stable vertical calibration of electricity switches liquid crystal device outward

Repeat embodiment 17, different is, uses the ITO side of coat substrates as described above according to the polymkeric substance H of embodiment 8 preparations.Yet, not wiping polymer layer.In addition, the nematic material MLC6884 (Merck, Germany) with Δ ε=-5.0 fills interlayer element.

As shown in Figure 3, under the voltage (U) of 5.2V, are respectively measured rising and time of lag about 2.7 and 2.7ms.

Embodiment 20: the face with surface orientation device alignment layer of the stable plane calibration of electricity switches liquid crystal device outward

With according to the polymkeric substance J of the embodiment 10 preparation ITO side of coat substrates as described above.Yet, should be noted that any structure that can use in this embodiment according among the formula XXIII-XXXIV.

Folk prescription cooperates the uniform planar calibration of side group and assembles this unit afterwards with the meso of guaranteeing polymkeric substance to wiping polymer layer (about 100nm).

Use the nematic material E7 (BDH/Merck) of Δ ε＞0 to fill interlayer element (cell gap is about 3 microns) then.

With polarizing microscope, observe after cool to room temperature this unitary calibration and be found to be uniform planar.

In the device that contains polarizing microscope, photodetector, oscilloscope and surge generator, measure rise time and time of lag.

Applying under low frequency (about 1Hz) unipolar pulse, this unitary photoelectricity with plane calibration is replied, and finds to rise and be respectively about 0.5ms and 4ms time of lag.

Embodiment 21: the face with surface orientation device alignment layer of the stable plane calibration of electricity switches liquid crystal device outward

Repeat embodiment 20, different is to use the nematic material E70A (BDH/Merck) of Δ ε=+ 10.8 to fill interlayer element.

As shown in Figure 4, under the voltage (U) of 5.6V, are respectively measured rising and time of lag about 1.1 and 1.6ms.

Although described the present invention in detail with reference to specific embodiments of the present invention, for those skilled in the art, it is evident that, can under the situation that does not break away from the spirit and scope of the present invention, make various variations and change.

Claims

1. be used as the polymkeric substance of surface orientation device alignment layer in liquid crystal device, described polymkeric substance comprises main polymer chain and the side chain that is connected thereto, and it is characterized in that:

This main polymer chain do not have direct link coupled ring structure and

Each side chain at least some side chains:

(i) comprise by being selected from following at least two phenyl that do not replace and/or replace of coupling base link coupled: the unit of carbon-to-carbon singly-bound (-), carbon-carbon double key (CH=CH-), carbon containing-carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), ester units (COO-) and the azo unit (N=N-),

(ii) demonstrate permanent and/or the inductive moment of dipole, described moment of dipole with the ordered phase form provide dielectric anisotropy and

(iii) be connected on the main polymer chain by at least two interval atoms.

2. the polymkeric substance of claim 1, wherein said side chain by at least 5 at interval atoms be connected on the main polymer chain.

3. claim 1 or 2 polymkeric substance, wherein main polymer chain comprises:

Unit according to the first kind random distribution of following formula:

S wherein ₁Represent first side chain, described first side chain comprises by being selected from following two phenyl that do not replace and/or replace of coupling base link coupled at least: the unit of carbon-to-carbon singly-bound (-), carbon-carbon double key (CH=CH-), carbon containing-carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), ester units (COO-) and the azo unit (N=N-), demonstrate permanent and/or inductive moment of dipole with these side chains, described moment of dipole provides dielectric anisotropy with the ordered phase form, with comprise at least two at interval atoms, wherein first side chain is connected on the main polymer chain by described interval atom; With

Unit according to the second class random distribution of following formula:

4. the polymkeric substance of claim 3, wherein main polymer chain comprises the unit according to the 3rd class random distribution of following formula:

S wherein ₂Represent second side chain, described second side chain is different from S ₁, comprise by being selected from following at least two phenyl that do not replace and/or replace of coupling base link coupled: the unit of carbon-to-carbon singly-bound (-), carbon-carbon double key (CH=CH-), carbon containing-carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), ester units (COO-) and the azo unit (N=N-), and demonstrate permanent and/or inductive moment of dipole, described moment of dipole provides dielectric anisotropy with the ordered phase form and comprises at least two atoms at interval, and wherein second side chain is connected on the main polymer chain by described interval atom.

5. claim 3 or 4 polymkeric substance, wherein main polymer chain comprises the unit according to the random distribution of the other type of following formula:

S wherein ₃The expression side chain, described side chain is different from S ₁And S ₂, it does not demonstrate any permanent and/or inductive moment of dipole and therefore dielectric anisotropy is not provided.

6. any one the method for polymkeric substance of preparation claim 1-5, it is characterized in that comprising the side chain precursor and the main polymer chain of the ring structure that does not have direct coupling are reacted, wherein said side chain precursor comprises by being selected from following two phenyl that do not replace and/or replace of coupling base link coupled at least: the unit of carbon-to-carbon singly-bound (-), carbon-carbon double key (CH=CH-), carbon containing carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), (COO-) (N=N-), these side chains demonstrate permanent and/or inductive moment of dipole to ester units, and described moment of dipole provides dielectric anisotropy with the ordered phase form with the azo unit.

7. the method for claim 6, wherein main polymer chain is a polyvinyl alcohol.

8. any one the preparation method of polymkeric substance of claim 1-5, the monomer polymerization that it is characterized in that having side chain becomes not have the main polymer chain of direct link coupled ring structure, and wherein each side chain at least some side chains comprises by being selected from following two phenyl that do not replace and/or replace of coupling base link coupled at least: the unit of carbon-to-carbon singly-bound (-), carbon-carbon double key (CH=CH-), carbon containing-carbon triple-linked unit (C ≡ C-), methylene ether unit (CH ₂O-), ethyleneether units (CH ₂CH ₂O-), (COO-) (N=N-), these side chains demonstrate permanent and/or inductive moment of dipole to ester units, and described moment of dipole provides dielectric anisotropy with the ordered phase form with the azo unit.

9. in liquid crystal device, be used as the composition of surface orientation device alignment layer, it is characterized in that, comprise any one the polymkeric substance and second polymkeric substance of at least a claim 1-5.

10. the composition of claim 9, wherein second polymkeric substance is a polyvinyl acetal.

11. the composition of claim 9, wherein second polymkeric substance is any one a polymkeric substance of claim 1-5.

12. the surface orientation device alignment layer that uses in liquid crystal device is characterized in that comprising any one polymkeric substance of at least a claim 1-5.

13. any one polymkeric substance of claim 1-5 in liquid crystal device as the purposes of surface orientation device alignment layer.

14. a method of making liquid crystal device is characterized in that comprising:

-on the surface of at least one substrate, provide to contain right and require any one the surface orientation device alignment layer of polymkeric substance of 1-5; With

15. the method for claim 14 wherein by apply the solution that contains described polymkeric substance and solvent on described surface, is removed described solvent from this surface then, thereby described surface orientation device alignment layer is provided.