TW201041912A - Maleimide-N-vinyllactam based sidechain polymers for LCD alignment layers - Google Patents

Abstract

A polymer for use in a surface-director alignment layer is provided, said polymer being a co-polymer comprising maleimide and/or derivatives thereof and N-vinyllactam and/or derivatives thereof, wherein at least some of said repeating units are functionalized with a pendant side-chain. The polymer of the invention is suitable for use in or as alignment layer material in a liquid crystal device.

Description

201041912

I. Description of the Invention: [Technical Field] The present invention relates to a polymer for a surface-guided sub-calibration layer, a surface-guided sub-calibration layer material comprising the polymer, and a material comprising the polymer The liquid crystal device of the calibration layer. [Prior Art] A liquid crystal device generally includes a liquid crystal material layer disposed on a substrate or sandwiched between a pair of substrates. ° Liquid crystal molecules are generally relatively rigid molecules with significant shape anisotropy's ability to align their long axes with a certain preferred direction. The average direction of the molecules is determined by the vector and is referred to as the leader. In liquid crystal displays, the required initial calibration of the liquid crystal layer in the absence of an external magnetic field, such as an electric field, is generally achieved by limiting the surface treatment of the solid substrate surface, such as by applying a so-called alignment layer (orientation layer). ) to the surface of the limiting substrate facing the liquid crystal. The initial liquid crystal calibration is defined by the solid surface/liquid crystal interaction in the interface between the liquid layer 3 and the calibration layer. B / The direction of the liquid crystal molecules adjacent to the confining surface is elastically transferred into the liquid 3 knife body, whereby substantially the same calibration of all liquid crystal host molecules. A liquid crystal molecular guide (also referred to herein as a surface guide) adjacent to the interface between the liquid crystal layer and the alignment layer is constrained to a position in a particular direction, such as perpendicular to the surface of the confinement substrate (also referred to as a vertical or vertical pair). Quasi (VA)), parallel to the surface of the limiting substrate (also known as parallel or planar alignment (PA)) or to the surface of the substrate of 146603.doc 201041912 and having a certain σΑ». Πs VIII, the specific tilt angle (also known as the tilt alignment 罾 type of slave depends on the required method for establishing the calibration D. For example, the inorganic film vapor deposition method and the organic film friction method. In the film vapor deposition method, the inorganic film is formed by vapor deposition of an inorganic substance (such as oxygen cutting) on the substrate surface, which is inclined to the confinement substrate such that the liquid crystal molecules are based on the material and the vapor condition. However, the inorganic film is oriented in a certain direction. Since the 1k cost is better than the horse's, the method is not suitable for large-scale manufacturing, and this method cannot be practically used. According to the organic film rubbing method, an organic coating system such as polyimine is formed. On the surface of the substrate. Thereafter, the organic coating is rubbed in a predetermined direction using a cloth such as cotton, nylon or polyester such that the liquid crystal molecules in contact with the layer are oriented in the rubbing direction. Due to its rather advantageous characteristics, Such as chemical stability, thermal stability, etc., in most cases it is used as an organic surface coating. The application of the polyimide layer generally includes the following as follows: Baking step under 0-3001 Polyimine can be prepared according to, for example, the following Scheme I or Scheme: 146603.doc 201041912

heating

〇η〇-〇-〇ν4 polyglycine

Polyimine

Option I

~ο—Νη|- H〇r

Ip OH o heating

Polyimine polyisamic acid

方案 Scheme II In a first step, a molar amount of a tetracarboxylic acid anhydride and a diamine are mixed in a monoamine solvent such as N-decylpyrrolidone (NMP). A spontaneous-reaction occurs and the formation of poly-proline (prepolymer of polyimine) occurs. In this state, the prepolymer is distributed to its users, wLCD manufacturers. However, since the prepolymer solution is unstable at room temperature, the solution is typically cooled during transport and storage to avoid degradation, or any other undesired chemical reaction of the prepolymer. In general, polyacrylic acid is made up of liquid crystals.

The manufacturer of the Xin Ri Ri device is usually diluted to about 5% with a mixture of NMP 146603.doc •5- 201041912 and ethylene glycol butadiene 4:l (w/w). 6. Ethylene glycol butyl ether

NMP The polyamic acid is typically applied to a transparent, patterned indium tin oxide (IT〇) electrode layer coated glass substrate using, for example, spin coating or some type of printing technique. The layer of polyamic acid is then dried in an oven at about 1 Torr and thereafter heated at about 200 ° C for 丨 2 h. In this heating cycle, the polyacrylic acid is converted to a polynymine. The resulting polyimine heat is quite stable and insoluble in any solvent. The polymer can only be removed by, for example, degrading it using an alkaline medium. One of the disadvantages of this organic film application method is the baking step, which results in long manufacturing time and high manufacturing cost. In addition, high temperatures, such as about 2 Å, are desirable in the manufacture of, for example, lc〇sr thin film transistors (TFTs) because high temperatures cause a decrease in yield and thus film defects. The baking temperature is too high for the plastic substrate. It is also difficult to control the tin-bonding strength between the organic film and the liquid crystal bulk layer applied by the organic film application method. One of the disadvantages of the amine process is that the polyamic acid is quite unstable and needs to be stored at low temperatures, such as in a cold room. It would be advantageous if some or all of the above disadvantages could be avoided. [Summary of the Invention] 146603.doc 201041912 Addressing the object overcomes at least some of the prior art & problems and enhancements may be advantageous, such as for liquid crystal devices for or as a calibration layer material. The inventors have discovered that according to the inventive arrangement, by providing a butadiene-based a polymer of at least a portion of the quinone imine and the N_B (10) amine repeating unit, at least partially meeting the above objectives. In a first aspect, the present invention relates to a polymer for a surface-guided sub-calibration layer, the poly a second polymer comprising repeating units of maleimide and/or derivatives thereof and N-vinyl decylamine and/or derivatives thereof, at least some of which have significant shape orientation The pendant side group S1 is functionalized. In an embodiment of the invention, at least some of the repeating units of maleimide and/or derivatives thereof comprise a hydrogen atom and a group sX, wherein the group Sx is selected from methyl; ethyl; the wrong side group is widely selected from the branched or linear aliphatic and aromatic groups, polyether, decane or leaver S5 which are optionally substituted or functionalized. ; ion motion inhibition side group s6; reactivity, preferably light

The reactive side group S7; and the side group of the light-responsive side group S8. The polymers of the present invention are highly photo and thermally stable. Copolymers of ethyl maleimide and vinyl pyrrolidone have been shown to promote temperature stable and high quality calibration layers, which are comparable to those of the traders. The copolymers are relatively stable as long as the side chains are suitably selected without degrading the stability characteristics due to their own instability. Copolymers with a wide variety of different side chains have comparable solubility in standard solvents such as NMP and PGMEA. 146603.doc 201041912 The polymers of the present invention are much more stable in solution than conventional polyimine and do not require cryopreservation. Further, the polymer of the present invention is easier and faster to process than the quinone imine because it does not need to be baked at a high temperature and does not require curing, and the polymer film can be smoothly formed on a glass or plastic substrate. The pendant group Sx can be attached to the repeating units via a spacer group L. The number of repeating units of maleimide and N-ethylglycolamine can be at least 50%, such as at least 75%, for example at least 90%, of the repeating units of the polymer backbone. Further, the ratio between the maleimide and the n-vinyl indoleamine unit in the polymer backbone may range from 1:10 to 1〇:1, such as 1:2 to 2:1, For example, about 1:1. The N-vinyl decylamine of the polymer of the present invention may be selected from the group consisting of *N_vinylpyrrolidone, N-ethinyl nitrile and N-vinylcaprolactam. Further, the polymer comprises a repeating unit selected from the group consisting of: an anchored pendant group s4, which is selected from a branched or linear aliphatic and aromatic group (such as an alkyl group or an aryl group) which is optionally substituted or halogenated. a repeating unit functionalized with a pendant group S5 of an alkylaryl group, a polyether, a decane or an alcohol; a repeating unit functionalized by an ion motion-inhibiting pendant group s6; a reactive, preferably photoreactive side group 87 functionalized repeat unit; a repeat unit functionalized with a light responsive side group S8. The polymer may optionally comprise a crosslinking group. In an embodiment of the invention, the pendant group s having significant shape anisotropy may be selected from the side groups sp which induce planar alignment of the liquid crystal material and the side bases S1b which induce vertical alignment of the liquid crystal material. At least a portion of the pendant groups can be attached via the maleimide-nitrogen to the repeating units of 146603.doc 201041912. In another aspect, the invention is directed to a surface guide sub-calibration layer. A polymer according to the present invention deposited on a solid substrate is included. In another aspect, the present invention relates to a liquid crystal device including at least a chip limiting substrate, a liquid crystal body, and a surface guiding sub-alignment layer disposed between the at least one of the limiting substrate and the liquid crystal body. (which is in contact with the surface of the liquid crystal), wherein the surface-directed sub-calibration layer comprises a polymer according to the invention. For example, the liquid crystal device may include: first and second confinement substrates sandwiching the liquid BB body layer; and a first surface alignment sub-alignment layer disposed between the first confinement substrate and the liquid crystal body, Contacting the surface of the liquid crystal; and a second surface guiding sub-alignment layer disposed between the second limiting substrate and the liquid crystal, in contact with the surface of the liquid crystal, wherein the first and the flute At least one, preferably both, of the first surface-directed sub-calibration layer comprises a polymer according to the invention. In another aspect, the invention relates to a method for surface alignment of a surface alignment sub-calibration layer, which comprises: providing a material of a registration layer according to the invention; Linearly polarized electromagnetic radiation having a wavelength in the range of 3 〇〇 nm illuminates the calibration layer material. In particular, the linearly polarized electromagnetic radiation may have a wavelength in the range of 230 to 27 Gnm, e.g., about nm. [Embodiment] Calibration layer material of the device The present invention relates to a polymer suitable for or as a liquid crystal. 146603.doc 201041912 The polymer system of the present invention includes maleic iodide, N vinyl decylamine (such as N-ethylene, pirone, & ethylene base bite and N_ a copolymer of vinyl caprolactam) and a repeating unit thereof, wherein at least a portion of the repeating units are functionalized via pendant groups. As used herein, 'a copolymer comprising a repeating unit of maleimide and N-vinyl decylamine" means a monomer derived from a maleimide monomer and a vinyl ruthenium amide. Copolymer obtained by polymerization of a mixture of N-vinyl decylamine is a compound of the following formula: r (ch2) x Ό (1) - x in (CH2)X is an integer between 2 and 10. , generally 3 to 5. As used herein, maleimide is a compound of the following chemical formula: 〇

Qn- L-SX (II) 0 wherein S4X is hydrogen (H) or a pendant group selected from the group consisting of methyl, ethyl or a group selected from the group consisting of ss, s, s6, s7 and s8 as described herein, and ^ Depending on the desired spacer group, the pendant group SX is attached to the maleimide ring nitrogen. In the absence of the spacer spacer L, the pendant group 0 is directly attached to the maleimide ring nitrogen. A mixture of N-vinyl indoleamine and maleimide can be polymerized by a method known in the art 146603.doc 201041912, generally by free radical addition copolymerization to form maleicylene. a copolymer of an amine and N-vinyl decylamine. In the mixture of the N-vinyl decylamine and the maleimide, a blend of different maleimide, that is, at least two different cis-butene diimine, and Blends of different Sx and/or spacer L. This results in a copolymer having more than one side group and/or a linking group attached to the polymer backbone. 0 A non-limiting example of the blend of different maleimide that can be used to adjust the blend of the resulting polymer to the maleimide of the resulting polymer will be further illustrated in the following invention. . Examples of suitable and polymeric reactions will be set forth in the examples below. The result of the polyfluorene effect is a copolymer according to the present invention comprising repeating units having the following formulas of maleimide and vinyl decylamine:

The obtained copolymer towel is not regularly distributed, and thus the exact structural formula of the polymer cannot be produced because the polymers are not as indicated in the figure. The perfect alternating copolymer. However, at a 1.1 molar ratio of maleimide to small vinyl decylamine monomer in the reaction mixture, the configuration in the resulting polymer is substantially prone to alternating maleimide·N_ Vinyl decylamine _cisabiene 146603.doc • 11 - 201041912 Amine-N-vinyl decylamine structure β As is known to those skilled in the art, the polymers of the present invention may also include non-cis-butene Additional repeating units in addition to the diphenylimine and hydrazine-vinyl endoamine repeating units. Examples of such repeating units include monomers or prepolymers which can be incorporated into the polymer chain by free radical addition polymerization, generally any polymerizable vinyl known to those skilled in the art. Unsaturated compound. Examples of such polymerizable, ethylenically unsaturated compounds include, but are limited to, styrene and (meth) acrylate. In the examples of the present invention, the amount of the maleimide and the fluorene-ethylene endo-amine can be repeated together to a large portion of the repeating unit in the polymer. In general, the number of repeating units based on the polymer chain is at least about 5%, such as at least about 75%, such as at least about 9%. Also included are blue cis-butenylene and fluorene-ethylene decylamine. In the polymer of the present invention, the number ratio between the repeating unit of the cis-butanylimine repeating unit and the vinyl indoleamine repeating unit may be, for example, in the range β between 丨: (7) to (7): 丨, preferably at 1. : in the range between 2 and 2:1, for example, about Η. A close to 1:1 ratio results in a more stable polymer composition and does not require tight control of the feed composition to maintain the same polymer composition during polymerization' because the polymerization system is nearly alternating. A high ratio (excess in maleimide) will result in a shorter polymer. A low ratio (excessive Ν-vinyl decylamine) will result in a polymer having a low degree of pendant (S) content because the cis-butadiene diamine is typically loaded with the pendant group Sx. 146603.doc -12- 201041912 The copolymer of the present invention is soluble in a standard solvent such as NMp and PTMEA, and a solution of the polymer can be deposited on a substrate by a conventional deposition method, such as However, it is not limited to spin coating, spray coating, blade coating (d0ct0rblade eoating), pro-coating, flexographic printing, blasting, and the like. By: the polymer can be obtained and dissolved in its polymerization state, and the calibration layer can be easily obtained by evaporating the solvent only after it is accumulated on a substrate. This makes it possible to make a temperature-sensitive substrate because it is not necessary to add excessive heat to the calibration layer. Moreover, since the polymer does not require curing after deposition, the total time for forming the alignment layer on the substrate is fast because it includes only deposition and subsequent evaporation of a relatively thin solvent film. The pendant group sx typically attached to the maleimide monomer via a maleimide ring nitrogen includes pendant groups selected from the group consisting of, if desired, substituted, such as fluorinated straight or branched chains Alkyl, aryl and alkylaryl (collectively referred to herein as pendant S5), anchoring pendant groups (referred to herein as side groups S4), ion motion inhibiting side groups (referred to herein as side groups s6), Reactive, preferably photoreactive side groups (referred to herein as side groups s?), photoresponsive side groups (referred to herein as side groups s8), and side groups having significant shape anisotropy (in This is referred to herein as a pendant group s. • The reactive pendant group can include cross-linking pendant groups. However, other pendant groups are also contemplated for use in the present invention. The pendant group Sx can be 'optional, respectively, by a spacer group L Attached to the polymer backbone 'This group L generally comprises from 0 to 30 linking atoms, such as 0 or 5 to 15, wherein one of the linking atoms represents the side group via 146603.doc -13· 201041912 Direct bonding is directly attached to the polymer backbone. However, spacer groups longer than 30 connected atoms are also covered. In the present invention, the spacer group L can be used, for example, to promote attachment of the pendant sx to the maleimide ring nitrogen and can also be used to increase the mobility of the attached pendant groups. A saturated or unsaturated smoky bond, such as a decyl, an alkenyl, an aryl, an alkylarylalkoxy or a polyether, an aryloxy group, a oxalyl chain, optionally substituted. Typical examples include c5_Ci5 alkyl or Alkoxy chain. In the embodiment of the present invention, a side group sl having significant shape anisotropy may be attached to the polymer of the present invention. For example, the molecule of the liquid crystal material (liquid crystal original) is generally exhibited. Such molecules having significant anisotropy shape. As used herein, the term 'side group with significant shape anisotropy' refers to a molecule having significant shape anisotropy in its actual environment. The side having significant shape anisotropy The base exhibits a significant difference between its minor axis (axis) and its long axis (axis) and is relatively rigid in its structure. In an embodiment of the invention, the side-based liquid crystal former having significant anisotropy of shape Side group. Such as Handbook of Liqui d Crystals, Vol. 1 Fundamentals, pub., as defined in John Wiley & Sons Inc, 1998, the term "liquid crystal former" refers to a structure that is generally compatible with the mesophase. This definition is used throughout the present invention. Therefore, the liquid crystal source side is a side group having a liquid crystal original structure. In "Handbook of Liquid Crystals, (SUpra)", the liquid crystal system is equivalent to "a mesomorphic compound", that is, a temperature, a gas pressure and a concentration of 146,603. .doc -14- 201041912 A compound which may be present in the mesophase (ie liquid crystal phase) under suitable conditions. The liquid crystal precursor is a typical example of a molecule having significant shape anisotropy. Therefore, the side groups including the liquid crystal precursor are covered by this definition. On the other hand, the side groups of the liquid crystal source may be used as the liquid crystal original side group and also the non-liquid crystal. The original liquid crystal original side substrate is encompassed by the present invention. • The side group s1 having significant shape anisotropy according to the present invention has a linear shape, a rod shape (such as a rod shape or a strip shape), a disk shape, a strip shape, a cone shape, and a bow shape (also called: ", 香二i ) Human form or other shape that exhibits significant shape anisotropy. The surface characteristics of the substrate affect the orientation of the liquid crystal of the liquid crystal layer in contact with the surface of the substrate (at least in the interface between the surface of the substrate and the liquid crystal layer). In general, the interface conditions transmit the liquid crystal layer so that the entire liquid crystal layer is oriented to be affected by the orientation on the interface. There are two main paths currently used to influence the orientation of the liquid crystal layer. A path Y surface energy path) uses (iv) surface characteristics to increase compatibility with liquid crystal material tails, which can promote vertical alignment (low surface energy) or increase phase with the original core of the liquid crystal as in Example 1 below. Capacitance, which can facilitate planar calibration (high surface energy) as in Example 12 below. The other path uses space to interact with each other. The spatial interactions are particularly apparent when the liquid crystal layer is in contact with a substrate surface having a group having a significant anisotropy (such as a linear 'rod and strip shape), and thus, is disposed on the liquid crystal layer and the substrate The liquid crystal precursor of the interface between the surfaces tends to align with the orientation of the groups present on the surface of the substrate and having an anisotropy of defined shape. J and β have a substrate surface having a shape anisotropy (such as a line shape, a strip shape, and 146603.doc -15-201041912), a substrate substantially aligned with the surface of the substrate, and a liquid crystal original facing the interface of the substrate surface It also tends to be planarly aligned with the surface of the substrate. On the other hand, the surface of a substrate having a shape anisotropy and vertically aligned with the surface of the substrate faces the surface of the substrate, and the liquid crystal in the surface also tends to be vertically aligned with the surface of the substrate. . Alternatively, the side groups having an apparent shape anisotropy are aligned with the orientation of the liquid crystal precursor of the liquid crystal layer on the interface. By using a side group 'liquid crystal material having a defined shape anisotropy in the polymer of the present invention (such as an Lc_ layer in a liquid crystal device) tends to align with a side group attached to the polymer backbone orientation. The polymer of the present invention having a side form having significant shape anisotropy can thereby be used as a calibration layer in a liquid crystal device because it affects the orientation of the liquid crystal original in contact with the alignment layer (at least the alignment layer) In the interface with the liquid crystal layer). In one embodiment, the side groups Sla having significant shape anisotropy (such as line, strip, and dish) that cause planar alignment of the liquid crystal precursors in the interface: that is, substantially parallel to the substrate surface' can be attached To the poly person of the present invention. A calibration layer based on the polymer can be used to promote the intersection of the liquid crystal layer. Illustrative, non-limiting examples of such polymers are set forth in the following "you"--in the examples, side groups having significant shape anisotropy (such as linear, 2-like, and dish-like) The vertical alignment of the liquid crystal is substantially perpendicular to the surface of the substrate, and can be attached to the poly 146603.doc •16·201041912 composition of the present invention. The calibration layer based on the polymer can be used to promote the vertical alignment of the liquid crystal molecules. "Explanatory, non-limiting examples of such polymers are set forth in Examples 1 through 3 below. For example, for linear side groups having significant shape anisotropy, the side groups attached from the side can promote levels ( Plane) calibration with a long axis along the surface of the polymer. On the other hand, the linear side base attached from the end point promotes vertical (vertical) alignment with a long axis perpendicular to the polymer surface. In the case of a side group having a 弓-bow shape (so-called banana type), attachment from the side to the polymer backbone promotes tilt alignment of the liquid crystal molecules, and attachment from the end points facilitates planar alignment of the liquid crystal molecules. Significant shape The anisotropic "line" side of the base line at its different terms, such as a rod, bar, and rod-like side groups. The linear side groups have a well defined long axis along the main extension of the molecule and a short axis perpendicular to the long axis. As used herein, the term "attach to an end point" refers to a linear side group having a significant shape of an anisotropy, which is attached to the side of the end of the long axis of the pendant molecule by a spacer Attached to the polymer backbone in such a manner that the spacer is substantially parallel to the long axis of the pendant group. By way of example, § 'in a rod-like side group, such as a rod-like liquid crystal primordial group, the attachment point is on one end of the side group or adjacent one end of the side group. As used herein, the term "attach from the side" refers to a linear pendant having significant shape anisotropy attached to the polymer backbone by attachment to a spacer on the pendant. The spacer is made substantially perpendicular to the long axis of the pendant molecule. 146603.doc -17- 201041912 For definitions of liquid crystal terms and related terms, please refer to "Definitions of basic terms relating to low-molar-mass and polymer liquid crystals" (IUPAC Recommendations 2001, Pure Appl Chem, Volume 73) , No. 5, pp. 845-895, 2001), the entire contents of which is incorporated herein by reference. In the embodiment of the invention, the anchoring side group S4 is preferably used to anchor the polymer onto the underlying substrate. The tin-forming pendant group S4 generally functions as a hydrocarbon chain having a functionalized group in the c2 to C2〇', such as C2 to C8, and having a functional group in or near the end of the polymer backbone. A bond, such as a covalent bond, an ionic bond, or a hydrogen bond, can be formed to bind to a chemical group on the surface of the substrate, such as, but not limited to, a free hydroxyl group on the surface of the glass or, for example, by initial activation of the surface of the substrate An epoxy group, an amine group, a thiol group or an isocyano group introduced. Non-limiting examples of such functional groups suitable for anchoring pendant groups include amine groups, rhodium groups, isocyano groups, and glycidyl groups. Those skilled in the art will be able to select suitable functional groups on the anchoring pendant groups based on the substrate material. Non-limiting examples of anchoring side groups S are disclosed in the following structural formulae (HI) to (VI) where Z represents a portion of the polymer backbone and [system spacing = 'preferably has 1 to 10' Length alkyl spacers such as 丨 to 5 spacer atoms:

Z

L NCO (V) Z ' (VI)

Physical and chemical properties of the polymer of the present invention such as glass transition temperature 146603.doc • 18- 201041912

Tg, modulus of elasticity, adhesion of deposited film, film smoothness, wettability, surface energy, etc. may be included by inclusion including substitution from an optional substitution (such as substitution by a hetero atom), toothing (such as fluorination). The repeating unit of a branched or straight chain aliphatic and aromatic group (such as an alkyl group, an aryl group or an alkylaryl group), a polyether, a decane or an alcohol = a 'S5' is mediated in the polymer backbone To the desired value. These characteristics, in particular, the surface energy is known to seriously affect the orientation direction of the liquid crystal and the anchoring strength. ◎ Typical examples of S5 side groups include fluorination (such as perfluorination) as needed

Ci-Cu-alkyl (such as C4_Ci2_alkyl) or alcohol, and those defined above as spacer L. For example, when the pendant s5 group is an alkyl chain, the Tg of the polymer generally decreases in proportion to the length of the X alkyl chain. On the other hand, when the & side group is an aryl group, the Tg of the polymer generally rises. In the polymer of the present invention, a part of the repeating unit is functionalized with a side group S1 having a remarkable shape anisotropy, and as described above, the polymer preferably includes a repeating unit functionalized by a side group s5. In the polymer, the ratio of S1 to S5 is in the range of 1:100 to 100:1, and is generally in the range of about 1:1 to 1:2 Torr. However, it will be appreciated that for certain applications, polymers of the invention having only § 1 or 85 pendant groups are also effective. In an embodiment of the invention, the ion motion inhibition group can be used in the calibration layer to reduce the concentration of flowing ions in the IX material and thereby reduce the conductivity of the lc material. The ion motion-inhibiting group is generally a strong, non-ionic group that attracts ions. Examples of feed motion inhibiting groups are warp groups and others, which include materials commonly referred to as ion traps, such as crown compounds. 146603.doc 201041912 One polymer and another polymer. In an embodiment of the invention, the polymer in the composition of the invention crosslinks the crosslinking groups of two separate repeating units, such as by internal crosslinks in the same polymer backbone (four) repeats The unit or two external polymer backbones are linked by an external hexa-link, wherein the two represent a polymer of the invention. It is also possible to use the photoreactive group (such as those described below) to complete the crosslinking. However, it can also be carried out using any reactive group-heat-inducing reaction attached to the polymer. The copolymer of the present invention may include reactivity, preferably a photoreactive pendant group s7. Reactive side groups can be used to immobilize the resulting alignment layer configuration so that it is less susceptible to temperature-induced changes. The photoreactive side groups having shape anisotropy can be aligned to a desired direction by irradiation with, for example, linearly polarized light, and light can be used to dimerize/polymerize only the phases in which the polarized light has a specific direction. Thereby, a preferred orientation of the groups in the polymer is obtained. This may have the benefit that photo-orientation can generally be a step-by-step method of calibrating the material and aligning it with the parent, so that the alignment orientation also achieves higher thermal stability. The photo-orientation also has the benefit of not causing dust 'scratches or electrostatic discharges as the friction method currently used. This also makes it easier to control precisely to get a high yield. Dimerization/polymerization of reactive pendant groups can be between two reactive side groups attached to one identical polymer backbone or attached to two reactive sides of a separate polymer backbone Achieved between the base. 146603.doc -20- 201041912 Possible photoreactive groups having anisotropy of shape include, but are not limited to, chalcone, coumarin, cinnamic acid. The copolymer of the present invention includes a light responsive side group S8. The light responsive side groups having shape anisotropy can be aligned in a desired direction by, for example, linearly polarized light illumination. For example, light can be used to orient the pendant groups in combination with reactive groups, and then the dimerization/polymerization as described above can be used to irreversibly immobilize the resulting orientation, which has a photoreactive group pair as described above. The same benefits of liquid crystal calibration. In this case, the photoreactive group does not have shape anisotropy because the orientation can be carried out by a photoresponsive group having shape anisotropy. Alternatively, the <photoresponsive group can be determined by light at elevated temperatures and then by lowering the temperature, thereby achieving an irreversible fixation of the orientation. Photoresponsive groups suitable for use in the present invention include, but are not limited to, azo-containing groups, ethylene, and the like. Furthermore, the photo-orientation of the polymer according to the present invention can be achieved by using uv light by the photo-orientation of the 〇f-compound backbone to be unaffected by any photoresponsiveness and/or photoreactive side groups. The photo-orientation of these polymer primary bonds is illustrated in the form of a graph! in. First, a calibration layer material comprising at least one polymer according to the present invention is provided. Second, to achieve the photo-orientation of the polymer backbone, the alignment layer material is illuminated with linearly polarized UV light having a wavelength in the range of (10). For example, the uv light can have a wavelength in the range of 230 to 27 Gnm, such as about (10) (d). The linker and/or pendant functionalized cis-butyl quinone imine monomer as defined in the context of the present invention can be synthesized according to methods known in the art. 146603.doc 201041912 Exemplary synthetic methods are set forth in the Examples section below. For example, 'maleic anhydride can be reacted with an amine to form a functionalized maleimide monomer. Alternatively, maleimide, which has a hydrogen attached to the ring nitrogen of the maleimide ring, can be reacted with an alcohol to form a functionalized maleimide. The double-sided liquid crystal device 100 is described in Fig. 2 and includes a first limiting substrate 101 and a second limiting substrate 1〇2 which are spaced apart from each other. The liquid crystal material 1〇3 is located between the substrates 101 and 102, and is sandwiched between the substrates 1〇1 and 1〇2. The surface guiding sub-calibration layer 104 of the present invention is disposed on the first substrate 101 in contact with the liquid crystal material 103. The surface directing sub-calibration layer 104 can be chemically bonded to the substrate 101 in accordance with the presence of anchoring pendant groups on the polymer of the present invention. The surface-directed sub-calibration layer i 04 includes at least one of the present invention as described above. The surface alignment. The sub-calibration layer 104 facilitates vertical alignment of the liquid crystal material 103 at least at or adjacent the interface facing the surface-directed sub-calibration layer 1-4. Those skilled in the art will appreciate that the liquid crystal device 1 of the present invention may include means for obtaining an electric field in the liquid crystal material 1〇3. Variations in the electric field generally affect the switching of the liquid crystal material. In the embodiment described in the figure, the first electrode 105 is disposed between the alignment layer 1〇4 and the substrate 1〇1 and the second electrode 107 is disposed on the second substrate 1〇2. The surface guiding sub-calibration layer 104 induces a straight alignment of the surface director of the liquid crystal material 1〇3. 146603.doc -22- 201041912 The second alignment layer 106 is disposed between the second substrate 102 and the liquid crystal material 103. This second alignment layer may also comprise a polymer of the invention, or alternatively another layer of calibration layer material. EXAMPLES The invention will now be illustrated with reference to the following examples to further illustrate the invention. It is to be understood that the experimental examples are provided to illustrate the invention and not to limit the scope of the invention. The scope of the invention is only defined by the scope of the accompanying application. Commercially available chemical compounds are used in the received state unless the following exceptions are made: i) N-vinyl-pyrrolidone (NVP) and N-vinyl-caprolactam are passed through alumina prior to use. The added stabilizer is removed, ii) when dry THF is required, the usual THF is dried through alumina prior to use. Aluminium oxide activated neutral Brockmann 1,58 A, (CAS 1344-28-1) was used to dry THF and purify NVP. In all of the following examples, standard reactions well known to those skilled in the art are used to prepare polymers. The polymeric calibration material can be made, for example, by copolymerization of functionalized maleimide and N-vinylpyrrolidone. The preparation of these materials and the side groups used is given below.

146603.doc -23· 201041912

XV Scheme IV: Synthesis of sample liquid crystals and alkyl monomers. N-dodecylmethyleneimine (VIII): Dodecylamine was dissolved in chloroform and an equivalent amount of maleic anhydride was added. After stirring at room temperature for two hours, the solvent was discharged. The formed valine acid was used without being purified and dissolved in acetic anhydride and an equivalent amount of sodium acetate was added. The mixture was refluxed for six to eight hours, and then the solvent was discharged under vacuum. The residue was passed through a short cartridge column using petroleum ether/ethyl acetate 2/1 or 4/1 as the eluent. The maleimide is then recrystallized from ethanol or methanol. This procedure is quite effective for octyl to at least hexadecylamine. The base and the shorter imine are liquid and must be chromatographed more carefully using the same conditions as above. Yield: 41%. NMR (CDC13): δ, pattern, proton 146603.doc -24- 201041912 number; 0.85, t, 3; 1.25, m ; 2.6, m, 2 ; 3.5, t ' 2 ; 6 7, s, 2 ° Iridylimine XI: 4·2 g (9.55 mmol) n, 〇93 g (9 H mM) maleimide and 2.5 g (9.55 mmol) of triphenylphosphine Dissolved in 40 ml of dry tetrahydrofuran. 9 55 mmoles of diethyl azodicarboxylate (DEAD) (4.4 ml of a 40% solution in toluene) was added dropwise to the reaction mixture. The mixture was stirred at room temperature for three hours and evaporated to dryness. The residual oxime was dissolved in petroleum ether / ethyl acetate 2 / 1 and purified by chromatography. Production: 2.8 g 56%. NMR (CDC13); δ, pattern, number of protons; 1〇, t, 3; 1·ΐ_ι·6, 3 m, about 2〇; h8,m,4 ; 3 5,t,2 ; 4 , t,2 4.4,t,2 ; 6.7,s,2 ; 7.0,d,2 ; 7.6,2d,4 ; 8·1 , d , 2 . Maleimide XIII: 6.5 g (13 mmol) IX, i 26 g (i3 mmol) of maleimide and 3.4 g (13 mmol) of triphenylphosphine In 1 〇〇ml of dry tetrahydrofuran. 13 mmoles of diethyl arsenazo dicarboxylate (5.9 ml of a 40% solution in toluene) was added dropwise to the reaction mixture. The mixture was stirred at room temperature for three hours and then evaporated to dryness. (4) The residue was dissolved in toluene/acetic acid ethyl acetate and purified by chromatography. Yield: 4〇\ 53%. NMR (CDCl3); δ, pattern, number of protons; 〇9, 卜3;]. Bu 1.6 >3m; 1.8 . m . 4; 3.5, t >2; 3.9 ^ t ^ 2 ; 4.1 , t , 2 ; 6.7' s, 2; 6.9, 2d' 4; 7.1, d, 2; 8], d, 2. Cis-butadiene-imine XV: 1.5 g (4 mmol) χιν, 〇4〇 to 4" house Moer) maleimide and 1.13 g (4l millimolar) triphenyl scale Dissolve in W dry THF and add 0.72 g (4a mmol) of thiophene sulphonic acid 146603.doc •25·201041912 ester in 2.19 hydrazine solution. Stir the reaction mixture for 5 hours at room temperature. The residue was taken up in petroleum ether / ethyl acetate 2 / 1 and filtered hot. The solvent was removed in vacuo and residue was taken from methanol to <RTI ID=0.0> Ester 2/1 was chromatographed as an eluent, yielding a low yield of pure product due to loss in the recrystallization test. 0_3 g 0.6 mmol, 17%. NMR (CDCl3); δ, pattern 'proton number; 〇.9, 卜3; HU, 3m, 12; h8, m, 4; 3·6, 卜2; 4' 4; 6· 7, s, 2; 6.93, m, 4; 7 45,

m, 4.

Wanlai V: used for planar calibration (p; especially early liquid crystal original monomer. One by one, 'for these monomers, use one of the questions described in the method ++ ++. The use of diimine in the art is known, and his method is used to prepare Η 146603.doc * 26 - 201041912

1·5 parts HMDS +1 part ZnBr2 1 hour under 80° ο XXII Scheme VI: Ethyl benzyl succinimide is shown in the above scheme. All the steps are in 〇

A third method of preparing maleimide is in VI. All materials used are from suppliers. It is carried out under a nitrogen atmosphere. Ethylaniline (1 G millimolar '(10) mg) was added dropwise to a stirred solution of 30 ml of toluene containing cis-succinic anhydride (10 mmol, 980 mg). The solution was stirred for one hour until a precipitate formed. Add ZnBr2 (1 mM millimolar, mg) and incubate the solution to 8 (rc. Add hexamethylene diazoxide (HMDS) (14 mmol, 2250 mg) dropwise at high temperature with a syringe. 15 minutes 'addition too fast will lead to the formation of coke. After heating for one hour, the reaction mixture was poured into 180 ml of 0.5% HCl and the aqueous phase was extracted twice with 150 mi EtAc. Then 150 ml of saturated NaHC〇3 and brine were used. The organic phase was washed successively. The solution was dried and purified by chromatography using eluent/Et Ac 19/1 as eluent. Yield: 66%. Polymer Synthesis Example 1: Promoting copolymerization of vertical alignment (VA) 146603.doc -27- 201041912

Scheme VII: Preparation of VA copolymer 0.4 mmol (225 mg) cis-butyl diimide XIII, 1.6 mmol (424 mg) N-dodecyl maleimide VIII, 2.0 Millol (222 mg) NVP was purified by oxidation and 0.12 mmol (19 mg) of 2,2i-azobis(2-methylpropionitrile) in a rubber septum sealed round bottom flask. (AIBN) is dissolved in 10 ml of benzene. It is vacuumed through the septum via a syringe needle, followed by nitrogen. Ten vacuum-nitrogen feed cycles were repeated for removal of oxygen from the flask. The flask was heated in an oil bath to a constant temperature of 60 °C. After 15 h, the solution was poured into decyl alcohol and the resulting polymer produced a precipitate. The polymer from the gas sample was added to methanol, reprecipitated twice, and at least once was added to the acetone/nonanol 1/3 mixture from the gas. The solvent was decanted and pure sterol was added. Finally, the polymer was placed in a tube and heated on a hot plate to remove residual solvent. The final trace of solvent was heated to 60 by placing the polymer in a vacuum oven. . Removed after 2 hours. Yield: 0·7 g, 80%. NMR (CDC13); δ, pattern; 0.9, t; 1-5 side-based signal on a broad backbone signal; 6.9, 2d; 7.1, d; 8.1, d. The liquid crystal raw/alkyl ratio of the polymer composition was determined to be 1/4.2 using the thiol group and the aromatic signal in 1H NMR. This means that the side groups (excluding pyrrolidone groups) of 1 9.2% 146603.doc -28- 201041912 are liquid crystals. This material is deposited on the inner surface of a glass substrate of a multilayer component prepared according to the procedure in a calibration layer. This element is filled with nematic liquid crystal MLC 6608 (which has a negative dielectric anisotropy (Δε < 0)), and the element is first examined under a polarizing microscope for defining the liquid crystal alignment promoted by the calibration layer. Types of. The calibration observed in this component is vertical, ie perpendicular to the substrate. The pretilt angle of the preferred direction of liquid crystal alignment from the vertical of the substrate is then determined by a Miller matrix spectrometer. If the calibration layer is mechanically rubbed, a small pretilt angle of less than 1 degree is obtained. The calibration layer also exhibits good thermal stability.

Example 2: Copolymer XXVI

Scheme VIII. Preparation of VA Copolymer VA Copolymer from Fluorinated Hydrocarbon: 0.5 mmol (331 mg) of Liquid Crystalline Maleimide XIII, 0.5 mmol (228 mg) of Perfluorohexylpropyl Butenimide XXV, 1.5 millimolar (400 mg) dodecyl maleimide, 2.5 millimolar (277 mg) NVP purified by alumina, and 0.15 146603 .doc -29· 201041912 Molar (25 mg) 2,2'-azo chelate *Work* wA bis(2-methylpropionitrile) (AIBN) is dissolved in 25 such as benzene. In the oil at 60 ° C, the flattened in the field 1 gentleman ^ 仃 σ effect for 4 〇 hours. Hunting was carried out by adding it to a small amount of ml milk imitation and adding it to methanol for three times to purify it, and its medium-subsystem was added to methanol/propion 2/1 to obtain a final polymer χχνι. The materials were tested in the same manner as in Example 1 to obtain similar yields and characteristics. This material provides a vertical alignment with low fill speed due to the low surface energy possessed by the fluorinated group. Example 3: High Tg VA Polymer 0

Scheme IX: High TgVA copolymer will be 40 mM (180 mg) cis-butane diimine XIII, 1.6 millimolar (277 mg) N-phenyl cis-butane quinone imine, 2 〇 Mohr (222 alkenyl hydrazine (tetra) and 0.12 mmol (19 mg) 22, azobis (2-methylpropionitrile KAIBN) was dissolved in 10 m benzene. The mixture was polymerized according to the expression in Example i Processing: yield: 〇26 g 38%qNmr(cdci3); δ, pattern '0.9, bs; i"_5 side-based signal on wide main chain signal; 6 9, 146603.doc •30- 201041912 bs,7· 0 -7.6,bs 〇Ο For softer smoked chains, the glass temperature with hard groups and liquid crystals can be raised. This material shows (10) generations (4). This material is deposited as a calibration layer according to the procedure. The inner surface of the glass substrate of the multilayer component. The element is filled with a nematic liquid crystal MLC (4) having a negative dielectric anisotropy (Δε <〇) and the element is first examined under a polarizing microscope to Used to define the type of liquid crystal calibration promoted by the calibration layer. The alignment observed in this component is vertical 'ie vertical along the substrate. Next by Miller The Muller matrix spectrometer measures the pretilt angle from the preferred direction of liquid crystal alignment of the substrate. If the calibration layer is mechanically rubbed, a pretilt angle is obtained. The calibration layer also exhibits good Thermal stability. Example 4

VAV-copolymer with N-vinyl hexamethyleneamine: 〇4 mmol (225 mg) of maleimide χιπ, i 6 mM (424 claw phantom dodecyl Maleimide, 2.0 mM (278 mg) N-vinyl hexyl 146603.doc • 31- 201041912 indoleamine and 0_12 millimolar (19 mg) 2,2,-azobis ( 2-Mercaptopropionitrile KAIBN) was dissolved in 1 〇 benzene in a round bottom flask and the flask was sealed with a rubber septum. The syringe was passed through the septum to draw a vacuum, followed by nitrogen. Repeat 10 times. Vacuum_nitrogen enters the cycle for removal of oxygen from the k-bottle. The flask is heated to a constant temperature in an oil bath. After 15 h, the solution is poured into methanol and the resulting polymer produces a precipitate. The polymer was added to methanol, reprecipitated twice, and at least once was added to the acetone/methanol 1/3 mixture from the gas. The solvent was decanted and pure methanol was added. Finally, the polymer was placed in a : and heated on a hot plate to remove residual solvent. The final trace of solvent is placed by placing the polymer It was heated to 7 Torr in a vacuum oven for 4 hours. The yield was 0.75 g, 81%. This material was deposited on the inner surface 1 of a glass substrate of a multilayer component prepared according to the procedure with a calibration layer. The component is filled with nematic liquid crystal 6608 (which has a negative dielectric anisotropy (Δε < 〇)) and the element is first examined under a polarization mirror to define the type of liquid crystal alignment promoted by the calibration layer. The calibration observed in this component is straight, i.e., perpendicular along the substrate. The pretilt angle of the preferred direction of liquid crystal alignment from the vertical of the substrate is then determined by a Miller matrix spectrometer. If the calibration layer # binds to the numb & + layer; mechanical friction, a small pretilt angle of less than 1 degree is obtained. Example 5: Copolymer for promoting planar calibration (pA) 146603.doc •32· 201041912

方案 Scheme XI: Copolymerization will be 0.4 millimolar (265 mg) maleimide XVI, 1.6 millimolar (334 mg) N-octyl maleimide, 2 mM millimolar (222 mg Nvp was purified by passing through alumina, and 0.12 mmol (19 mg) of 2,2,-azobis(2- mercaptopropionitrile) (AIBN) was dissolved in 10 ml of stupid. Polymerization and treatment were carried out according to the preparation in Example 1. Yield: 0.66 g, 80%. NMR (CDC13). δ pattern, 〇·9 ′ t; see the 1 _5 side group signal on the main chain signal; 6.5, d; 6.9, d ·, 7.1, d; 8.0, d. The liquid crystal raw/alkyl ratio of the polymer composition was determined to be 1/1.8 using the methyl group and aromatic signals in 1H NMR. This means that 36% of the pendant groups (excluding pyrrolidone groups) are liquid crystals. This material is deposited on the inner surface of a glass substrate of a multilayer component prepared according to the procedure in a calibration layer. This element is a nematic liquid crystal coffee cell 6873_1 (which has a positive dielectric anisotropy (Δ,) fill, and the element is first: examined under a polarizing microscope' for defining the liquid crystal calibration promoted by the calibration layer) Type. The calibration observed in this component is parallel, 146603.doc -33· 201041912 is essentially parallel to the substrate. The calibration layer also exhibits good thermal stability.

Scheme XII. Photoreactive PA copolymer 0.1 0.1 mmol (67 mg) maleimide XVII, 0.4 mmol (106 mg) N-hexyl maleimide, 0.5 mmol (54 mg) NVP was purified by passing through alumina, and 0.03 mmol (5 mg) of 2,2'-azobis(2-mercaptopropionitrile) (AIBN) was dissolved in a round bottom flask. The flask was filled with ML and the flask was sealed with a rubber septum. It is vacuumed through the septum via a syringe needle, followed by nitrogen. Ten vacuum-nitrogen inlet cycles were repeated for removal of oxygen from the flask. The flask was heated to a constant temperature of 60 ° C in an oil bath. After 17 h, most of the benzene was evaporated in a rotary evaporator and the solution, such as methanol, and the resulting polymer were precipitated. The polymer from 146603.doc •34- 201041912 was added to methanol and reprecipitated twice. Finally, polymer XXXIV was placed in a tube and the residual solvent was removed at room temperature. Yield: 0.10 g, 4 4 %. This material was deposited on the inner surface of a glass substrate of a multilayer element prepared according to the procedure in a calibration layer. However, the sample was placed in linearly polarized light. Instead of rubbing the sample, the sample was oriented at 5 mW/cm2 for 15 minutes. This element is filled with nematic liquid crystal MLC 6873-100 (which has positive dielectric anisotropy (Δε > 0)), and the element is first examined under a polarizing microscope to define the calibration layer. The type of LCD calibration that is promoted. The alignment observed in this element is parallel, ie parallel to the substrate. Example 7: A VA copolymer was prepared according to the procedure of Example 6 above using XVIII as a monomer.

Scheme XIII: Photoreactive VA copolymer 0.2 mumol (118 mg) maleimide XVIII, 1.8 millimolar (477 mg) N-octyl maleimide, 2.0 millimolar ( 222 mg) NVP was purified by passing through alumina and 0.12 mmol (19 mg) of 2,2'-azobis 146603.doc -35 - 201041912 (2-methylpropionitrile) (AIBN) was dissolved in l 〇mi benzene. According to the example! The preparation process is carried out by polymerization and treatment.

Yield: 0.66 g '81%, cinnamate 5. /〇 Dodecyl 95〇 / 〇. NMR (CDC13); δ, pattern; 〇.9, t; 1-5 broad signal, 6_5, d; 6.9, d; 7.08, d; 7.5, d; 7.8, d. This material is deposited on the inner surface of a glass substrate of a multilayer component prepared according to the procedure in a calibration layer. This element is filled with nematic liquid crystal mlc 6608 (which has a negative dielectric anisotropy (Δε < 〇)), and the element is first examined under a polarizing microscope for defining the calibration of the liquid crystal promoted by the calibration layer. Types of. The calibration observed in this component is vertical, ie perpendicular to the substrate. The calibration layer also exhibits good thermal stability. Example 8: alkyl chain

Scheme XIV: A copolymer having only pendant alkyl groups. 209 mg (1. 〇 mmol) Ν_octyl cis-butane ruthenium imine, (1) mg (1.0 mmol) NVP was purified by oxidation, and Μ ^ (〇·12 mmol) 2,2'-azobis(2-methylpropionitrile) (A_dissolved in 5(6) benzene. Polymerization and treatment according to the preparation of the above VA copolymer. Yield: 0.23 g, 72%. NMR (CDC13) Pattern; 〇85, s. i 2 . 1.5, s ; 1.6 - 4.5 wide signal. ' This material is deposited on a glass substrate of a multilayer element 146603.doc -36- 201041912 prepared according to the procedure with a calibration layer. Inner surface 1. This element is a nematic liquid crystal like 6873-100 (which has a positive dielectric anisotropy (&>〇" filling and the element is first examined under a polarizing microscope to define the calibration layer Types of liquid crystal calibrations that are promoted. The calibrations observed in this component are based on friction and thermal conditions. Materials with only burn (4) have low misalignment and sensitivity calibration.

Solution XV: Low Surface Energy Materials "Hai materials generally have lower anchor strength and more sensitive calibration without liquid crystal.

2 〇〇mg fluorinated chain (〇·44 mmol), 184 mg alkyl chain (0.88 mmol), 146 mg N_vinylpyrrolidone (132 mmol) activated by Rongguo Purified with aluminum and 13 mg of AIBN was dissolved in 13 ml of benzene. Polymerization and treatment were carried out according to Example 1. Yield: j80 mg, 34 〇 / 〇. "Hai materials are used to prepare the elements in the same manner as in Example 8. This is due to the relatively low surface energy caused by the fluorinated linkage, which provides poor wettability compared to the polymer χχχνι. Example 10 146603.doc -37- 201041912

Scheme XVI: Copolymers of alkyl groups having different lengths. Copolymers having different alkane chain lengths, such as 8+12 alkane chains. 1 mM (209 mg) of N-octyl succinimide, i milole, decyl succinimide, 2 mM (222 mg) of NVP by oxidation Purified and 〇12 mmol (b mg) 2 2,_ azobis(2-methylpropionitrile) (AIBN) was dissolved in 1 〇 (4) order. The polymerization and treatment are carried out according to the preparation in solid. Yield: 〇 55 g, 79%. This material was used to prepare the elements in the same manner as in the examples. It provides parallel calibration. By incorporating an additional longer alkane oxime than in Example 8, the VA stability of the material was improved and the material showed parallel calibration when tested using the method described in Example 8. This calibration is more frictional and temperature dependent than when using the crystal precursor in the example. Example 11 0

, XXXIX 0

Benzene Benzene Scheme XVII: Copolymer Ears with Short Alkane Chains (111 1 mM 13⁄4 Moule (153 mg) N. Butyl Maleimide 146603.doc -38 - 201041912 mg) NVP by passing alumina Purification, and 0.06 millimolar (97 mg) of 2'2'-even 1 bis (2-methylpropion) (AIBN) was dissolved in 5 ml of stupid. Polymerization and treatment were carried out according to the preparation in Example 。. Yield: 〇1 g. When compared to the previous examples, it uses a shorter alkyl chain with enhanced reinforcing properties and a copolymer based on butyl cis-butanediamine provides PA calibration and a more astringent glass temperature. This material was used to mount the k-element in the same manner as in Example 8 for a plane calibration with a tilt angle caused by friction.

When it is described by the general method as follows;

Scheme XVIII. Ethylphenyl-based PA copolymer PA copolymer: 1 mm 〇l (2 〇l mg) ethyl-phenyl butyl succinimide XXII, 1 millimolar (111 mg) NVP was purified by passing through alumina and 0. 06 mmol (1 〇 mg) of 2,2,-azobis(2-methylpropy) (aibn) was dissolved in 10 ml of benzene. The polymerization was carried out overnight in a 60 degree oil bath. Purification was carried out by adding a little ml of chloroform to methanol and reprecipitating three times. Yield 〇18〇g ' NMR(CDCl3)S 'pattern; number of protons; 1.1-1.2 broad doublet from the end ethyl carbon; 3, 丨5 side base signal of the broad backbone signal; 69_7 35 ; The broad peak of the aromatic proton (due to the width of the adjacent polymer backbone), 4. This material is deposited as a multilayer layer prepared according to the procedure with a calibration layer. 146603.doc •39· 201041912

Baishen is examined under a polarizing microscope to define the type of liquid crystal calibration for that phase. Observed in this element and substantially parallel to the substrate. The calibration layer also shows that the component is filled with nematic liquid crystal Mlc anisotropy (Δε > 0), and the element is used to define the calibration layer parallel k plate observed in the component. The calibration layer also shows good thermal stability in 4P. As a main chain with a high glass temperature, this is for the addition of other groups. This material is soluble in PGMEA and NMP. As a general r-extension backbone with and for planar alignment, this (optional) is a good choice for burning hydrocarbon chains. It also provides a good consistent planar alignment when oriented by uv light as described in general method c2 below. Example 13

Scheme XIX PA copolymer: 丨mmol (2〇l mg) ethyl phenyl maleimide, 0.5 millimolar (175 mg) 2-hexyloxybiphenyl maleimide 1.5 mmol (166 mg) of NVP was purified by alumina and dissolved in 0 〇9 mM (15 mg) 2,2,-azobis(2-methylpropionitrile) (AIBN) In 15 ml benzene 146603.doc -40- 201041912. The polymerization was carried out in an oil bath of 60 degrees for 22 hours. Purified by adding a little μ of chloroform to methanol and then sinking three times. It is soluble in NMP and PGMEA. This material is deposited on the inner surface 1 of the glass substrate of the multilayer component prepared according to the procedure with a calibration layer. This element is a nematic liquid crystal 6873-100 (which has a positive dielectric anisotropy (heart > 〇 fill), and the element is first examined under a polarizing microscope for defining the calibration layer to promote Ο The type of liquid crystal calibration. The calibration observed in this element is 'that is substantially parallel to the substrate forward' but has a tilt that is highly sensitive to friction conditions. The calibration layer also shows good thermal stability. The plane calibration is also provided by the light extraction (4) as described in the following general method. x Example 14 〇

+

XUV

Scheme XX Maleimide copolymer (197 mg) 6-hydroxyhexyl-butene: functionalized with a hydroxyl group. 1.0 mmol of diimine, 1.0 mmol (2〇7 mg) 146603.doc 201041912 N-octyl maleimide, 2.0 mmol (222 mg) N-vinylpyrrolidone and 0.12 mmol (19 mg) of 2,2'-azobis(2- mercaptopropionitrile) (AIBN) was dissolved in a mixture of 5 ml of benzene and 5 ml of ethanol. The mixture was polymerized at 6 ° C for 15 h. The polymer was precipitated in diethyl ether and reprecipitated therefrom from benzene/ethanol to ether. Yield: 0.29 g. NMR (CDC13) J, pattern, number of protons; 0.75' bs; 1.35 -1.75, 2 broad unimodal and one shoulder; ι·8 -4.5 wide signal, respectively, from adjacent 33 and 3 6 unseparated signals of imine nitrogen and methylene protons of alcohol. An optical copolymer obtained by functionalizing 100 mg (corresponding to about 0.16 mM-mercapto) of the obtained copolymer XLIII, 50 mg (0.20 mmol) of 4 hexyloxycinnamic acid (XLIV), 10 Ml dichloromethane and a catalytic amount of 4-mercaptoamine group are stirred with pyridine until all the materials are completely dissolved. The mixture was cooled in an ice bath and 50 mg (0.24 mmol) of DCC (dicyclohexylurea) was dissolved in a small portion of dichloromethane and added to the mixture. The ruthenium mixture was stirred at room temperature overnight. The formed urea precipitate was filtered off and most of the solvent was removed under vacuum. The polymer failed to precipitate in the fermentation. The solvent was removed under vacuum and methanol was added to the residue and heated to reflux. The solvent was decanted while hot and the procedure was repeated twice. This treatment needs to be improved to produce 40 mg of polymer XLV. NMR (CDC13); δ, pattern. 0.85, ί; the broad-chain signal is the side-base signal, shown as the residue of the shoulder peak on N_CH2 -CH2-OH; 6.25,d; 6.85,d; 7.45,d ; 6, d. The cinnamate/alkyl ratio is W1 5 and the conversion of hydroxy to ester is about 66%. This material was deposited on the inner surface of a glass substrate of a multilayer element 146603.doc • 42- 201041912 prepared according to the procedure in a calibration layer. This element is filled with nematic liquid crystal mlc 6873-100 (which has positive dielectric anisotropy (Δε > 〇)), and the element is first examined under a polarizing microscope for defining the liquid crystal promoted by the alignment layer. The type of calibration. The calibrations observed in this component are parallel 'and along the substrate. The calibration layer also exhibits good thermal stability and can be photo-aligned by UV. This example only shows one of a number of alternative methods for preparing a side chain maleimide/vinyl caprolactam copolymer by functionalization. ^ General Method for Preparing Liquid Crystal Element a. Preparation of Polymer Solution The calibration layer prepared from the copolymer of the present invention was deposited from a solution of 2% to 5% of a copolymer contained in a solvent such as NMP and PGMEA. The copolymer solution was first filtered through a 0.2 μηι filter. B_Copolymer deposition The copolymer solution is dispersed, for example, by a spinner (at a speed of 3 rps) onto the surface of a clean glass substrate having a pre-fabricated transparent conductive electrode (made from ITQ) on. The substrate was then held at room temperature for a period of time to remove the solvent. If the substrate is maintained at a high temperature (8 〇Μ 2 〇 β (:), then the process cl. mechanically processes the substrate covered by the calibrated layer (which includes the copolymer of the present invention), for example to facilitate planar calibration, along a certain - Mechanical rubbing in the direction. No friction is required in the case of calibration from a copolymer that promotes vertical alignment. 〃 c2. Photodirection of copolymer 146603.doc -43· 201041912 Test substrate covered with light (tetra) silk UV irradiation was carried out in a standard 〇 〇 device using a 5 m MW linearly polarized light containing no _遽^. The green polymer was spun by a 1% m polymer solution contained in the pG run. The substrate is deposited on the glass substrate. Subsequently, the substrate is exposed to uv irradiation at normal incidence. The irradiation time is .min. d. The component preparation test component is composed of two combined substrates which are parallel to each other and separated by several distances. The distance between them is usually fixed by a glass or polymer spacer. The surfaces of the substrates which are covered by the alignment layer face each other. The element gap formed by the liquid crystal is filled by capillary force. Object calibration Evaluation of the calibration of the liquid crystal in the evaluation test element, which is reinforced by the calibration layer made of the copolymer of the present invention, is carried out by: • Light polarization microscopy • Miller matrix spectrometer (Muller matrix spectr〇meter) (] [Th., Meas. Sci. Technol. 12, 1938 2001). In summary, the polymers of the present invention are shown to be suitable for use as or as a calibration layer for liquid crystal devices. The invention is in no way limited by the above preferred embodiments. Instead, modifications and changes can be made within the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a calibration layer for use in the present invention. A block diagram of a method of light directing of a material. 146603.doc • 44- 201041912 FIG. 2 illustrates a liquid crystal device using a calibration layer of the present invention. [Main element symbol description] 101 First confinement substrate 102 Second confinement substrate 103 Liquid crystal material. 104 Surface guide sub-calibration layer 105 first electrode 106 second calibration layer Ο 107 second electrode 〇 146603.doc -45-

Claims (1)

201041912 VII. Patent Application Range: 1. A polymer for a surface-guided sub-calibration layer comprising maleimide and/or a derivative thereof and a fluorene vinylamine and/or A copolymer of repeating units of a derivative, wherein at least some of the repeating units are functionalized with a pendant group S1 having significant shape anisotropy. 2. A polymer, wherein at least some of the repeating units of the maleimide and/or derivatives thereof comprise a hydrogen atom or a group SX, the group SX being selected from the group consisting of methyl groups: methyl ; ethyl; anchoring pendant group S4, selected from the group of optionally substituted, dentate branched or linear aliphatic and aromatic groups, side groups S5 of oxoxane or alcohol; ion motion inhibition side group s The reactivity 'is preferably a photoreactive side group s7; and a photoresponsive side group S8. 3. The polymer of claim 1, wherein the cis-butane quinone imine and the vinyl-decalamine repeating unit are present in an amount of at least 5 Å/0 of the repeating unit of the polymer backbone, such as At least 75〇/. , for example at least. a polymer of 0 long term 1 wherein the ratio of the maleic iminoimine to the N-vinyl indoleamine unit in the primary bond of the polymer is in the range of 1:10 to 1 Å, such as 1:2 to 2:1, for example about 1:1. 5. The polymer of claim 1, wherein the N-vinyl lactam is selected from the group consisting of Ν·vinylpyrrolidone 'N-vinylpiperidine and N•vinylcaprolactam . 6. The polymer of claim 2, wherein the polymer comprises a repeating unit selected from the group consisting of: 绖 anchoring pendant group S4 functionalized repeating unit; 146603.doc 201041912 selected from the group consisting of, if desired, substituted a repeating unit functionalized by a branched or straight-bonded aliphatic and aromatic group (such as an alkyl group, an aryl group or an alkylaryl group), a polyether, a decane or a pendant group of an alcohol; S6 functionalized repeating unit; reactive, preferably repeating unit functionalized by photoreactive side group S7; and repeating unit functionalized with photoresponsive side group S8. 7. The polymer of claim ,, which comprises a crosslinking group. 8. The polymer of claim 1 or 2 wherein the pendant groups and/or at least a portion of the hydrogen atoms are attached to the repeating unit via a maleimide-nitrogen. The polymer of claim 1 or 2, wherein the pendant groups "and/or are attached to the repeating unit via a spacer group L. 10. The polymer of claim 1 wherein the distinctive shape is The side group s of the opposite sex is selected from the side substrate of the planar alignment for inducing the liquid crystal material and the side substrate S1b for inducing the vertical alignment of the liquid crystal material. 11. A surface guide sub-calibration layer comprising at least one deposited to a polymer on a solid substrate, the polymer being a repeating unit comprising: cis-butyl diimide and/or/or a derivative and N-acetyl-decalamine and/or a derivative thereof, wherein At least some of the repeating units are functionalized with pendant groups si having significant shape anisotropy, and/or at least some of the maleimide and/or derivatives thereof t repeating units include -H atoms or a group SX, the group Sx is selected from the group consisting of sx: fluorenyl; ethyl; anchoring side group S, selected from the group Substituted or functionalized branched or linear aliphatic 146603.doc 201041912 and pendant group s5 of aromatic group, polyether, decane or alcohol; ion motion inhibition side group s6; reactivity, preferably photoreaction And a light-responsive side group s8. 12. The surface-directed sub-calibration layer of claim 11 comprising the polymer of any one of claims 3 to 10. 13. A liquid crystal device The surface guide sub-calibration layer includes at least one piece of the limiting substrate, a liquid crystal body, and a surface guiding sub-alignment layer disposed between the at least one of the limiting substrate and the liquid crystal body and in contact with a surface of the liquid crystal body, wherein the surface guiding sub-calibration layer 14. The liquid crystal device of claim 13, comprising: the first and second confinement substrates sandwiching the liquid crystal layer; disposed on the first confinement substrate and the liquid crystal a first surface guiding sub-alignment layer which is in surface contact with one of the liquid crystal bodies; and a second surface guiding sub-alignment layer disposed between the second confinement substrate and the liquid crystal body, It is connected to one surface of the liquid crystal Touching; wherein at least one of the first and second surface guiding sub-calibration layers, or preferably both, is as defined by claim 11 or 丨2 card. Light orientation for surface guiding sub-calibration layer material The method includes providing a surface-directed sub-calibration layer material as claimed in claim 11 or 12; and illuminating the surface-guided sub-calibration layer material with linearly polarized electromagnetic radiation having a wavelength in the range of 200 to 300 nm.